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Institute
- Institut für Chemie (2231) (remove)
The use of a catalyst support for the design of nanoscale heterogeneous catalysts based on cerium oxide offers vast possibilities for future catalyst development, particularly with regard to an increased focus on the use of renewable biogas and an emerging hydrogen economy. In this study, zirconia-supported ceria catalysts were synthesized, activated by using different thermochemical treatments, and characterized by way of temperature-programmed reduction (TPR), oxygen storage capacity, Xray diffraction, electron microscopy, and luminescence spectroscopy using Eu3+ as a spectroscopic probe. Through reduction-oxidation pretreatment routines, reactive pyrochlore structures were created at temperatures as low as 600 degrees C and identified through TPR and electron microscopy experiments. A structural relationship and alignment of the crystal planes is revealed in high-resolution scanning transmission electron microscopy experiments through the digital diffraction patterns. Low-temperature pretreatment induces the formation of reactive pyrochlore domains under retention of the surface area of the catalyst system, and no further morphological changes are detected. Furthermore, the formation of pyrochlore domains achieved through severe reduction and mild reoxidation (SRMO) treatments is reversible. Over multiple alternating SRMO and severe reduction and severe reoxidation (SRSO) treatments, europium spectroscopy and TPR results indicate that pyrochlore structures are recreated over consecutive treatments, whenever the mild oxidation step at 500 degrees C is the last treatment (SRMO, SRMO-SRSO-SRMO, etc.).
The shape and the actuation capability of state of the art robotic devices typically relies on multimaterial systems from a combination of geometry determining materials and actuation components. Here, we present multifunctional 4D-actuators processable by 3D-printing, in which the actuator functionality is integrated into the shaped body. The materials are based on crosslinked poly(carbonate-urea-urethane) networks (PCUU), synthesized in an integrated process, applying reactive extrusion and subsequent water-based curing. Actuation capability could be added to the PCUU, prepared from aliphatic oligocarbonate diol, isophorone diisocyanate (IPDI) and water, in a thermomechanical programming process. When programmed with a strain of epsilon(prog) = 1400% the PCUU networks exhibited actuation apparent by reversible elongation epsilon'(rev) of up to 22%. In a gripper a reversible bending epsilon'(rev)((be)(nd)()) in the range of 37-60% was achieved when the actuation temperature (T-high) was varied between 45 degrees C and 49 degrees C. The integration of actuation and shape formation could be impressively demonstrated in two PCUU-based reversible fastening systems, which were able to hold weights of up to 1.1 kg. In this way, the multifunctional materials are interesting candidate materials for robotic applications where a freedom in shape design and actuation is required as well as for sustainable fastening systems.
Gadolinium-doped ceria or gadolinium-stabilized ceria (GDC) is an important technical material due to its ability to conduct O2- ions, e.g., used in solid oxide fuel cells operated at intermediate temperature as an electrolyte, diffusion barrier, and electrode component. We have synthesized Ce1-xGdxO2-y:Eu3+ (0 <= x <= 0.4) nanoparticles (11-15 nm) using a scalable spray pyrolysis method, which allows the continuous large-scale technical production of such materials. Introducing Eu3+ ions in small amounts into ceria and GDC as spectroscopic probes can provide detailed information about the atomic structure and local environments and allows us to monitor small structural changes. This study presents a novel approach to structurally elucidate europium-doped Ce1-xGdxO2-y:Eu3+ nanoparticles by way of Eu3+ spectroscopy, processing the spectroscopic data with the multiway decomposition method parallel factor (PARAFAC) analysis. In order to perform the deconvolution of spectra, data sets of excitation wavelength, emission wavelength, and time are required. Room temperature, time-resolved emission spectra recorded at lambda(ex) = 464 nm show that Gd3+ doping results in significantly altered emission spectra compared to pure ceria. The PARAFAC analysis for the pure ceria samples reveals a high-symmetry species (which can also be probed directly via the CeO2 charge transfer band) and a low-symmetry species. The GDC samples yield two low-symmetry spectra in the same experiment. High-resolution emission spectra recorded under cryogenic conditions after probing the D-5(0)-F-7(0) transition at lambda(ex) = 575-583 nm revealed additional variation in the low-symmetry Eu3+ sites in pure ceria and GDC. The total luminescence spectra of CeO2-y:Eu3+ showed Eu3+ ions located in at least three slightly different coordination environments with the same fundamental symmetry, whereas the overall hypsochromic shift and increased broadening of the D-5(0)-F-7(0) excitation in the GDC samples, as well as the broadened spectra after deconvolution point to less homogeneous environments. The data of the Gd3+-containing samples indicates that the average charge density around the Eu3+ ions in the lattice is decreased with increasing Gd3+ and oxygen vacancy concentration. For reference, the Judd-Ofelt parameters of all spectra were calculated. PARAFAC proves to be a powerful tool to analyze lanthanide spectra in crystalline solid materials, which are characterized by numerous Stark transitions and where measurements usually yield a superposition of different contributions to any given spectrum.
Azobenzenes easily photoswitch in solution, while their photoisomerization at surfaces is often hindered. In recent work, it was demonstrated by nonadiabatic molecular dynamics with trajectory surface hopping [Titov et al., J. Phys. Chem. Lett. 2016, 7, 3591-3596] that the experimentally observed suppression of trans -> cis isomerization yields in azobenzenes in a densely packed SAM (self-assembled monolayer) [Gahl et al., J. Am. Chem. Soc. 2010, 132, 1831-1838] is dominated by steric hindrance. In the present work, we systematically study by ground-state Langevin and nonadiabatic surface hopping dynamics, the effects of decreasing packing density on (i) UV/vis absorption spectra, (ii) trans -> cis isomerization yields, and (iii) excited-state lifetimes of photoexcited azobenzene. Within the quantum mechanics/ molecular mechanics models adopted here, we find that above a packing density of similar to 3 molecules/nm(2), switching yields are strongly reduced, while at smaller packing densities, the "monomer limit" is quickly approached. The UV/vis absorption spectra, on the other hand, depend on packing density over a larger range (down to at least similar to 1 molecule/nm(2)). Trends for excited-state lifetimes are less obvious, but it is found that lifetimes of pi pi* excited states decay monotonically with decreasing coverage. Effects of fluorination of the switches are also discussed for single, free molecules. Fluorination leads to comparatively large trans -> cis yields, in combination with long pi pi* lifetimes. Furthermore, for selected systems, also the effects of n pi* excitation at longer excitation wavelengths have been studied, which is found to enhance trans -> cis yields for free molecules but can lead to an opposite behavior in densely packed SAMs.
Aminolysis induced functionalization of (RAFT) polymer-dithioester with thiols and disulfides
(2020)
A series of polystyrene- and poly(methyl methacrylate)-dithioesters was subjected to aminolysis under ambient atmospheric conditions, i.e., in the presence of oxygen. Polymer disulfide coupling by oxidation occurred within tens of minutes and the yield of disulfide-coupled polymer increased with decreasing polymer molar mass. Oxidation of thiolates is usually an unwanted side reaction, here it is employed to obtain exclusively polymeric mixed disulfides through in situ aminolysis/functionalization in the presence of a thiol. The in situ aminolysis/functionalization in the presence of a disulfide, Ellman's reagent or polymer disulfide, resulted in the exclusive formation of polymer-dithionitrobenzoic acid, which can be further reacted with a thiol to exchange the terminal functionality, or block copolymer with dynamic disulfide linker, respectively.
Total syntheses of prenylated isoflavones from Erythrina sacleuxii and their antibacterial activity
(2020)
The prenylated isoflavones 5-deoxyprenylbiochanin A (7-hydroxy-4'-methoxy-3'-prenylisoflavone) and erysubin F (7,4'-dihydroxy-8,3'-diprenylisoflavone) were synthesized for the first time, starting from mono-or di-O-allylated chalcones, and the structure of 5-deoxy-3'-prenylbiochanin A was corroborated by single-crystal X-ray diffraction analysis. Flavanones are key intermediates in the synthesis. Their reaction with hypervalent iodine reagents affords isoflavones via a 2,3-oxidative rearrangement and the corresponding flavone isomers via 2,3-dehydrogenation. This enabled a synthesis of 7,4'-dihydroxy-8,3'-diprenylflavone, a non-natural regioisomer of erysubin F. Erysubin F (8), 7,4'-dihydroxy-8,3'-diprenylflavone (27), and 5-deoxy-3'prenylbiochanin A (7) were tested against three bacterial strains and one fungal pathogen. All three compounds are inactive against Salmonella enterica subsp. enterica (NCTC 13349), Escherichia coli (ATCC 25922), and Candida albicans (ATCC 90028), with MIC values greater than 80.0 mu M. The diprenylated natural product erysubin F (8) and its flavone isomer 7,4'-dihydroxy-8,3'diprenylflavone (27) show in vitro activity against methicillin-resistant Staphylococcus aureus (MRSA, ATCC 43300) at MIC values of 15.4 and 20.5 mu M, respectively. In contrast, the monoprenylated 5-deoxy-3'-prenylbiochanin A (7) is inactive against this MRSA strain.
A thermoresponsive NIPAAm-based polymer is combined with the selective acetylcholinesterase inhibitor tacrine in order to create a strict in sense on/off switch for enzymatic activity. This polymer-inhibitor conjugate inhibits AChE at room temperature and enables reactivation of AChE by heating above the cloud point of the conjugate.
Depletion-induced flocculation of concentrated emulsions probed by photon density wave spectroscopy
(2020)
Stable, creaming-free oil in water emulsions with high volume fractions of oil (phi = 0.05-0.40, density matched to water) and polysorbate 80 as an emulsifier were characterized without dilution by Photon Density Wave spectroscopy measuring light absorption and scattering behavior, the latter serving as the basis for droplet size distribution analysis. The emulsion with phi = 0.10 was used to investigate flocculation processes induced by xanthan as a semi-flexible linear nonabsorbing polymer. Different time regimes in the development of the reduced scattering coefficient mu(s)' could be identified. First, a rapid, temperature-dependent change in mu(s)' during the depletion process was observed. Second, the further decrease of mu(s)' follows a power law in analogy to a spinodal demixing behavior, as described by the Cahn-Hilliard theory.
We discuss an efficient Hierarchical Effective Mode (HEM) representation of a high-dimensional harmonic oscillator bath, which describes phonon-driven vibrational relaxation of an adsorbate-surface system, namely, deuterium adsorbed on Si(100). Starting from the original Hamiltonian of the adsorbate-surface system, the HEM representation is constructed via iterative orthogonal transformations, which are efficiently implemented with Householder matrices. The detailed description of the HEM representation and its construction are given in the second quantization representation. The hierarchical nature of this representation allows access to the exact quantum dynamics of the adsorbate-surface system over finite time intervals, controllable via the truncation order of the hierarchy. To study the convergence properties of the effective mode representation, we solve the time-dependent Schrodinger equation of the truncated system-bath HEM Hamiltonian, with the help of the multilayer extension of the Multiconfigurational Time-Dependent Hartree (ML-MCTDH) method. The results of the HEM representation are compared with those obtained with a quantum-mechanical tier-model. The convergence of the HEM representation with respect to the truncation order of the hierarchy is discussed for different initial conditions of the adsorbate-surface system. The combination of the HEM representation with the ML-MCTDH method provides information on the time evolution of the system (adsorbate) and multiple effective modes of the bath (surface). This permits insight into mechanisms of vibration-phonon coupling of the adsorbate-surface system, as well as inter-mode couplings of the effective bath.
We search for homovalent alternatives for A, B, and X-ions in ABX(3) type inorganic halide perovskites suitable for tandem solar cell applications. We replace the conventional A-site organic cation CH3NH3, by 3 inorganic cations, Cs, K, and Rb, and the B site consists of metals; Cd, Hg, Ge, Pb, and Sn This work is built on our previous high throughput screening of hybrid perovskite materials (Kar et al 2018 J. Chem. Phys. 149, 214701). By performing a systematic screening study using Density Functional Theory (DFT) methods, we found 11 suitable candidates; 2 Cs-based, 3 K-based and 6 Rb-based that are suitable for tandem solar cell applications.
A method for the fabrication of well-defined metallic nanostructures is presented here in a simple and straightforward fashion. As an alternative to lithographic techniques, this routine employs microcontact printing utilizing wrinkled stamps, which are prepared from polydimethylsiloxane (PDMS), and includes the formation of hydrophobic stripe patterns on a substrate via the transfer of oligomeric PDMS. Subsequent backfilling of the interspaces between these stripes with a hydroxyl-functional poly(2-vinyl pyridine) then provides the basic pattern for the deposition of citrate-stabilized gold nanoparticles promoted by electrostatic interaction. The resulting metallic nanostripes can be further customized by peeling off particles in a second microcontact printing step, which employs poly(ethylene imine) surface-decorated wrinkled stamps, to form nanolattices. Due to the independent adjustability of the period dimensions of the wrinkled stamps and stamp orientation with respect to the substrate, particle arrays on the (sub)micro-scale with various kinds of geometries are accessible in a straightforward fashion. This work provides an alternative, cost-effective, and scalable surface-patterning technique to fabricate nanolattice structures applicable to multiple types of functional nanoparticles. Being a top-down method, this process could be readily implemented into, e.g., the fabrication of optical and sensing devices on a large scale.
Bioinspired confinement of upconversion nanoparticles for improved performance in aqueous solution
(2020)
The resonance energy transfer (RET) from NaYF4:Yb,Er upconverting nanoparticles (UNCPs) to a dye (5-carboxytetramethylrhodamine (TAMRA)) was investigated by photoluminescence experiments and microscale thermophoresis (MST). The dye was excited via RET from the UCNPs which was excited in the near-infrared (NIR). The change of the dye diffusion speed (free vs coupled) was investigated by MST. RET shows significant changes in the decay times of the dye as well as of the UCNPs. MST reveals significant changes in the diffusion speed. A unique amphiphilic coating polymer (customized mussel protein (CMP) polymer) for UCNP surface coating was used, which mimics blood protein adsorption and mussel food protein adhesion to transfer the UCNP into the aqueous phase and to allow surface functionalization. The CMP provides very good water dispersibility to the UCNPs and minimizes ligand exchange and subsequent UCNP aging reactions because of the interlinkage of the CMP on the UCNP surface. Moreover, CMP provides N-3-functional groups for dick chemistry-based functionalization demonstrated with the dye 5-carboxytetramethylrhodamine (TAMRA). This establishes the principle coupling scheme for suitable biomarkers such as antibodies. The CMP provides very stable aqueous UCNP dispersions that are storable up to 3 years in a fridge at 5 degrees C without dissolution or coagulation. The outstanding properties of CMP in shielding the UCNP from unwanted solvent effects is reflected in the distinct increase of the photoluminescence decay times after UCNP functionalization. The UCNP-to-TAMRA energy transfer is also spectroscopically investigated at low temperatures (4-200 K), revealing that one of the two green Er(III) emission bands contributes the major part to the energy transfer. The TAMRA fluorescence decay time increases by a factor of 9500 from 2.28 ns up to 22 mu s due to radiationless energy transfer from the UCNP after NIR excitation of the latter. This underlines the unique properties of CMP as a versatile capping ligand for distinctly improving the UCNPs' performance in aqueous solutions, for coupling of biomolecules, and for applications for in vitro and in vivo experiments using UCNPs as optical probes in life science applications.
Its properties make copper one of the world’s most important functional metals. Numerous megatrends are increasing the demand for copper. This requires the prospection and exploration of new deposits, as well as the monitoring of copper quality in the various production steps. A promising technique to perform these tasks is Laser Induced Breakdown Spectroscopy (LIBS). Its unique feature, among others, is the ability to measure on site without sample collection and preparation. In this work, copper-bearing minerals from two different deposits are studied. The first set of field samples come from a volcanogenic massive sulfide (VMS) deposit, the second part from a stratiform sedimentary copper (SSC) deposit. Different approaches are used to analyze the data. First, univariate regression (UVR) is used. However, due to the strong influence of matrix effects, this is not suitable for the quantitative analysis of copper grades. Second, the multivariate method of partial least squares regression (PLSR) is used, which is more suitable for quantification. In addition, the effects of the surrounding matrices on the LIBS data are characterized by principal component analysis (PCA), alternative regression methods to PLSR are tested and the PLSR calibration is validated using field samples.
The spatial magnetic properties, through-space NMR shieldings (TSNMRS), of isolated as well as B-C bond length varied model compounds (BR3 trapped NHCs) have been calculated using the GIAO perturbation method employing the nucleus independent chemical shift (NICS) concept and the results visualized as iso-chemical-shielding surfaces (ICSS) of various size and direction. The TSNMRS values (actually the anisotropy effects measurable in H-1 NMR spectroscopy) are employed to qualify and quantify the present dative vs. coordinative bond character of the boron-carbon bond in the trapped NHCs. Results are confirmed by bond lengths and B-11/C-13 chemical shift variations in the BR3 trapped NHCs.
This paper presents a study of the surface properties of two Ce/Zr mixed oxides with different reducibility, obtained by applying distinct thermal ageing treatments to an oxide with the composition Ce0.62Zr0.38O2. The surface composition was investigated by XPS. Chemical reactivity of the surface was studied by adsorption of the probe molecules CO2, D-2 and methanol. Nanostructural characterization was carried out by XRD, Raman and high-resolution Eu3+ spectroscopy (FLNS). The characterization showed only slight variations in surface composition and bulk Ce-Zr distribution, but hardy differences concerning the type and strength of acidic surface centres, as well as strong differences in the ability to dissociate hydrogen. Structural variations between both samples were identified by comparing the optical spectra of Eu3+ in surface doped samples.
Five known compounds (1-5) were isolated from the extract of Mundulea sericea leaves. Similar investigation of the roots of this plant afforded an additional three known compounds (6-8). The structures were elucidated using NMR spectroscopic and mass spectrometric analyses. The absolute configuration of 1 was established using ECD spectroscopy. In an antiplasmodial activity assay, compound 1 showed good activity with an IC50 of 2.0 mu M against chloroquine-resistant W2, and 6.6 mu M against the chloroquine-sensitive 3D7 strains of Plasmodium falciparum. Some of the compounds were also tested for antileishmanial activity. Dehydrolupinifolinol (2) and sericetin (5) were active against drug-sensitive Leishmania donovani (MHOM/IN/83/AG83) with IC50 values of 9.0 and 5.0 mu M, respectively. In a cytotoxicity assay, lupinifolin (3) showed significant activity on BEAS-2B (IC50 4.9 mu M) and HePG2 (IC50 10.8 mu M) human cell lines. All the other compounds showed low cytotoxicity (IC50 > 30 mu M) against human lung adenocarcinoma cells (A549), human liver cancer cells (HepG2), lung/bronchus cells (epithelial virus transformed) (BEAS-2B) and immortal human hepatocytes (LO2)
The contamination of barley by molds on the field or in storage leads to the spoilage of grain and the production of mycotoxins, which causes major economic losses in malting facilities and breweries. Therefore, on-site detection of hidden fungus contaminations in grain storages based on the detection of volatile marker compounds is of high interest. In this work, the volatile metabolites of 10 different fungus species are identified by gas chromatography (GC) combined with two complementary mass spectrometric methods, namely, electron impact (EI) and chemical ionization at atmospheric pressure (APCI)-mass spectrometry (MS). The APCI source utilizes soft X-radiation, which enables the selective protonation of the volatile metabolites largely without side reactions. Nearly 80 volatile or semivolatile compounds from different substance classes, namely, alcohols, aldehydes, ketones, carboxylic acids, esters, substituted aromatic compounds, alkenes, terpenes, oxidized terpenes, sesquiterpenes, and oxidized sesquiterpenes, could be identified. The profiles of volatile and semivolatile metabolites of the different fungus species are characteristic of them and allow their safe differentiation. The application of the same GC parameters and APCI source allows a simple method transfer from MS to ion mobility spectrometry (IMS), which permits on-site analyses of grain stores. Characterization of IMS yields limits of detection very similar to those of APCI-MS. Accordingly, more than 90% of the volatile metabolites found by APCI-MS were also detected in IMS. In addition to different fungus genera, different species of one fungus genus could also be differentiated by GC-IMS.
The article describes a systematic investigation of the effects of an aqueous NaOH treatment of 3D printed poly(lactic acid) (PLA) scaffolds for surface activation. The PLA surface undergoes several morphology changes and after an initial surface roughening, the surface becomes smoother again before the material dissolves. Erosion rates and surface morphologies can be controlled by the treatment. At the same time, the bulk mechanical properties of the treated materials remain unaltered. This indicates that NaOH treatment of 3D printed PLA scaffolds is a simple, yet viable strategy for surface activation without compromising the mechanical stability of PLA scaffolds.
Nanoporous carbon materials (NCMs) provide the "function" of high specific surface area and thus have large interface area for interactions with surrounding species, which is of particular importance in applications related to adsorption processes. The strength and mechanism of adsorption depend on the pore architecture of the NCMs. In addition, chemical functionalization can be used to induce changes of electron density and/or electron density distribution in the pore walls, thus further modifying the interactions between carbons and guest species. Typical approaches for functionalization of nanoporous materials with regular atomic construction like porous silica, metal-organic frameworks, or zeolites, cannot be applied to NCMs due to their less defined local atomic construction and abundant defects. Therefore, synthetic strategies that offer a higher degree of control over the process of functionalization are needed. Synthetic approaches for covalent functionalization of NCMs, that is, for the incorporation of heteroatoms into the carbon backbone, are critically reviewed with a special focus on strategies following the concept "from molecules to materials." Approaches for coordinative functionalization with metallic species, and the functionalization by nanocomposite formation between pristine carbon materials and heteroatom-containing carbons, are introduced as well. Particular focus is given to the influences of these functionalizations in adsorption-related applications.
The visible-light photocatalyticE/Zisomerization of olefins can be mediated by a wide spectrum of triplet sensitizers (photocatalysts). However, the search for the most efficient photocatalysts through screenings in photo batch reactors is material and time consuming. Capillary and microchip flow reactors can accelerate this screening process. Combined with a fast analytical technique for isomer differentiation, these reactors can enable high-throughput analyses. Ion mobility (IM) spectrometry is a cost-effective technique that allows simple isomer separation and detection on the millisecond timescale. This work introduces a hyphenation method consisting of a microchip reactor and an infrared matrix-assisted laser desorption ionization (IR-MALDI) ion mobility spectrometer that has the potential for high-throughput analysis. The photocatalyzedE/Zisomerization of ethyl-3-(pyridine-3-yl)but-2-enoate (E-1) as a model substrate was chosen to demonstrate the capability of this device. Classic organic triplet sensitizers as well as Ru-, Ir-, and Cu-based complexes were tested as catalysts. The ionization efficiency of theZ-isomer is much higher at atmospheric pressure which is due to a higher proton affinity. In order to suppress proton transfer reactions by limiting the number of collisions, an IM spectrometer working at reduced pressure (max. 100 mbar) was employed. This design reduced charge transfer reactions and allowed the quantitative determination of the reaction yield in real time. Among 14 catalysts tested, four catalysts could be determined as efficient sensitizers for theE/Zisomerization of ethyl cinnamate derivativeE-1. Conversion rates of up to 80% were achieved in irradiation time sequences of 10 up to 180 s. With respect to current studies found in the literature, this reduces the acquisition times from several hours to only a few minutes per scan.
Ammonia (NH3) synthesis by the electrochemical N-2 reduction reaction (NRR) is increasingly studied and proposed as an alternative process to overcome the disadvantages of Haber-Bosch synthesis by a more energy-efficient, carbon-free, delocalized, and sustainable process. An ever-increasing number of scientists are working on the improvement of the faradaic efficiency (FE) and NH3 production rate by developing novel catalysts, electrolyte concepts, and/or by contributing theoretical studies. The present Minireview provides a critical view on the interplay of different crucial aspects in NRR from the electrolyte, over the mechanism of catalytic activation of N-2, to the full electrochemical cell. Five critical questions are asked, discussed, and answered, each coupled with a summary of recent developments in the respective field. This article is not supposed to be a complete summary of recent research about NRR but provides a rather critical personal view on the field. It is the major aim to give an overview over crucial influences on different length scales to shine light on the sweet spots into which room for revolutionary instead of incremental improvements may exist.
A Cu(I)-based metallo-supramolecular polymer with a perpendicularly twisted structure was synthesized by a 1:1 complexation of tetrakis(acetonitrile)copper(I) triflate with the pi-conjugated dibenzoeilatin ligand. Stepwise complexation behavior of Cu(I) with the ligand was revealed by titrimetric ultraviolet- visible (UV-vis) spectroscopic analysis. Formation of a high-molecular-weight polymer (M-w = 1.21 x 10(5) Da) was confirmed by a size-exclusion chromatography-viscometry-right-angle laser light scattering study. A bundle structure of the polymer chains was observed by scanning electron microscopy. A cyclic voltammogram of the polymer film showed reversible redox waves at a negative potential. A device consisting of indium tin oxide (ITO) glass coated with a film of the polymer exhibited reversible green-to-black electrochromism upon alternate application of -3 and +1 V.
Ethylene oxide sterilization of electrospun poly(L-lactide)/poly(D-lactide) core/shell nanofibers
(2021)
The application of polymers in medicine requires sterilization while retaining material structure and properties. This demands detailed analysis, which we show exemplarily for the sterilization of PLLA/PDLA core-shell nanofibers with ethylene oxide (EtO). The electrospun patch was exposed to EtO gas (6 vol% in CO2, 1.7 bar) for 3 h at 45 degrees C and 75% rel. humidity, followed by degassing under pressure/vacuum cycles for 12 h. GC-MS analysis showed that no residual EtO was retained. Fiber diameters (similar to 520 +/- 130 nm) of the patches remained constant as observed by electron microscopy. Young's modulus slightly increased and the elongation at break slightly decreased, determined at 37 degrees C. No changes were detected in H-1-NMR spectra, in molar mass distribution (GPC) or in crystallinity measured for annealed samples with comparable thermal history (Wide Angle X-Ray Scattering). Altogether, EtO emerged as suitable sterilization method for polylactide nanofibers with core-shell morphology.
Porous, layered materials containing sp(2)-hybridized carbon and nitrogen atoms, offer through their tunable properties, a versatile route towards tailormade catalysts for electrochemistry and photochemistry. A key molecule interacting with these quasi two-dimensional materials (2DM) is water, and a photo(electro)chemical key reaction catalyzed by them, is water splitting into H-2 and O-2, with the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) as half reactions. The complexity of some C/N-based 2DM in contact with water raises special needs for their theoretical modelling, which in turn is needed for rational design of C/N-based catalysts. In this work, three classes of C/N-containing porous 2DM with varying pore sizes and C/N ratios, namely graphitic carbon nitride (g-C3N4), C2N, and poly(heptazine imides) (PHI), are studied with various computational methods. We elucidate the performance of different models and model chemistries (the combination of electronic structure method and basis set) for water and water fragment adsorption in the low-coverage regime. Further, properties related to the photo(electro)chemical activity like electrochemical overpotentials, band gaps, and optical excitation energies are in our focus. Specifically, periodic models will be tested vs. cluster models, and density functional theory (DFT) vs. wavefunction theory (WFT). This work serves as a basis for a systematic study of trends for the photo(electro)chemical activity of C/N-containing layered materials as a function of water content, pore size and density.
Four combinations of type-I olefins isoeugenol and 4-hydroxy-3-methoxystyrene with type-II olefins acrolein and crotonaldehyde were investigated in cross-metathesis (CM) reactions. While both type-I olefins are suitable CM partners for this transformation, we observed synthetically useful conversions only with type-II olefin crotonaldehyde. For economic reasons, isoeugenol, a cheap xylochemical available from renewable lignocellulose or from clove oil, is the preferred type-I CM partner. Nearly quantitative conversions to coniferyl aldehyde by the CM reaction of isoeugenol and crotonaldehyde can be obtained at ambient temperature without a solvent or at high substrate concentrations of 2 mol.L-1 with the second-generation Hoveyda-Grubbs catalyst. Under these conditions, the ratio of reactants can be reduced to 1:1.5 and catalyst loadings as low as 0.25 mol % are possible. The high reactivity of the isoeugenol/crotonaldehyde combination in olefin metathesis reactions was demonstrated by a short synthesis of the natural product 7-methoxywutaifuranal, which was obtained from isoeugenol in a 44% yield over five steps. We suggest that the superior performance of crotonaldehyde in the CM reactions investigated can be rationalized by "methylene capping", i.e., the steric stabilization of the propagating Ru-alkylidene species.
Low-energy (5-20 eV) electron-induced single and double strand breaks in well-defined DNA sequences
(2022)
Ionizing radiation is used in cancer radiation therapy to effectively damage the DNA of tumors. The main damage is due to generation of highly reactive secondary species such as low-energy electrons (LEEs). The accurate quantification of DNA radiation damage of well-defined DNA target sequences in terms of absolute cross sections for LEE-induced DNA strand breaks is possible by the DNA origami technique; however, to date, it is possible only for DNA single strands. In the present work DNA double strand breaks in the DNA sequence 5'-d(CAC)(4)/5'd(GTG)(4) are compared with DNA single strand breaks in the oligonucleotides 5'-d(CAC)(4) and 5'-d(GTG)(4) upon irradiation with LEEs in the energy range from 5 to 20 eV. A maximum of strand break cross section was found around 7 and 10 eV independent of the DNA sequence, indicating that dissociative electron attachment is the underlying mechanism of strand breakage and confirming previous studies using plasmid DNA.
The photoinduced nonadiabatic dynamics of the enol-keto isomerization of 10-hydroxybenzo[h]quinoline (HBQ) are studied computationally using high-dimensional quantum dynamics. The simulations are based on a diabatic vibronic coupling Hamiltonian, which includes the two lowest pi pi* excited states and a n pi* state, which has high energy in the Franck-Condon zone, but significantly stabilizes upon excited state intramolecular proton transfer. A procedure, applicable to large classes of excited state proton transfer reactions, is presented to parametrize this model using potential energies, forces and force constants, which, in this case, are obtained by time-dependent density functional theory. The wave packet calculations predict a time scale of 10-15 fs for the photoreaction, and reproduce the time constants and the coherent oscillations observed in time- resolved spectroscopic studies performed on HBQ. In contrast to the interpretation given to the most recent experiments, it is found that the reaction initiated by 1 pi pi* <- S-0 photoexcitation proceeds essentially on a single potential energy surface, and the observed coherences bear signatures of Duschinsky mode-mixing along the reaction path. The dynamics after the 2 pi pi* <- S-0 excitation are instead nonadiabatic, and the n pi* state plays a major role in the relaxation process. The simulations suggest a mainly active role of the proton in the isomerization, rather than a passive migration assisted by the vibrations of the benzoquinoline backbone. <br /> [GRAPHICS] <br /> .
The spatial magnetic properties, through-space NMR shieldings (TSNMRSs), of stable O, S and Hal analogues of N-heterocyclic carbenes (NHCs) have been calculated using the GIAO perturbation method employing the nucleus-independent chemical shift (NICS) concept and the results visualized as iso-chemical-shielding surfaces (ICSSs) of various sizes and directions. The TSNMRS values (actually the anisotropy effects measurable in H-1 NMR spectroscopy) are employed to qualify and quantify the position of the present mesomeric equilibria (carbenes <-> ylides). The results are confirmed by geometry (bond angles and bond lengths), IR spectra, UV spectra, and C-13 chemical shifts of the electron-deficient carbon centers.
Highly K+ selective probes with fluorescence emission wavelengths higher than 500 nm in water
(2020)
Herein, we report on the synthesis of highly K+/Na+ selective fluorescent probes in a feasible number of synthetic steps. These K+ selective fluorescent probes, so called fluoroionophores, 1 and 2 consists of different highly K+/Na+ selective building blocks the alkoxy-substituted N-phenylaza-18-crown-6 lariat ethers (ionophores) and "green" (cf. coumarin unit in 1) or "red" (cf. nile red unit in 2) fluorescent moieties (fluorophores). The fluorescent probes 1 and 2 show K+ induced fluorescence enhancement factors of 4.1 for 1 and 1.9 for 2 and dissociation constants for the corresponding K+ complexes of 43 mM (1+K+) and 18 mM (2+K+) in buffered aqueous solution. The fluorescence signal of 1 and 2 is changed by less than 5 % by pH values in the range of 6.8 to 8.8. Thus, 1 and 2 are capable fluorescent tools to determine extracellular K+ levels by fluorescence enhancements at wavelengths higher than 500 nm.
In this paper the development, use, and evaluation of tasks based on the construct of school-related content knowledge are described. The tasks were used in seminars on organic chemistry for bachelor and master preservice chemistry teachers at a German university. For the evaluation a questionnaire with open and closed items was used. The tasks were rated by the preservice chemistry teachers as relevant for their future profession as a chemistry teacher if the content of the tasks is part of the school curriculum. If the content does not belong to the school curriculum, they rated the nature of the tasks still as relevant; they seem to recognize the importance of conceptual knowledge for their future profession. However, the master's preservice teachers argued with this conceptual knowledge more often than the bachelor's preservice teachers. Although the study is cross-sectional, a certain shift from the focus on the content to conceptual knowledge from bachelor's to master's preservice teachers can be observed.
Halogenated uracil derivatives are of great interest in modern cancer therapy, either as chemotherapeutics or radiosensitisers depending on their halogen atom. This work applies UV-Vis spectroscopy to study the radiation damage of uracil, 5-bromouracil and 5-fluorouracil dissolved in water in the presence of gold nanoparticles upon irradiation with an Nd:YAG ns-pulsed laser operating at 532 nm at different fluences. Gold nanoparticles absorb light efficiently by their surface plasmon resonance and can significantly damage DNA in their vicinity by an increase of temperature and the generation of reactive secondary species, notably radical fragments and low energy electrons. A recent study using the same experimental approach characterized the efficient laser-induced decomposition of the pyrimidine ring structure of 5-bromouracil mediated by the surface plasmon resonance of gold nanoparticles. The present results show that the presence of irradiated gold nanoparticles decomposes the ring structure of uracil and its halogenated derivatives with similar efficiency. In addition to the fragmentation of the pyrimidine ring, for 5-bromouracil the cleavage of the carbon-halogen bond could be observed, whereas for 5-fluorouracil this reaction channel was inhibited. Locally-released halogen atoms can react with molecular groups within DNA, hence this result indicates a specific mechanism by which doping with 5-bromouracil can enhance DNA damage in the proximity of laser irradiated gold nanoparticles.
The spatial magnetic properties, through-space NMR shieldings (TSNMRS), of bent cyclobutylcarbene 8, 1,2-diboretane-3-ylidene 9, and some carbene analogues of boron 14-18 as most intriguing examples of carbenes, which can be stabilized as homoaromatic systems with 3c,2e bonding, have been calculated using the GIAO perturbation method employing the nucleus independent chemical shift (NICS) concept and the results visualized as iso-chemical-shielding surfaces (ICSS) of various size and direction. The TSNMRS values (actually, ring current effect/anisotropy effects as measurable in H-1 NMR spectroscopy) are employed to qualify and quantify the degree of present 3c,2e-homoaromaticity. Results are confirmed by geometry (bond angles and bond lengths) and spectroscopic data, the delta(B-11)/ppm data and the C-13 chemical shifts of the carbene electron-deficient centre.
A convenient method for the synthesis of gamma-spirolactams in only three steps is described. Birch reduction of inexpensive and commercially available aromatic carboxylic acids in the presence of chloroacetonitrile affords nitriles in moderate to good yields. Suitable precursors are methyl-substituted benzoic acids, naphthoic, and anthroic acid. Subsequent catalytic hydrogenation proceeds smoothly with PtO2 or Raney Ni as catalysts and lactams are isolated in excellent yields and stereoselectivities. Thus, up to 3 new stereogenic centers can be constructed as sole diastereomers from achiral benzoic acids. Furthermore, it is possible to control the degree of saturation at different pressures, affording products with 0, 1, or 2 double bonds. Overall, more than 15 new gamma-spirolactams have been synthesized in analytically pure form.
An efficient method for the preparation of arylnaphthalene lignans (ANLs) was developed, which is based on thePhoto-Dehydro-DIELS-ALDER(PDDA) reaction. While intermolecular PDDA reactions turned out to be inefficient, theintramolecular variant using suberic acid as tether linking two aryl propiolic esters smoothly provided naphthalenophanes. Theirradiations were performed with a previously developed annular continuous-flow reactor and UVB lamps. In this way, the naturalproducts Alashinol D, Taiwanin C, and an unnamed ANL could be prepared.
Azobenzene-containing molecules may associate with each other in systems such as self-assembled monolayers or micelles. The interaction between azobenzene units leads to a formation of exciton states in these molecular assemblies. Apart from local excitations of monomers, the electronic transitions to the exciton states may involve charge transfer excitations. Here, we perform quantum chemical calculations and apply transition density matrix analysis to quantify local and charge transfer contributions to the lowest electronic transitions in azobenzene dimers of various arrangements. We find that the transitions to the lowest exciton states of the considered dimers are dominated by local excitations, but charge transfer contributions become sizable for some of the lowest pi pi* electronic transitions in stacked and slip-stacked dimers at short intermolecular distances. In addition, we assess different ways to partition the transition density matrix between fragments. In particular, we find that the inclusion of the atomic orbital overlap has a pronounced effect on quantifying charge transfer contributions if a large basis set is used.
We introduce a thermofield-based formulation of the multilayer multiconfigurational time-dependent Hartree (MCTDH) method to study finite temperature effects on non-adiabatic quantum dynamics from a non-stochastic, wave function perspective. Our approach is based on the formal equivalence of bosonic many-body theory at zero temperature with a doubled number of degrees of freedom and the thermal quasi-particle representation of bosonic thermofield dynamics (TFD). This equivalence allows for a transfer of bosonic many-body MCTDH as introduced by Wang and Thoss to the finite temperature framework of thermal quasi-particle TFD. As an application, we study temperature effects on the ultrafast internal conversion dynamics in pyrazine. We show that finite temperature effects can be efficiently accounted for in the construction of multilayer expansions of thermofield states in the framework presented herein. Furthermore, we find our results to agree well with existing studies on the pyrazine model based on the pMCTDH method.
In the search of new DNA groove binding agents a series of substituted 9,10-methylpyridiniumanthracenes have been synthesized and their interactions with DNA have been studied by UV/vis absorption, CD and fluorescence spectroscopy. A minor groove binding mode is confirmed by DNA melting studies, strong CD effects, the dependence of the binding affinity on ionic strength, and the differentiation between AT and GC base pairs. No binding occurs to GC sequences. Binding constants to calf thymus DNA (ct-DNA) and poly(dA:dT) in the range between 1 x 10(4) and 3 x 10(5) M-1 have been determined. The binding strength decreases with the size of substituents attached at the anthracene site. Variation of the substitution pattern of the charged groups shows that methyl groups in meta position cause slightly stronger binding than methyl groups in para position. In contrast, with these groups in ortho position, no binding interaction has been observed. The strongest binding is achieved with an expansion of the peripheral heterocycle from pyridine to quinoline. Molecular modeling reveals the pivotal role of the substitution pattern: Anthracenes with para and meta pyridines align along the minor grooves. On the other hand, the ortho derivative adopts no groove-alignment.
Educational Scaffolding was first mentioned in 1976 by Wood et al. Several examples for scaffolding in chemistry are also known from the literature. As written scaffolds, stepped supporting tools to support students while solving problems in organic chemistry were developed, applied, and evaluated. Although the students rated the tool as very helpful, a think-aloud study showed that the support given by this scaffold was not sufficient. As a further development of stepped supporting tools, task navigators were therefore developed, applied, and evaluated. This new scaffold gives tips on strategy, knowledge, and application of knowledge after the STRAKNAP concept. The evaluation of this tool shows that the students rated the tool as being very helpful. A think-aloud study showed that the scaffold supports the students while they solve a problem. Because of the stepwise construction of the task navigators and the providing of the knowledge needed for the application, the students can solve parts of the task successfully even if they do not solve all parts correctly; the students can always start from scratch. When students use the tool regularly, their knowledge of organic chemistry increases compared to students who did not use the tool at all. The task navigator is not only a scaffold for the content of the task but also for the development of methodological competences on the field of strategies and applying knowledge.
Epoxidized 1,4-polymyrcene
(2020)
1,4-Polymyrcene was synthesized by anionic polymerization and epoxidized using meta-chloroperbenzoic acid. Samples with different degrees of epoxidation (25%, 49%, 74%, and 98%) were prepared and examined according to their chemical and thermal properties. Epoxidation was found to increase the glass transition temperature (T-g = 14 degrees C for the 98% epoxidized 1,4-polymyrcene) as well as the shelf live (>10 months). The trisubstituted epoxide groups were remarkably stable against nucleophiles under basic conditions but cross-linked or hydrolyzed in the presence of an acid. Also, highly epoxidized 1,4-polymyrcene readily cross-linked upon annealing at 260 degrees C to produce an epoxy resin.
Thirteen N-butylpyridinium salts, including three monometallic [C4Py](2)[MCl4], nine bimetallic [C4Py](2)[(M1-xMxCl4)-M-a-Cl-b] and one trimetallic compound [C4Py](2)[(M1-y-zMyMz (c) Cl4)-M-a-M-b] (M=Co, Cu, Mn; x=0.25, 0.50 or 0.75 and y=z=0.33), were synthesized and their structure and thermal and electrochemical properties were studied. All compounds are ionic liquids (ILs) with melting points between 69 and 93 degrees C. X-ray diffraction proves that all ILs are isostructural. The conductivity at room temperature is between 10(-4) and 10(-8) S cm(-1). Some Cu-based ILs reach conductivities of 10(-2) S cm(-1), which is, however, probably due to IL dec. This correlates with the optical bandgap measurements indicating the formation of large bandgap semiconductors. At elevated temperatures approaching the melting points, the conductivities reach up to 1.47x10(-1) S cm(-1) at 70 degrees C. The electrochemical stability windows of the ILs are between 2.5 and 3.0 V.
Umbrella inversion of ammonia is a prototypical example of large-amplitude vibrational motion, described with a symmetric double-well potential. The transition state of the latter corresponds to a planar (D-3h) molecular geometry, whereas the two equilibrium configurations are equivalent (C-3v) pyramidal structures, with the nitrogen atom being either 'above' or 'below' the plane of the hydrogen atoms. As commonly understood, inversion motion of ammonia corresponds to the coherent, anharmonic, vibrational motion of the molecule, which shuttles back and forth between the two potential wells; that is, oscillation of the nitrogen atom from one side of the H-3 plane to the other, via coherent tunneling. However, this intuitively appealing view of umbrella inversion results from a reduced description of the dynamics, which includes only the inversion vibrational coordinate and fully neglects all the other molecular degrees of freedom. As such, this textbook picture of inversion motion ignores the fact that the two equilibrium structures of ammonia are superimposable, and can only be distinguished by labelling the identical hydrogen nuclei. A correct description of umbrella inversion, which incorporates nuclear permutations, requires the inclusion of other molecular modes. Indeed, it is well known that the quantum symmetrization postulate engenders entanglement between ammonia's nuclear-spin, inversion, and rotation. Using the explicit expressions of the corresponding zeroth-order eigenstates, we clearly show that the inversion density of any multilevel wavepacket of ammonia, including the case of perfectly aligned molecules, is symmetrically distributed between the two potential wells, at all times. This follows from a rigorous demonstration based on the evaluation of the expectation values of the inversion coordinate or equivalent projection operators. However, provided that these wavepackets involve inversion-rotation levels with opposite parity, the inversion density may exhibit dynamical spatial localization. In the latter case, the space-fixed inversion density or, equivalently, the expectation values of the projections of the inversion coordinate on the space-fixed axes, may oscillate between opposite directions in the space-fixed frame. Nevertheless, in all cases, localization of ammonia in a single potential well is impossible, even partially or transiently. This is equivalent to saying that the nitrogen atom has the same probability (one-half) to be on either side of the H-3 plane, for any wavepacket of the molecule and at all times-a conclusion which is in perfect accord with the principle of the indistinguishability of identical particles (nuclei).
This opinion article describes recent approaches to use the "biorefinery" concept to lower the carbon footprint of typical mass polymers, by replacing parts of the fossil monomers with similar or even the same monomer made from regrowing dendritic biomass. Herein, the new and green catalytic synthetic routes are for lactic acid (LA), isosorbide (IS), 2,5-furandicarboxylic acid (FDCA), and p-xylene (pXL). Furthermore, the synthesis of two unconventional lignocellulosic biomass derivable monomers, i.e., alpha-methylene-gamma-valerolactone (MeGVL) and levoglucosenol (LG), are presented. All those have the potential to enter in a cost-effective way, also the mass market and thereby recover lost areas for polymer materials. The differences of catalytic unit operations of the biorefinery are also discussed and the challenges that must be addressed along the synthesis path of each monomers.
The synthesis of sp(2)-conjugated, heteroatom-rich, "carbonaceous" materials from economically feasible raw materials and salt templates is reported. Low cost citrazinic acid (2,6-dihydroxy-4-pyridinecarboxylic acid) and melamine are used as components to form a microporous, amorphous framework, where edges of the covalent frameworks are tightly terminated with nitrogen and oxygen moieties. ZnCl2 as the porogen stabilizes structural microporosity as well as nitrogen and oxygen heteroatoms up to comparably high condensation temperatures of 750 and 950 degrees C. The specific surface area up to 1265 m(2) g(-1) is mainly caused by micropores and typical of heteroatom-rich carbon materials with such structural porosity. The unusually high heteroatom content reveals that the edges and pores of the covalent structures are tightly lined with heteroatoms, while C-C or C-H bonds are expected to have a minor contribution as compared to typical carbon materials without or with minor content of heteroatoms. Adsorption of water vapor and carbon dioxide are exemplarily chosen to illustrate the impact of this heteroatom functionalization under salt-templating conditions on the adsorption properties of the materials. 27.10 mmol g(-1) of H2O uptake (at p/p(0) = 0.9) can be achieved, which also proves the very hydrophilic character of the pore walls, while the maximum CO2 uptake (at 273 K) is 5.3 mmol g(-1). At the same time the CO2/N-2 adsorption selectivity at 273 K can reach values of up to 60. All these values are beyond those of ordinary high surface area carbons, also differ from those of N-doped carbons, and are much closer to those of organized framework species, such as C2N.
In this communication the development of an online course on the topic organic chemistry for nonmajor chemistry students is described and discussed. For this online course, the existing classroom course was further developed. New elements such as podcasts, task navigators, and a forum for discussing the solving of tasks or problems with the content were added. This new online course was evaluated. Therefore, a questionnaire was developed. This consists of questions with regard to the longtime learning behavior of the students and to the online learning. The results of this evaluation show that a preference for online learning and a preference for classroom teaching can be measured separately in two scales. Students values on the scale representing a preference for online learning correlate positively and significantly with confidence in the choice of the study subject, enthusiasm about the subject, and the ability to organize their learning, learning environment, and time management. They correlate also with the satisfaction concerning the materials provided. Students values for one of those teaching methods also correlate with their rating with regard to their exam preparation. Values representing a preference for online teaching correlate positively with students better feeling of exam preparation. Values representing a preference for classroom teaching show negative correlations with the values representing students similar or even better preparation for the exams as a result of online teaching. It is therefore not surprising that the ratings for the two scales correlate with the wish for a combination of online teaching and classroom teaching in the future. As a solution, a new course concept for the time after the corona virus crisis that suits all students is outlined in the outlook.
In this paper, we describe a study on tasks following the construct of school-related content knowledge. We know from previous studies that such tasks were rated by the preservice chemistry teachers as important for their future profession. Those studies were conducted in a traditional course on organic chemistry which was organized around chemical families. Therefore, we used and evaluated the tasks again in a new course on organic chemistry which is organized around basic concepts in organic chemistry. The results of this evaluation show that the students rate the tasks equally well but use other arguments for their rating. They do not focus only on the content of the tasks and whether this content belongs to the school curriculum or not. The students of the conceptual course rated the content more often (95%) as important for their future profession compared with the students in the traditional course (57%). Both groups of students rated the importance of the nature of the task the same way.
In this paper, we introduce a fluorescent dye 1, which is able to detect selectively Pd2+ by a clear fluorescence enhancement (FE) in THF. In the presence of eight Pd2+ equivalents, we observed a fluorescence enhancement factor (FEF) of 28.3. The high Pd2+ induced FEF can be explained by an off switching of multiple quenching processes within 1 by Pd2+. In the free dye 1 a photoinduced electron transfer (PET) and energy transfer (ET) takes place and quenches the anthracenic fluorescence. The coordination of eight Pd2+ units by the alkylthio-substituted porphyrazine receptor suppresses the PET and ET quenching process and the anthracenic fluorescence is switched on.
We report a modified approach to the batch scale preparation of completely engulfed core-shell emulsions or partially engulfed Janus emulsions with colorful optical properties, containing water, olive oil, and silicone oil. The in situ reduction of gold chloride, forming gold nanoparticles (AuNPs) at the olive oil interface in the absence or presence of chitosan, leads to the formation of compartmentalized olive-silicone oil emulsion droplets in water. In the absence of additional reducing components, time-dependent morphological transformations from partial engulfment to complete engulfment were observed. Similar experiments in the presence of chitosan or presynthesized AuNPs show an opposite time-dependent trend of transformation of core-shell structures into partially engulfed ones. This behavior can be understood by a time-dependent rearrangement of the AuNPs at the interface and changes of the interfacial tension. The Pickering effect of AuNPs at oil-water and oil-oil interfaces brings not only color effects to individual microdroplets, which are of special relevance for the preparation of new optical elements, but also a surprising self-assembly of droplets.
Due to the COVID pandemic, the introductory course on organic chemistry was developed and conducted as anonline course. To ensure methodical variety in this course,educational games and quizzes have been developed, used, and evaluated. The attendance of the course, and therefore also the use of the quizzes and games, was voluntary. The quizzes'main goalwas to give the students the opportunity to check whether they had memorized the knowledge needed in the course. Another goal was to make transparent which knowledge the students shouldmemorize by rote. The evaluation shows that the students hadnot internalized all knowledge which they should apply in severaltasks on organic chemistry. They answered multiselect questions in general less well than single-select questions. The games shouldcombine fun with learning. The evaluation of the games shows that the students rated them very well. The students used thosegames again for their exam preparation, as the monitoring of accessing the games showed. Students'experiences with usingelectronic devices in general or for quizzes and games have also been evaluated, because their experience could influence thestudents'assessment of the quizzes and games used in our study. However, the students used electronic devices regularly and shouldtherefore be technically competent to use our quizzes and games. The evaluation showed that the use of digital games for learningpurposes is not very common, neither at school nor at university, although the students had worked with such tools before. Thestudents are also very interested in using and developing such digital games not only for their own study, but also for their future work at school
The spatial magnetic properties, through-space NMR shieldings (TSNMRS), of bent allene 1, the corresponding C-extended 1,3-butadiene derivative 2, and a number of related compounds 3 -20 have been calculated using the gauge-independent atomic orbital perturbation method, employing the nucleus-independent chemical shift concept and visualized as isochemical shielding surfaces of various sizes and directions. Prior to that, both structures and C-13 chemical shifts were calculated and compared with available experimental bond lengths and delta(C-13)/ppm values (also, as a quality criterion for the computed structures). Bond lengths, the delta(C-13)/ppm, and the TSNMRS values are employed to qualify and quantify the electronic structure of the studied compounds in terms of dative or classical electron-sharing bonds.
Both the C-13 chemical shift and the calculated anisotropy effect (spatial magnetic properties) of the electron-deficient centre of stable, crystalline, and structurally characterized carbenes have been employed to unequivocally characterize potential resonance contributors to the present mesomerism (carbene, ylide, betaine, and zwitter ion) and to determine quantitatively the electron deficiency of the corresponding carbene carbon atom. Prior to that, both structures and C-13 chemical shifts were calculated and compared with the experimental delta(C-13)/ppm values and geometry parameters (as a quality criterion for obtained structures).
Infrared matrix-assisted desorption and ionization (IR-MALDI) enables the transfer of sub-micron particles (sMP) directly from suspensions into the gas phase and their characterization with differential mobility (DM) analysis. A nanosecond laser pulse at 2940 nm induces a phase explosion of the aqueous phase, dispersing the sample into nano- and microdroplets. The particles are ejected from the aqueous phase and become charged. Using IR-MALDI on sMP of up to 500 nm in diameter made it possible to surpass the 100 nm size barrier often encountered when using nano-electrospray for ionizing supramolecular structures. Thus, the charge distribution produced by IR-MALDI could be characterized systematically in the 50-500 nm size range. Well-resolved signals for up to octuply charged particles were obtained in both polarities for different particle sizes, materials, and surface modifications spanning over four orders of magnitude in concentrations. The physicochemical characterization of the IR-MALDI process was done via a detailed analysis of the charge distribution of the emerging particles, qualitatively as well as quantitatively. The Wiedensohler charge distribution, which describes the evolution of particle charging events in the gas phase, and a Poisson-derived charge distribution, which describes the evolution of charging events in the liquid phase, were compared with one another with respect to how well they describe the experimental data. Although deviations were found in both models, the IR-MALDI charging process seems to resemble a Poisson-like charge distribution mechanism, rather than a bipolar gas phase charging one.
With recent experimental advances in laser-driven electron dynamics in polyatomic molecules, the need arises for their reliable theoretical modelling. Among efficient, yet fairly accurate methods for many-electron dynamics are Time-Dependent Configuration Interaction Singles (TD-CIS) (a Wave Function Theory (WFT) method), and Real-Time Time-Dependent Density Functional Theory (RT-TD-DFT), respectively. Here we compare TD-CIS combined with extended Atomic Orbital (AO) bases, TD-CIS/AO, with RT-TD-DFT in a grid representation of the Kohn-Sham orbitals, RT-TD-DFT/Grid. Possible ionization losses are treated by complex absorbing potentials in energy space (for TD-CIS/AO) or real space (for RT-TD-DFT), respectively. The comparison is made for two test cases: (i) state-to-state transitions using resonant lasers (pi-pulses), i.e., bound electron motion, and (ii) large-amplitude electron motion leading to High Harmonic Generation (HHG). Test systems are a H-2 molecule and cis- and trans-1,2-dichlorethene, C2H2Cl2, (DCE). From time-dependent electronic energies, dipole moments and from HHG spectra, the following observations are made: first, for bound state-to-state transitions enforced by pi-pulses, TD-CIS nicely accounts for the expected population inversion in contrast to RT-TD-DFT, in agreement with earlier findings. Secondly, when using laser pulses under non-resonant conditions, dipole moments and lower harmonics in HHG spectra are obtained by TD-CIS/AO which are in good agreement with those obtained with RT-TD-DFT/Grid. Deviations become larger for higher harmonics and at low laser intensities, i.e., for low-intensity HHG signals. We also carefully test effects of basis sets for TD-CIS/AO and grid size for RT-TD-DFT/Grid, different exchange-correlation functionals in RT-TD-DFT, and absorbing boundaries. Finally, for the present examples, TD-CIS/AO is observed to be at least an order of magnitude more computationally efficient than RT-TD-DFT/Grid.
Influence of functional groups on the ene reaction of singlet oxygen with 1,4-cyclohexadienes
(2021)
The photooxygenation of 1,4-cyclohexadienes has been studied with a special focus on regio- and stereoselectivities. In all examples, only the methyl-substituted double bond undergoes an ene reaction with singlet oxygen, to afford hydroperoxides in moderate to good yields. We explain the high regioselectivities by a "large-group effect" of the adjacent quaternary stereocenter. Nitriles decrease the reactivity of singlet oxygen, presumably by quenching, but can stabilize proposed per-epoxide intermediates by polar interactions resulting in different stereoselectivities. Spiro lactams and lactones show an interesting effect on regio- and stereoselectivities of the ene reactions. Thus, singlet oxygen attacks the double bond preferentially anti to the carbonyl group, affording only one regioisomeric hydroperoxide. If the reaction occurs from the opposite face, the other regioisomer is exclusively formed by severe electrostatic repulsion in a perepoxide intermediate. We explain this unusual behavior by the fixed geometry of spiro compounds and call it a "spiro effect" in singlet oxygen ene reactions.
The so-called DBD ([1,3]dioxolo[4,5-f][1,3]benzodioxole) dyes are a new class of fluorescent dyes, with tunable photophysical properties like absorption, fluorescence lifetime, and Stokes shift. With the development of sulfur based DBDs, this dye class is extended even further for possible applications in spectroscopy and microscopy. In this paper we are investigating the basic photophysical properties and their implications for future applications for S-4-DBD as well as O-4-DBD. On the basis of time-resolved laser fluorescence spectroscopy, transient absorption spectroscopy, and UV/vis-spectroscopy, we determined the rate constants of the radiative and nonradiative deactivation processes as well as the energy of respective electronic states involved in the electronic deactivation of S-4-DBD and of O-4-DBD. For S-4-DBD we unraveled the triplet formation with intersystem crossing quantum yields of up to 80%. By TD-DFT calculations we estimated a triplet energy of around 13500-14700 cm(-1) depending on the DBD dye and solvent. Through solvent dependent measurements, we found quadrupole moments in the range of 2 B.
The use of organic materials with reversible redox activity holds enormous potential for next-generation Li-ion energy storage devices. Yet, most candidates are not truly sustainable, i.e., not derived from renewable feedstock or made in benign reactions. Here an attempt is reported to resolve this issue by synthesizing an organic cathode material from tannic acid and microporous carbon derived from biomass. All constituents, including the redox-active material and conductive carbon additive, are made from renewable resources. Using a simple, sustainable fabrication method, a hybrid material is formed. The low cost and ecofriendly material shows outstanding performance with a capacity of 108 mAh g(-1) at 0.1 A g(-1) and low capacity fading, retaining approximately 80% of the maximum capacity after 90 cycles. With approximately 3.4 V versus Li+/Li, the cells also feature one of the highest reversible redox potentials reported for biomolecular cathodes. Finally, the quinone-catecholate redox mechanism responsible for the high capacity of tannic acid is confirmed by electrochemical characterization of a model compound similar to tannic acid but without catecholic groups.
Photosensitive azobenzene-containing surfactants have attracted great attention in past years because they offer a means to control soft-matter transformations with light. At concentrations higher than the critical micelle concentration (CMC), the surfactant molecules aggregate and form micelles, which leads to a slowdown of the photoinduced trans -> cis azobenzene isomerization. Here, we combine nonadiabatic dynamics simulations for the surfactant molecules embedded in the micelles with absorption spectroscopy measurements of micellar solutions to uncover the reasons responsible for the reaction slowdown. Our simulations reveal a decrease of isomerization quantum yields for molecules inside the micelles. We also observe a reduction of extinction coefficients upon micellization. These findings explain the deceleration of the trans -> cis switching in micelles of the azobenzene-containing surfactants.
The catalytic activity of metal nanoparticles (NPs) supported on porous supports can be controlled by various factors, such as NPs size, shape, or dispersivity, as well as their interaction with the support or the properties of the support material itself. However, these intrinsic properties are not solely responsible for the catalytic behavior of the overall reaction system, as the local environment and surface coverage of the catalyst with reactants, products, intermediates and other invloved species often play a crucial role in catalytic processes as well. Their contribution can be particularly critical in liquid-phase reactions with gaseous reactants that often suffer from low solubiltiy. One example is (D)-glucose oxidation with molecular oxygen over gold nanoparticles supported on porous carbons. The possibility to promote oxygen delivery in such aqueous phase oxidation reactions via the immobilization of heterogenous catalysts onto the interface of perfluorocarbon emulsion droplets is reported here. Gold-on-carbon catalyst particles can stabilize perfluorocarbon droplets in the aqueous phase and the local concentration of the oxidant in the surroundings of the gold nanoparticles accelerates the rate-limiting step of the reaction. Consequently, the reaction rate of a system with the optimal volume fraction of fluorocarbon is higher than a reference emulsion system without fluorocarbon, and the effect is observed even without additional oxygen supply.
Herein, we represent cation-responsive fluorescent probes for the divalent cations Zn2+, Mg2+ and Ca2+, which show cation-induced fluorescence enhancements (FE) in water. The Zn2+-responsive probes Zn1, Zn2, Zn3 and Zn4 are based on o-aminoanisole-N,N-diacetic acid (AADA) derivatives and show in the presence of Zn2+ FE factors of 11.4, 13.9, 6.1 and 8.2, respectively. Most of all, Zn1 and Zn2 show higher Zn2+ induced FE than the regioisomeric triazole linked fluorescent probes Zn3 and Zn4, respectively. In this set, ZN2 is the most suitable probe to detect extracellular Zn2+ levels. For the Mg2+-responsive fluorescent probes Mg1, Mg2 and Mg3 based on o-aminophenol-N,N,O-triacetic acid (APTRA) derivatives, we also found that the regioisomeric linkage influences the fluorescence responds towards Mg2+ (Mg1+100 mM Mg2+ (FEF=13.2) and Mg3+100 mM Mg2+ (FEF=2.1)). Mg2 shows the highest Mg2+-induced FE by a factor of 25.7 and an appropriate K-d value of 3 mM to measure intracellular Mg2+ levels. Further, the Ca2+-responsive fluorescent probes Ca1 and Ca2 equipped with a 1,2-bis(o-aminophenoxy)ethane-N,N,N',N'-tetraacetic acid (BAPTA) derivative show high Ca2+-induced FEs (Ca1 (FEF=22.1) and Ca2 (FEF=23.0)). Herein, only Ca1 (K-d=313 nM) is a suitable Ca2+ fluorescent indicator to determine intracellular Ca2+ levels.
Somewhat surprisingly, inverted ("O-down") CO adsorbates on NaCl(100) were recently observed experimentally after infrared vibrational excitation (Lau et al., Science, 2020, 367, 175-178). Here we characterize these species using periodic density functional theory and a quantum mechanical description of vibrations. We determine stationary points and minimum energy paths for CO inversion, for low (1/8 and 1/4 monolayers (ML)) and high (1 ML) coverages. Transition state theory is applied to estimate thermal rates for "C-down" to "O-down" isomerization and the reverse process. For the 1/4 ML p(1 x 1) structure, two-dimensional and three-dimensional potential energy surfaces and corresponding anharmonic vibrational eigenstates obtained from the time-independent nuclear Schrodinger equation are presented. We find (i) rather coverage-independent CO inversion energies (of about 0.08 eV or 8 kJ mol(-1) per CO) and corresponding classical activation energies for "C-down" to "O-down" isomerization (of about 0.15 eV or 14 kJ mol(-1) per CO); (ii) thermal isomerization rates at 22 K which are vanishingly small for the "C-down" to "O-down" isomerization but non-negligible for the back reaction; (iii) several "accidentally degenerate" pairs of eigenstates well below the barrier, each pair describing "C-down" to "O-down" localized states.
A set of new functionalized poly(2-oxazoline) homopolymers and copolymers carrying protected catecholic side chains were prepared by microwave-assisted cationic ring-opening (co)polymerization. The copolymerizations of 2-ethyl-2-oxazoline with either 2-(3,4-dimethoxyphenyl)-, 2-(3,4-dimethoxybenzyl)-, or 2-(3,4-dimethoxycinnamyl)-2-oxazoline (comonomer ratio 90 : 10) produced gradient or random copolymers with narrow molar mass distributions. During the copolymerization with the 2-(3,4-dimethoxycinnamyl)-2-oxazoline, however, chain coupling reactions occurred at monomer conversions of >50%, supposedly via Michael-type addition of intermediately formed ketene N,O-acetal end groups to 3,4-dimethoxycinnamyl amide side chains. A poly[(2-ethyl-2-oxazoline)-grad-(2-(3,4-dimethoxyphenyl)-2-oxazoline)] was examplarily subjected to partial demethylation and acidic hydrolysis to give a hydrophilic copolymer carrying both catecholic and cationic units, which is designed as a bioinspired adhesive copolymer mimicking mussel adhesive protein.
In this article, we report on the synthesis of acyclic bis(monoalkylamino)maleonitriles and on the intended synthesis of macrocyclic bis(dialkylamino)maleonitriles to get fluorescent probes for cations. During our efforts to synthesize macrocyclic bis(dialkylamino)maleonitriles, we were only able to isolate macrocyclic bis(dialkylamino)-fumaronitriles. The synthesis of macrocyclic bis(dialkylamino)maleonitriles is challenging, due to the fact that bis-(dialkylamino)fumaronitriles are thermodynamically more stable than the corresponding bis(dialkylamino)-maleonitriles. Further, it turned out that the acyclic bis(monoalkylamino)maleonitriles and macrocyclic bis-(dialkylamino)fumaronitriles are no suitable tools to detect cations by a strong fluorescence enhancement. Further, only the bis(monoalkylamino)maleonitriles, which are bearing a 2-pyridyl unit as an additional complexing unit, are able to selectively recognize copper(II) by a color change from yellow to red.
Electrical actuation of coated and composite fibers based on poly[ethylene-co-(vinyl acetate)]
(2020)
Robots are typically controlled by electrical signals. Resistive heating is an option to electrically trigger actuation in thermosensitive polymer systems. In this study electrically triggerable poly[ethylene-co-(vinyl acetate)] (PEVA)-based fiber actuators are realized as composite fibers as well as polymer fibers with conductive coatings. In the coated fibers, the core consists of crosslinked PEVA (cPEVA), while the conductive coating shell is achieved via a dip coating procedure with a coating thickness between 10 and 140 mu m. The conductivity of coated fibers sigma = 300-550 S m(-1) is much higher than that of the composite fibers sigma = 5.5 S m(-1). A voltage (U) of 110 V is required to heat 30 cm of coated fiber to a targeted temperature of approximate to 65 degrees C for switching in less than a minute. Cyclic electrical actuation investigations reveal epsilon '(rev) = 5 +/- 1% reversible change in length for coated fibers. The fabrication of such electro-conductive polymeric actuators is suitable for upscaling so that their application potential as artificial muscles can be explored in future studies.
The combination of a highly stereoselective tethered olefin metathesis reaction and a Julia-Kocienski olefination is presented as a strategy for the synthesis of conjugated polyenes with at least one Z-configured C=C bond. The strategy is exemplified by the synthesis of the marine natural product (+)-bretonin B.
Recent experiments and theory suggest that ground state properties and reactivity of molecules can be modified when placed inside a nanoscale cavity, giving rise to strong coupling between vibrational modes and the quantized cavity field. This is commonly thought to be caused either by a cavity-distorted Born-Oppenheimer ground state potential or by the formation of light-matter hybrid states, vibrational polaritons. Here, we systematically study the effect of a cavity on ground state properties and infrared spectra of single molecules, considering vibration-cavity coupling strengths from zero up to the vibrational ultrastrong coupling regime. Using single-mode models for Li-H and O-H stretch modes and for the NH3 inversion mode, respectively, a single cavity mode in resonance with vibrational transitions is coupled to position-dependent molecular dipole functions. We address the influence of the cavity mode on polariton ground state energies, equilibrium bond lengths, dissociation energies, activation energies for isomerization, and on vibro-polaritonic infrared spectra. In agreement with earlier work, we observe all mentioned properties being strongly affected by the cavity, but only if the dipole self-energy contribution in the interaction Hamiltonian is neglected. When this term is included, these properties do not depend significantly on the coupling anymore. Vibro-polaritonic infrared spectra, in contrast, are always affected by the cavity mode due to the formation of excited vibrational polaritons. It is argued that the quantized nature of vibrational polaritons is key to not only interpreting molecular spectra in cavities but also understanding the experimentally observed modification of molecular reactivity in cavities.
In this paper, we report on the fluorescence behaviour of three regioisomers which consist of two 9-anthracenyl fluorophores and of differently substituted dithiodicyanoethene moieties. These isomeric fluorescent probes show different quantum yields (phi(f)). In these probes, an oxidative photoinduced electron transfer (PET) from the excited 9-anthracenyl fluorophore to the dithiodicyanoethene unit quenches the fluorescence. This quenching process is accelerated by an intramolecular charge transfer (ICT) of the push-pull pi-electron system of the dithiodicyanoethene group. The acceleration of the PET depends on the strength of the ICT unit. The higher the dipole moment of the ICT unit, the stronger the observed fluorescence quenching. To the best of our knowledge, this is the first report of a regioisomeric influence on an oxidative PET by an ICT.
We report on a further development of [1,3]-dioxolo[4.5-f]benzodioxole (DBD) fluorescent dyes by replacement of the four oxygen atoms of the heterocyclic core by sulfur atoms. This variation causes striking changes of the photophysical properties. Whereas absorption and emission significantly shifted to longer wavelength, the fluorescence lifetimes and quantum yields are diminished compared to DBD dyes. The latter effect is presumably caused by an enhanced intersystem crossing to the triplet state due to the sulfur atoms. The very large Stokes shifts of the S-4-DBD dyes ranging from 3000 cm(-1) to 7400 cm(-1) (67 nm to 191 nm) should be especially emphasized. By analogy with DBD dyes a broad variation of absorption and emission wavelength is possible by introducing different electron withdrawing substituents. Moreover, some derivatives for coupling with biomolecules were developed.
9,10-substituted anthracenes are known for their useful optical properties like fluorescence, which makes them frequently used probes in sensing applications. In this article, we investigate the fundamental photophysical properties of three pyridyl-substituted variants. The nitrogen atoms in the pyridinium six-membered rings are located in the ortho-, meta-, and para-positions in relation to the anthracene core. Absorption, fluorescence, and transient absorption measurements were carried out and were complemented by theoretical calculations. We monitored the photophysics of the anthracene derivatives in chloroform and water investigating the protonated as well as their nonprotonated forms. We found that the optical properties of the nonprotonated forms are strongly determined by the anthracene chromophore, with only small differences to other 9,10-substituted anthracenes, for example diphenyl anthracene. In contrast, protonation leads to a strong decrease in fluorescence intensity and lifetime. Transient absorption measurements and theoretical calculations revealed the formation of a charge-transfer state in the protonated chromophores, where electron density is shifted from the anthracene moiety toward the protonated pyridyl substituents. While the para- and ortho-derivatives' charge transfer is still moderately fluorescent, the meta-derivative is affected much stronger and shows nearly no fluorescence. This nitrogen-atom-position-dependent sensitivity to hydronium activity makes a combination of these fluorophores very attractive for pH-sensing applications covering a broadened pH range.
Hypothesis: Bimetallic magnetite-gold nanostructures are interesting candidates to combine and enhance individual properties of each metal element in catalytic and analytical applications. Microemulsions have been employed in templated synthesis of nanoparticles, and their combination with different types of nanoparticles can further mediate interactions at the water-oil interface, providing new forms of hybrid nanostructures.
Experiments: Reverse water-in-oil microemulsions of droplet sizes below 50 nm were prepared from ternary mixtures of Aerosol-OT (AOT) as surfactant, incorporating 4 nm sized superparamagnetic nanoparticles (MNPs) to the hexane-pentanol oil phase and 5 nmsized polyethyleneimine-stabilized gold nanoparticles (Au(PEI)-NPs) to the water phase. The resulting isotropic L-2 phase, Winsor phases and organized nanostructures were investigated using conductometry, calorimetry, UV-Vis spectroscopy, cryoSEM and HRTEM.
Findings: Droplet-droplet interactions, morphology and surfactant film properties of AOT microemulsions could be modulated in different ways by the presence of the different nanoparticles from each liquid phase. Additionally, phase separation into Winsor phases allows the formation upon solvent evaporation of films with bimetallic heterostructures on the micrometer scale. This demonstrates a new way of nanoparticle templated assembly at liquid interfaces by assisted interactions between microemulsions and nanoparticles, as a promising strategy to obtain thin films of small, isotropic nanoparticles with hierarchical ordering.
Prenylated flavanones were obtained from ortho-allyloxy chalcones through a one-pot sequence of Claisen rearrangement and 6-endo-trig cyclization, followed by olefin cross metathesis of the intermediate allyl flavanones with 2-methyl-2-butene. The synthetic utility of this route is illustrated for the synthesis of several naturally occurring prenyl flavanones.
Carbohydrate radical stabilities in the 1- and 2-position have been determined by a radical clock approach, starting from cyclopropanated sugars with xanthates as precursors. Various hexoses and pentoses afforded 1-deoxy sugars as main products, indicating that anomeric radicals are more stable than radicals in the 2-position. An additional influence of the configurations on radical stabilities has been observed. Our results should be interesting for the understanding of 1,2-radical rearrangements in carbohydrate chemistry and offer an easy access to deoxy-vinyl sugars.
Isoprene and beta-myrcene were polymerized by anionic polymerization in bulk and in the 'green' ether solvents cyclopentyl methyl ether and 2-methyltetrahydrofuran and, for comparison, in cyclohexane and tetrahydrofuran. The polydienes produced in bulk and in cyclohexane contained high amounts of 1,4 units (>90%) whereas those produced in ether solvents were rich in 1,2 and 3,4 units (36%-86%). Comparison of the microstructures and glass transition temperatures of the polydienes obtained in the various solvents suggests that conventionally used solvents can be substituted by environmentally more friendly alternatives.
Artificial light harvesting complexes find applications in artificial photosynthesis, photovoltaics and light harvesting chemical sensors. They are used to enhance the absorption of light of a reaction center which is often represented by a single acceptor. Here, we present different light harvesting systems on DNA origami structures and analyze systematically the light harvesting efficiency. By changing the number and arrangement of different fluorophores (FAM as donor, Cy3 as transmitter and Cy5 as acceptor molecules) the light harvesting efficiency is optimized to create a broadband absorption and to improve the antenna effect 1 (including two energy transfer steps) from 0.02 to 1.58, and the antenna effect 2 (including a single energy transfer step) from 0.04 to 8.7, i.e. the fluorescence emission of the acceptor is significantly higher when the light-harvesting antenna is excited at lower wavelength compared to direct excitation of the acceptor. The channeling of photo energy to the acceptor proceeds by Forster Resonance Energy Transfer (FRET) and we carefully analyze also the FRET efficiency of the different light harvesting systems. Accordingly, the antenna effect can be tuned by modifying the stoichiometry of donor, transmitter and acceptor dyes, whereas the FRET efficiency is mainly governed by the spectroscopic properties of dyes and their distances.
The acyclic monoterpene beta-myrcene is polymerized by anionic polymerization at room temperature using sec-butyllithium as the initiator and the cyclic monoterpene DL-limonene as an unsaturated hydrocarbon solvent. The polymerization is a living process and allows production of polymyrcenes with narrow molar mass distribution ((sic) similar to 1.06) and high content of 1,4 units (similar to 90%) as well as block copolymers.
The palladium-catalyzed oxidative Heck-reaction, also referred to as Fujiwara-Moritani-reaction, has been investigated for the synthesis of styrenylsulfonyl compounds. Acetanilides and vinylsulfonyl compounds undergo dehydrogenative coupling reactions in moderate to quantitative yields, using benzoquinone as the oxidant of choice. Potassium peroxodisulfate, which had previously been identified as a superior oxidant for the coupling with acrylates, did not provide any coupling products with these olefins. Traceless removal of the catalyst directing group through a deacetylation-diazotation-coupling (DDC) sequence was demonstrated for 2-arylethene sulfones.
Enzyme degradable polymersomes from chitosan-g-[poly-l-lysine-block-epsilon-caprolactone] copolymer
(2020)
The scope of this study includes the synthesis of chitosan-g-[peptide-poly-epsilon-caprolactone] and its self-assembly into polymeric vesicles employing the solvent shift method. In this way, well-defined core-shell structures suitable for encapsulation of drugs are generated. The hydrophobic polycaprolactone side-chain and the hydrophilic chitosan backbone are linked via an enzyme-cleavable peptide. The synthetic route involves the functionalization of chitosan with maleimide groups and the preparation of polycaprolactone with alkyne end-groups. A peptide functionalized with a thiol group on one side and an azide group on the other side is prepared. Thiol-ene click-chemistry and azide-alkyne Huisgen cycloaddition are then used to link the chitosan and poly-epsilon-caprolactone chains, respectively, with this peptide. For a preliminary study, poly-l-lysin is a readily available and cleavable peptide that is introduced to investigate the feasibility of the system. The size and shape of the polymersomes are studied by dynamic light scattering and cryo-scanning electron microscopy. Furthermore, degradability is studied by incubating the polymersomes with two enzymes, trypsin and chitosanase. A dispersion of polymersomes is used to coat titanium plates and to further test the stability against enzymatic degradation.
The reaction of flavanones with hypervalent iodine reagents was investigated with a view to the synthesis of naturally occurring isoflavones. In contrast to several previous reports in the literature, we did not observe the formation of any benzofurans via a ring contraction pathway, but could isolate only isoflavones, resulting from an oxidative 2,3-aryl rearrangement, and flavones, resulting from an oxidation of the flavanones. Although the 2,3-oxidative rearrangement allows a synthetically useful approach toward some isoflavone natural products due to the convenient accessibility of the required starting materials, the overall synthetic utility and generality of the reaction appear to be more limited than previous literature reports suggest.
The molecular structures of three closely related isoflavones have been determined by single crystal X-ray diffraction and have been analysed by geometry matching with the CSD, Hirshfeld surface analysis and analysis of stacking interactions with the Aromatic Analyser program (CSD). The formation of the supramolecular structure by non-covalent interactions was studied and substantial differences in the macroscopic properties e.g., the solubility, were correlated with hydrogen bonding and pi-stacking interactions. Moreover, a correlation between the supramolecular structure, the torsion angle (between benzopyran group and aryl group), and macroscopic properties was determined in the three compounds.
The replacement of oxygen by sulfur atoms of [1,3]-dioxolo[4.5-f]benzodioxole (DBD) fluorescent dyes is an efficient way to adjust the photophysical properties (sulfur tuning). While previously developed S-4-DBD dyes exhibit considerably red-shifted absorption and emission wavelength, the heavy atom effect of four sulfur atoms cause low fluorescence quantum yields and short fluorescence lifetimes. Herein, we demonstrate that the replacement of less than four sulfur atoms (S-1-DBD, 1,2-S-2-DBD, and 1,4-S-2-DBD dyes) permits a fine-tuning of the photophysical properties. In some cases, a similar influence on the wavelength without the detrimental effect on the quantum yields and lifetimes is observed. Furthermore, the synthetic accessibility of S-1- and S-2-DBD dyes is improved, compared with S-4-DBD dyes. For coupling with biomolecules a series of reactive derivatives of the new dyes were developed (azides, OSu esters, alkynes, maleimides).
Ruthenium-catalyzed sulfoalkenylation of acetanilides and dual-use of the catalyst directing group
(2021)
In contrast to vinylsulfonates and vinylsulfones, vinylsulfonamides are unreactive in Pd-catalyzed oxidative Heck-coupling reactions with acetanilides. This limitation has been resolved by using a C-H-activation protocol based on Ru-Cu-Ag-catalysis. Overall, the Ru-Cu-Ag-catalyzed conditions turned out to be more reliable and showed better reproducibility than the Pd-catalyzed C-H-activation. The coupling products thus obtained are functionalized styrenyl sulfones and -sulfonamides which can be used as starting materials for the synthesis of sulfonyl pyrroles and sulfonyl pyrrolo[2,3-c]quinolines.
Photodynamic therapy (PDT) is a mild but effective method to treat certain types of cancer upon irradiation with visible light. Here, three isomeric methylpyridinium alkynylanthracenes 1op were evaluated as sensitizers for PDT. Upon irradiation with blue or green light, all three compounds show the ability to initiate strand breaks of plasmid DNA. The mayor species responsible for cleavage is singlet oxygen (O-1(2)) as confirmed by scavenging reagents. Only isomers 1m and 1p can be incorporated into HeLa cells, whereas isomer 1o cannot permeate through the membrane. While isomer 1m targets the cell nucleus, isomer 1p assembles in the cellular cytoplasm and impacts the cellular integrity. This is in accordance with a moderate toxicity of 1p in the dark, whereas 1m exhibits no dark toxicity. Both isomers are suitable as PDT reagents, with a CC50 of 3 mu m and 75 nm, for 1p and 1m, respectively. Thus, derivative 1m, which can be easily synthesized, becomes an interesting candidate for cancer therapy.
Arsenolipids include a wide range of organic arsenic species that occur naturally in seafood and thereby contribute to human arsenic exposure. Recently arsenic-containing phosphatidylcholines (AsPCs) were identified in caviar, fish, and algae. In this first toxicological assessment of AsPCs, we investigated the stability of both the oxo- and thioxo-form of an AsPC under experimental conditions, and analyzed cell viability, indicators of genotoxicity and biotransformation in human liver cancer cells (HepG2). Precise toxicity data could not be obtained owing to the low solubility in the cell culture medium of the thioxo-form, and the ease of hydrolysis of the oxo-form, and to a lesser degree the thioxo-form. Hydrolysis resulted amongst others in the respective constituent arsenic-containing fatty acid (AsFA). Incubation of the cells with oxo-AsPC resulted in a toxicity similar to that determined for the hydrolysis product oxo-AsFA alone, and there were no indices for genotoxicity. Furthermore, the oxo-AsPC was readily taken up by the cells resulting in high cellular arsenic concentrations (50 μM incubation: 1112 ± 146 μM As cellular), whereas the thioxo-AsPC was substantially less bioavailable (50 μM incubation: 293 ± 115 μM As cellular). Speciation analysis revealed biotransformation of the AsPCs to a series of AsFAs in the culture medium, and, in the case of the oxo-AsPC, to as yet unidentified arsenic species in cell pellets. The results reveal the difficulty of toxicity studies of AsPCs in vitro, indicate that their toxicity might be largely governed by their arsenic fatty acid content and suggest a multifaceted human metabolism of food derived complex arsenolipids.
Bottom, top, or in between
(2022)
Attractive label-free plasmonic optical fiber sensors can be developed by cleverly choosing the arrangement of plasmonic nanostructures and other building blocks. Here, the final response depends very much on the alignment and position (stacking) of the individual elements. In this work, three different types of fiber optic sensing geometries fabricated by simple layer-by-layer stacking are presented, consisting of stimulus-sensitive poly-N-isopropylacrylamide (polyNIPAM) microgel arrays and plasmonic nanohole arrays (NHAs), namely NHA/polyNIPAM, polyNIPAM/NHA, polyNIPAM/NHA/polyNIPAM. Their optical response to a representative stimulus, namely temperature, is investigated. NHA/polyNIPAM monitors the volume phase transition of polyNIPAM microgels through changes in the spectral position and the amplitude of the reflection minimum of plasmonic NHA. In contrast, polyNIPAM/NHA shows a more complex response to the swelling and collapse of polyNIPAM microgels in their reflectance spectra. The most pronounced changes in optical response are observed by monitoring the amplitude of the reflectance minimum of this sensor during heating/cooling cycles. Finally, the triple stack of polyNIPAM/NHA/polyNIPAM at the end of a optical fiber tip combines the advantages of the NHA/polyNIPAM, polyNIPAM/NHA double stacks for optical sensing. The unique layer-by-layer stacking of microgel and nanostructure is customizable and can be easily adopted for other applications.
The photochemical fragmentation of N-aroylsulfonamides 9 (ASAP) is a powerful method for the preparation of various biaryls. Compounds 9 are easily accessible in two steps from amines by treatment with arenesulfonyl chlorides and aroyl chlorides. Many of these compounds were prepared for the first time. The irradiation takes place in a previously developed continuous-flow reactor using inexpensive UVB or UVC fluorescent lamps. Isocyanates and sulphur dioxide are formed as the only by-products. The ASAP tolerates a variety of functional groups and is even suited for the preparation of phenylnaphthalenes and terphenyls. The ASAP mechanism was elucidated by interaction of photophysical and quantum chemical (DFT) methods and revealed a spirocyclic biradical as key intermediate.
Structure and spatial magnetic properties, through-space NMR shieldings (TSNMRSs), of all ten cycl[2.2.2]azine to cycl[4.4.4]azine, hetero-analogues and the corresponding hydrocarbons have been calculated at the B3LYP/6-311G(d,p) theory level using the GIAO perturbation method and employing the nucleus independent chemical shift (NICS) concept. The TSNMRS values (actually, the ring current effect as measurable in H-1 NMR spectroscopy) are visualized as iso-chemical-shielding surfaces (ICSS) of various size and direction, and employed to readily qualify and quantify the degree of (anti)aromaticity. Results are confirmed by NMR [delta(H-1)/ppm, delta(N-15)/ppm] and geometry (planar, twisted, bow-shaped) data. The cyclazines N[2.2.2](-) up to N[2.4.4](-) are planar or at most slightly bowl-shaped and, due to coherent peripheral ring currents (except in N[2.3.3](-), N[2.3.4], N[3.3.4](+) and N[2.4.4](+)), develop aromaticity or anti-aromaticity of the whole molecules dependent on the number of peripheral conjugated pi electrons. The cyclazines N[2.3.3](-), N[2.3.4], N[3.3.4](+) and N[2.4.4](+) develop two ring currents of different direction within the same molecule, in which the dominating ring current proves to be paratropic (in N[3.3.4](+) diatropic) including the nodal N p(z) lone pair into the conjugation. The residual cyclazines N[3.4.4], N[4.4.4](-) and N[4.4.4](+) are heavily twisted and, therefore, are not developing peripheral or diverse ring currents. The TSNMRS information about cyclazines and the parent tricyclic annulene analogues is congruent subject to structure and number of peripheral or internal conjugated pi electrons, the corresponding (anti)aromaticity is in unequivocal accordance with Huckel's rule.
In our search for new antiplasmodial agents, the CH2Cl2/CH3OH (1:1) extract of the roots of Tephrosia aequilata was investigated, and observed to cause 100% mortality of the chloroquine-sensitive (3D7) strain of Plasmodium falciparum at a 10 mg/mL concentration. From this extract three new chalconoids, E-2,6-dimethoxy-3,4-(2,2-dimethyl)pyranoretrochalcone (1, aequichalcone A), Z-2,6-dimethoxy-3,4-(2,2-dimethyl)pyranoretrochalcone (2, aequichalcone B), 4-ethoxy-3-hydroxypraecansone B (3, aequichalcone C) and a new pterocarpene, 3,4:8,9-dimethylenedioxy-6a,11a-pterocarpene (4), along with seven known compounds were isolated. The purified compounds were characterized by NMR spectroscopic and mass spectrometric analyses. Compound 1 slowly converts into 2 in solution, and thus the latter may have been enriched, or formed, during the extraction and separation process. The isomeric compounds 1 and 2 were both observed in the crude extract. Some of the isolated constituents showed good to moderate antiplasmodial activity against the chloroquine-sensitive (3D7) strain of Plasmodium falciparum.
Recently, Nocera and co-workers (J. Am. Chem. Soc. 2018, 140, 13711) demonstrated that triaryl borate Lewis acids facilitate the direct electrochemical reduction of triphenylphosphine oxide (TPPO) to triphenylphosphine (TPP). In the present contribution, we report a quantum chemical study unravelling details of the reaction, which also supports the proposed ECrECi mechanism. Alternative electrochemical routes to TPPO reduction facilitated by other Lewis acids (CH3+), or by photocatalysis at semiconductor surfaces, are also briefly discussed.
microRNAs (miRNAs) have been identified as high-value drug targets. A widely applied strategy in miRNA inhibition is the use of antisense agents. However, it has been shown that oligonucleotides are poorly cell permeable because of their complex chemical structure and due to their negatively charged backbone. Consequently, the general application of oligonucleotides in therapy is limited. Since miRNAs’ functions are executed exclusively by the Argonaute 2 protein, we therefore describe a protocol for the design of a novel miRNA inhibitor class: antagonists of the miRNA-Argonaute 2 protein complex, so-called anti-miR-AGOs, that not only block the crucial binding site of the target miRNA but also bind to the protein’s active site. Due to their lower molecular weight and, thus, more drug-like chemical structure, the novel inhibitor class may show better pharmacokinetic properties than reported oligonucleotide inhibitors, enabling them for potential therapeutic use.
N-terminal methacrylation of peptide MAXI, which is capable of conformational changes variation of the pH, results in a peptide, named VK20. Increasing the reactivity of this terminal group enables further coupling reactions or chemical modifications of the peptidc. However, this end group functionalization may influence the ability of confonnational changes of VK20; as well as its properties. In this paper; the influence of pH on the transition between random coil and beta-sheet conformation of VK20; including the transition kinetics, were investigated. At pH values of 9 and higher, the kinetics beta-sheet formation increased tor VK(2 0, compared to MAXI. The self-assembly into beta-sheets recognized by the formation of a physically crosslinked gel was furthermore indicated by a significant increase of G. An increase in pH (from 9 to 9.5) led to a faster gelation of the peptide VK20. Simultaneously, G was increased from 460 +/- 70 Pa (at pH 9) to 1520 +/- 180 Pa (at pH 9.5). At the nanoscale, the gel showed a highly interconnected fibrillar/network structure with uniform fibril widths of approximately 3.4 +/- 0.5 nm (N=30). The recovery of the peptide conformation back to random coil resulted in the dissolution of the gel; whereby the kinetics of the recovery depended on the pH. Conclusively, the ability of MAXI to undergo confommtional changes was not affected by N-terminal methacrylation whereas the kinetics of pH-sensitive beta-sheet formations has been increased.
Background: In Kenya, several species of the genus Maytenus are used in traditional medicine to treat many diseases including malaria. In this study, phytochemical constituents and extracts of Maytenus undata, M. putterlickioides, M. senegalensis and M. heterophylla were evaluated to determine compound/s responsible for antimalarial activity.
Objective: To isolate antiplasmodial compounds from these plant species which could be used as marker compounds in the standardization of their extracts as a phytomedicine for malaria.
Methods: Constituents were isolated through activity-guided fractionation of the MeOH/CHCl3 (1:1) extracts and in vitro inhibition of Plasmodium falciparum. Cytotoxicity was evaluated using Vero cells and the compounds were elucidated on the basis of NMR spectroscopy.
Results: Fractionation of the extracts resulted in the isolation of ten known compounds. Compound 1 showed promising antiplasmodial activity with IC50, 3.63 and 3.95 ng/ml against chloroquine sensitive (D6) and resistant (W2) P. falciparum, respectively and moderate cytotoxicity (CC50, 37.5 ng/ml) against Vero E6 cells. The other compounds showed weak antiplasmodial (IC50 > 1.93 mu g/ml) and cytotoxic (CC50 > 39.52 mu g/ml) activities against P. falciparum and Vero E6 cells, respectively.
Conclusion: (20 alpha)-3-hydroxy-2-oxo-24-nor-friedela-1(10),3,5,7-tetraen-carboxylic acid-(29)-methyl-ester (pristimerin) (1) was the most active marker and lead compound that warrants further investigation as a template for the development of new antimalarial drugs. Pristimerin is reported for the first time in M. putterlickioides. 3-Hydroxyolean-12-en-28-oic acid (oleanolic acid) (5), stigmast-5-en-3-ol (beta-sitosterol) (6), 3-oxo-28-friedelanoic acid (7), olean-12-en-3-ol (beta-amyrin) (8), lup-20(29)-en-3-ol (lupeol) (9) and lup-20(29)-en-3-one (lupenone) (10) are reported for the first time in M. undata.
In this study, a multiblock copolymer containing oligo(3-methyl-morpholine-2, 5-dione) (oMMD) and oligo(3-sec-butyl-morpholine-2, 5-dione) (oBMD) building blocks obtained by ring-opening polymerization (ROP) of the corresponding monomers, was synthesized in a polyaddition reaction using an aliphatic diisocyanate. The multiblock copolymer (pBMD-MMD) provided a molecular weight of 40, 000 g·mol−1, determined by gel permeation chromatography (GPC). Incorporation of both oligodepsipeptide segments in multiblock copolymers was confirmed by 1H NMR and Matrix Assisted Laser Desorption/Ionization Time Of Flight Mass Spectroscopy (MALDI-TOF MS) analysis. pBMD-MMD showed two separated glass transition temperatures (61 °C and 74 °C) indicating a microphase separation. Furthermore, a broad glass transition was observed by DMTA, which can be attributed to strong physical interaction i.e. by H-bonds formed between amide, ester, and urethane groups of the investigated copolymers. The obtained multiblock copolymer is supposed to own the capability to exhibit strong physical interactions.
Non-Born–Oppenheimer quantum dynamics of H+ 2 excited by shaped one-cycle laser pulses linearly polarised along the molecular axis have been studied by the numerical solution of the time-dependent Schrödinger equation within a three-dimensional model, including the internuclear separation, R, and the electron coordinates z and ρ. Laser carrier frequencies corresponding to the wavelengths λ l = 25 nm through λ l = 400 nm were used and the amplitudes of the pulses were chosen such that the energy of H+ 2 was close to its dissociation threshold at the end of any laser pulse applied. It is shown that there exists a characteristic oscillation frequency ωosc ≃ 0.2265 au (corresponding to the period of τosc ≃ 0.671 fs and the wavelength of λosc ≃ 201 nm) that manifests itself as a ‘carrier’ frequency of temporally shaped oscillations of the time-dependent expectation values ⟨z ⟩ and ⟨∂V/∂z ⟩ that emerge at the ends of the laser pulses and exist on a timescale of at least 50 fs. Time-dependent expectation values ⟨ρ⟩ and ⟨∂V /∂ρ⟩ of the optically passive degree of freedom, ρ, demonstrate post-laser-field oscillations at two basic frequencies ωρ 1 ≈ ωosc and ωρ 2 ≈ 2ωosc. Power spectra associated with the electronic motion show higher- and lower-order harmonics with respect to the driving field.
Cryo-electron microscopy (cryo-EM) is a powerful structure determination technique that is well-suited to the study of protein and polymer self-assembly in solution. In contrast to conventional transmission electron microscopy (TEM) sample preparation, which often times involves drying and staining, the frozen-hydrated sample preparation allows the specimens to be kept and imaged in a state closest to their native one. Here, we give a short overview of the basic principles of Cryo-EM and review our results on applying it to the study of different protein and polymer self-assembled nanostructures. More specifically, we show how we have applied cryo-electron tomography (cryo-ET) to visualize the internal morphology of self-assembled poly(ionic liquid) nanoparticles and cryo-EM single particle analysis (SPA) to determine the three-dimensional (3D) structures of artificial protein microtubules.
The photooxygenation of naphthalene to the corresponding endoperoxide (EPO) under various conditions is described. Substantial conversion is only observed at -10 degrees C and after more than two days, indicating that the [4+2] cycloaddition of singlet oxygen to this acene proceeds much more slowly than corresponding reactions of substituted naphthalenes, a rate constant of k = 5.4 +/- 0.3 M(-1)s(-1) was determined by competition kinetics. Another problem is the thermal lability and photochemical cleavage of the naphthalene EPO. We investigated the mechanism of this radical process depending on the light source and sensitizer in comparison to known cyclohexadiene EPO. Thus, bisepoxides and keto epoxides are formed after homolysis of the O-O bond by irradiation with sodium lamps or blue LEDs and subsequent cyclization. This process is accelerated by the sensitizers methylene blue and 9,10-dicyanoanthracene, indicating an electron transfer mechanism. Finally, the cleavage of the peroxidic bond is inhibited with red LEDs, and photooxygenation under such conditions affords 20 % EPO. Thus, we could demonstrate that contrary to literature statements singlet oxygen does indeed react with naphthalene.
Contactless pressure monitoring based on Forster resonance energy transfer between donor/acceptor pairs immobilized within elastomers is demonstrated. The donor/acceptor energy transfer is employed by dispersing terbium(III) tris[(2-hydroxybenzoyl)-2-aminoethyl] amine complex (LLC, donor) and CdSe/ZnS quantum dots (QD655, acceptor) in styrene-ethylene/buthylene-styrene (SEBS) and poly(dimethylsiloxane) (PDMS). The continuous monitoring of QD luminescence showed a reversible intensity change as the pressure signal is alternated between two stable states indicating a pressure sensitivity of 6350 cps kPa(-1). Time-resolved measurements show the pressure impact on the FRET signal due to an increase of decay time (270 ms up to 420 ms) for the donor signal and parallel drop of decay time (170 mu s to 155 mu s) for the acceptor signal as the net pressure applied. The LLC/QD655 sensors enable a contactless readout as well as space resolved monitoring to enable miniaturization towards smaller integrated stretchable opto-electronics. Elastic FRET sensors can potentially lead to developing profitable analysis systems capable to outdo conventional wired electronic systems (inductive, capacitive, ultrasonic and photoelectric sensors) especially for point-of-care diagnostics, biological monitoring required for wearable electronics.
Training OC
(2021)
The course design "Training OC" for training the application of basic concepts consists of four topics: formula language, structure-property relations, reaction mechanisms, and complex tasks that the students should solve with the conceptual knowledge they acquired in the first three topics. A main goal of the course was to enable the students to solve reaction mechanisms. To achieve the goals of the course, several games were specially designed and used. The course was conducted at a German university with ca. 30 students who participated voluntarily. The course was evaluated by several tools: students' products were collected in the course, there were two pre/post-tests, and additionally, interviews on the strategy of designing reaction mechanisms were conducted. The performance of the teacher and the self-assessment of the students were also part of the evaluation. The results of the written exam were compared with the results of the bachelor chemistry major students. The course "Training OC" was rated very well by the students. They were of the opinion that they learned the application of basic concepts taught in this course. This is supported by the results of the evaluation and the written exams. The course concept of Training OC will therefore become a permanent part of the course "Organic Chemistry I" which will be redesigned for the next round in 2020-21.
The protein fraction, important for coffee cup quality, is modified during post-harvest treatment prior to roasting. Proteins may interact with phenolic compounds, which constitute the major metabolites of coffee, where the processing affects these interactions. This allows the hypothesis that the proteins are denatured and modified via enzymatic and/or redox activation steps. The present study was initiated to encompass changes in the protein fraction. The investigations were limited to major storage protein of green coffee beans. Fourteen Coffea arabica samples from various processing methods and countries were used. Different extraction protocols were compared to maintain the status quo of the protein modification. The extracts contained about 4–8 µg of chlorogenic acid derivatives per mg of extracted protein. High-resolution chromatography with multiple reaction monitoring was used to detect lysine modifications in the coffee protein. Marker peptides were allocated for the storage protein of the coffee beans. Among these, the modified peptides K.FFLANGPQQGGK.E and R.LGGK.T of the α-chain and R.ITTVNSQK.I and K.VFDDEVK.Q of β-chain were detected. Results showed a significant increase (p < 0.05) of modified peptides from wet processed green beans as compared to the dry ones. The present study contributes to a better understanding of the influence of the different processing methods on protein quality and its role in the scope of coffee cup quality and aroma. View Full-Text
The numerous applications of rare earth elements (REE) has lead to a growing global demand and to the search for new REE deposits. One promising technique for exploration of these deposits is laser-induced breakdown spectroscopy (LIBS). Among a number of advantages of the technique is the possibility to perform on-site measurements without sample preparation. Since the exploration of a deposit is based on the analysis of various geological compartments of the surrounding area, REE-bearing rock and soil samples were analyzed in this work. The field samples are from three European REE deposits in Sweden and Norway. The focus is on the REE cerium, lanthanum, neodymium and yttrium. Two different approaches of data analysis were used for the evaluation. The first approach is univariate regression (UVR). While this approach was successful for the analysis of synthetic REE samples, the quantitative analysis of field samples from different sites was influenced by matrix effects. Principal component analysis (PCA) can be used to determine the origin of the samples from the three deposits. The second approach is based on multivariate regression methods, in particular interval PLS (iPLS) regression. In comparison to UVR, this method is better suited for the determination of REE contents in heterogeneous field samples. View Full-Text
Label-free optical sensors are attractive candidates, for example, for detecting toxic substances and monitoring biomolecular interactions. Their performance can be pushed by the design of the sensor through clever material choices and integration of components. In this work, two porous materials, namely, porous silicon and plasmonic nanohole arrays, are combined in order to obtain increased sensitivity and dual-mode sensing capabilities. For this purpose, porous silicon monolayers are prepared by electrochemical etching and plasmonic nanohole arrays are obtained using a bottom-up strategy. Hybrid sensors of these two materials are realized by transferring the plasmonic nanohole array on top of the porous silicon. Reflectance spectra of the hybrid sensors are characterized by a fringe pattern resulting from the Fabry–Pérot interference at the porous silicon borders, which is overlaid with a broad dip based on surface plasmon resonance in the plasmonic nanohole array. In addition, the hybrid sensor shows a significant higher reflectance in comparison to the porous silicon monolayer. The sensitivities of the hybrid sensor to refractive index changes are separately determined for both components. A significant increase in sensitivity from 213 ± 12 to 386 ± 5 nm/RIU is determined for the transfer of the plasmonic nanohole array sensors from solid glass substrates to porous silicon monolayers. In contrast, the spectral position of the interference pattern of porous silicon monolayers in different media is not affected by the presence of the plasmonic nanohole array. However, the changes in fringe pattern reflectance of the hybrid sensor are increased 3.7-fold after being covered with plasmonic nanohole arrays and could be used for high-sensitivity sensing. Finally, the capability of the hybrid sensor for simultaneous and independent dual-mode sensing is demonstrated.
A convenient method for the synthesis of γ-spirolactones in only 2–3 steps is described. Birch reduction of inexpensive and commercially available aromatic carboxylic acids in the presence of ethylene oxide affords hydroxy acids, which undergo direct lactonization during work-up. Suitable precursors are methyl-substituted benzoic acids, naphthoic, and dicarboxylic acids. Subsequent hydrogenation proceeds smoothly with Pd/C as catalyst and saturated γ-spirolactones are isolated in excellent yields and stereoselectivities. Thus, up to 3 new stereogenic centers can be constructed as sole diastereomers from achiral benzoic acids. Furthermore, it is possible to control the degree of saturation with Raney nickel or Wilkinson's catalyst to obtain products with 1 double bond. Overall, more than 30 new γ-spirolactones have been synthesized in analytically pure form.