Refine
Year of publication
- 2015 (210) (remove)
Document Type
- Article (152)
- Postprint (31)
- Doctoral Thesis (17)
- Review (3)
- Conference Proceeding (2)
- Preprint (2)
- Monograph/Edited Volume (1)
- Habilitation Thesis (1)
- Other (1)
Is part of the Bibliography
- yes (210) (remove)
Keywords
- biomaterials (4)
- Arenes (3)
- Cross-coupling (3)
- Palladium (3)
- click chemistry (3)
- peptides (3)
- polymers (3)
- self-assembly (3)
- Anisotropy effect (2)
- Confocal microscopy (2)
Institute
- Institut für Chemie (210) (remove)
新型糖氨基酸类化合物的合成研究
(2015)
Sugar amino acids (SAAs) are carbohydrate derivatives bearing both amino and carboxylic acid functional groups. SAAs represent an important class of multifunctional building blocks, which are amenable to serve as glycomimetics or peptidomimetics with well-defined structures and useful properties. Because SAAs exist in nature in many forms with various biological activities, recently, many unnatural SAAs, as the demand for finding new molecules to discover new drugs and new materials, have been designed and synthesized by a number of research groups. In this paper, we have developed a convenient method for the synthesis of novel SAAs gluco-7 and galacto-7 for the first time. The structure of gluco-7 was similar to the natural SAA glucosaminuronic acid that was a component of many typical bacterial cell walls and could be used for the preparation of type D flu vaccine; while galacto-7 was similar to the natural SAA galactosaminuronic acid that was one of bacterial Vi-antigen components of Escherichia coli. Starting from unexpensive and commercially available 3,4,6-tri-O-acetyl-D-glucal and 3,4,6-tri-O-acetyl-D-galactal, two novel SAAs gluco-7 and galacto-7 were achieved in the linear 6 steps with 34% overall yield and 19% overall yield, respectively. The key reactions included radical addition, decarboxylation, iodine generation reaction, azide reaction and reductive amination reaction. The crucial step was the synthesis of the target compound gluco-7 from gluco-6. By using method A, the target compound gluco-7 was obtained in 4 steps with 63% overall yield. To optimize the transformation from gluco-6 to gluco-7, method B was developed to generate gluco-7 by using one-pot reaction successfully with 76% yield only in one step. It proved that method B was superior to method A with shorter steps and higher yields. All the new compounds were characterized by IR, H-1 NMR, C-13 NMR and HRMS data. Study on the synthesis and biological evaluation of linear and cyclic oligomers derived from gluco-7 and galacto-7 are currently in progress.
Co-doping of the MOF 3∞[Zn(2-methylimidazolate-4-amide-5-imidate)] (IFP-1 = Imidazolate Framework Potsdam-1) with luminescent Eu3+ and Tb3+ ions presents an approach to utilize the porosity of the MOF for the intercalation of luminescence centers and for tuning of the chromaticity to the emission of white light of the quality of a three color emitter. Organic based fluorescence processes of the MOF backbone as well as metal based luminescence of the dopants are combined to one homogenous single source emitter while retaining the MOF's porosity. The lanthanide ions Eu3+ and Tb3+ were doped in situ into IFP-1 upon formation of the MOF by intercalation into the micropores of the growing framework without a structure directing effect. Furthermore, the color point is temperature sensitive, so that a cold white light with a higher blue content is observed at 77 K and a warmer white light at room temperature (RT) due to the reduction of the organic emission at higher temperatures. The study further illustrates the dependence of the amount of luminescent ions on porosity and sorption properties of the MOF and proves the intercalation of luminescence centers into the pore system by low-temperature site selective photoluminescence spectroscopy, SEM and EDX. It also covers an investigation of the border of homogenous uptake within the MOF pores and the formation of secondary phases of lanthanide formates on the surface of the MOF. Crossing the border from a homogenous co-doping to a two-phase composite system can be beneficially used to adjust the character and warmth of the white light. This study also describes two-color emitters of the formula Ln@IFP-1a–d (Ln: Eu, Tb) by doping with just one lanthanide Eu3+ or Tb3+.
In cultures of unicellular algae, features of single cells, such as cellular volume and starch content, are thought to be the result of carefully balanced growth and division processes. Single-cell analyses of synchronized photoautotrophic cultures of the unicellular alga Chlamydomonas reinhardtii reveal, however, that the cellular volume and starch content are only weakly correlated. Likewise, other cell parameters, e.g., the chlorophyll content per cell, are only weakly correlated with cell size. We derive the cell size distributions at the beginning of each synchronization cycle considering growth, timing of cell division and daughter cell release, and the uneven division of cell volume. Furthermore, we investigate the link between cell volume growth and starch accumulation. This work presents evidence that, under the experimental conditions of light-dark synchronized cultures, the weak correlation between both cell features is a result of a cumulative process rather than due to asymmetric partition of biomolecules during cell division. This cumulative process necessarily limits cellular similarities within a synchronized cell population.
Optical properties of modified diamondoids have been studied theoretically using vibrationally resolved electronic absorption, emission and resonance Raman spectra. A time-dependent correlation function approach has been used for electronic two-state models, comprising a ground state (g) and a bright, excited state (e), the latter determined from linear-response, time-dependent density functional theory (TD-DFT). The harmonic and Condon approximations were adopted. In most cases origin shifts, frequency alteration and Duschinsky rotation in excited states were considered. For other cases where no excited state geometry optimization and normal mode analysis were possible or desired, a short-time approximation was used. The optical properties and spectra have been computed for (i) a set of recently synthesized sp(2)/sp(3) hybrid species with CQC double-bond connected saturated diamondoid subunits, (ii) functionalized (mostly by thiol or thione groups) diamondoids and (iii) urotropine and other C-substituted diamondoids. The ultimate goal is to tailor optical and electronic features of diamondoids by electronic blending, functionalization and substitution, based on a molecular-level understanding of the ongoing photophysics.
Optical properties of modified diamondoids have been studied theoretically using vibrationally resolved electronic absorption, emission and resonance Raman spectra. A time-dependent correlation function approach has been used for electronic two-state models, comprising a ground state (g) and a bright, excited state (e), the latter determined from linear-response, time-dependent density functional theory (TD-DFT). The harmonic and Condon approximations were adopted. In most cases origin shifts, frequency alteration and Duschinsky rotation in excited states were considered. For other cases where no excited state geometry optimization and normal mode analysis were possible or desired, a short-time approximation was used. The optical properties and spectra have been computed for (i) a set of recently synthesized sp2/sp3 hybrid species with C[double bond, length as m-dash]C double-bond connected saturated diamondoid subunits, (ii) functionalized (mostly by thiol or thione groups) diamondoids and (iii) urotropine and other C-substituted diamondoids. The ultimate goal is to tailor optical and electronic features of diamondoids by electronic blending, functionalization and substitution, based on a molecular-level understanding of the ongoing photophysics.
Optical properties of modified diamondoids have been studied theoretically using vibrationally resolved electronic absorption, emission and resonance Raman spectra. A time-dependent correlation function approach has been used for electronic two-state models, comprising a ground state (g) and a bright, excited state (e), the latter determined from linear-response, time-dependent density functional theory (TD-DFT). The harmonic and Condon approximations were adopted. In most cases origin shifts, frequency alteration and Duschinsky rotation in excited states were considered. For other cases where no excited state geometry optimization and normal mode analysis were possible or desired, a short-time approximation was used. The optical properties and spectra have been computed for (i) a set of recently synthesized sp2/sp3 hybrid species with C[double bond, length as m-dash]C double-bond connected saturated diamondoid subunits, (ii) functionalized (mostly by thiol or thione groups) diamondoids and (iii) urotropine and other C-substituted diamondoids. The ultimate goal is to tailor optical and electronic features of diamondoids by electronic blending, functionalization and substitution, based on a molecular-level understanding of the ongoing photophysics.
We have characterized ultraviolet (UV) photon-induced DNA strand break processes by determination of absolute cross sections for photoabsorption and for sequence-specific DNA single strand breakage induced by photons in an energy range from 6.50 to 8.94 eV. These represent the lowest-energy photons able to induce DNA strand breaks. Oligonudeotide targets are immobilized on a UV transparent substrate in controlled quantities through attachment to DNA origami templates. Photon-induced dissociation of single DNA strands is visualized and quantified using atomic force microscopy. The obtained quantum yields for strand breakage vary between 0.06 and 0.5, indicating highly efficient DNA strand breakage by UV photons, which is clearly dependent on the photon energy. Above the ionization threshold strand breakage becomes clearly the dominant form of DNA radiation damage, which is then also dependent on the nucleotide sequence.
Sixteen new ionic liquids (ILs) with tetraethylammonium, 1-butyl-3-methylimidazolium, 3-methyl-1-octylimidazolium and tetrabutylphosphonium cations paired with 2-substituted 4,5-dicyanoimidazolate anions (substituent at C2 = methyl, trifluoromethyl, pentafluoroethyl, N,N′-dimethyl amino and nitro) have been synthesized and characterized by using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA). The effects of cation and anion type and structure of the resulting ILs, including several room temperature ionic liquids (RTILs), are reflected in the crystallization, melting points and thermal decomposition of the ILs. ILs exhibited large liquid and crystallization ranges and formed glasses on cooling with glass transition temperatures in the range of −22 to −71 °C. We selected one of the newly designed ILs due to its bigger size, compared to the common conventional IL anion and high electron-withdrawing nitrile group leads to an overall stabilization anion that may stabilize the metal nanoparticles. Stable and better separated iron and silver nanoparticles are obtained by the decomposition of corresponding Fe2(CO)9 and AgPF6, respectively, under N2-atmosphere in newly designed nitrile functionalized 4,5-dicyanoimidazolate anion based IL. Very small and uniform size for Fe-nanoparticles of about 1.8 ± 0.6 nm were achieved without any additional stabilizers or capping molecules. Comparatively bigger size of Ag-nanoparticles was obtained through the reduction of AgPF6 by hydrogen gas. Additionally, the AgPF6 precursor was decomposed under microwave irradiation (MWI), fabricating nut-in-shell-like, that is, core-separated-from-shell Ag-nano-structures.
By overcoming the diffraction limit in light microscopy, super-resolution techniques, such as stimulated emission depletion (STED) microscopy, are experiencing an increasing impact on life sciences. High costs and technically demanding setups, however, may still hinder a wider distribution of this innovation in biomedical research laboratories. As far-field microscopy is the most widely employed microscopy modality in the life sciences, upgrading already existing systems seems to be an attractive option for achieving diffraction-unlimited fluorescence microscopy in a cost-effective manner. Here, we demonstrate the successful upgrade of a commercial time-resolved confocal fluorescence microscope to an easy-to-align STED microscope in the single-beam path layout, previously proposed as "easy-STED", achieving lateral resolution <lambda/10 corresponding to a five-fold improvement over a confocal modality. For this purpose, both the excitation and depletion laser beams pass through a commercially available segmented phase plate that creates the STED-doughnut light distribution in the focal plane, while leaving the excitation beam unaltered when implemented into the joint beam path. Diffraction-unlimited imaging of 20 nm-sized fluorescent beads as reference were achieved with the wavelength combination of 635 nm excitation and 766 nm depletion. To evaluate the STED performance in biological systems, we compared the popular phalloidin-coupled fluorescent dyes Atto647N and Abberior STAR635 by labeling F-actin filaments in vitro as well as through immunofluorescence recordings of microtubules in a complex epithelial tissue. Here, we applied a recently proposed deconvolution approach and showed that images obtained from time-gated pulsed STED microscopy may benefit concerning the signal-to-background ratio, from the joint deconvolution of sub-images with different spatial information which were extracted from offline time gating.
Upconversion NaYF4:Yb:Er nanoparticles co-doped with Gd3+ and Nd3+ for thermometry on the nanoscale
(2015)
In the present work, the upconversion luminescence properties of oleic acid capped NaYF4:Gd3+:Yb3+:Er3+ upconversion nanoparticles (UCNP) with pure β crystal phase and Nd3+ ions as an additional sensitizer were studied in the temperature range of 288 K < T < 328 K. The results of this study showed that the complex interplay of different mechanisms and effects, causing the special temperature behavior of the UCNP can be developed into thermometry on the nanoscale, e.g. to be applied in biological systems on a cellular level. The performance was improved by the use of Nd3+ as an additional dopant utilizing the cascade sensitization mechanism in tri-doped UCNP.
Upconversion NaYF4:Yb:Er nanoparticles co-doped with Gd3+ and Nd3+ for thermometry on the nanoscale
(2015)
In the present work, the upconversion luminescence properties of oleic acid capped NaYF4:Gd3+:Yb3+:Er3+ upconversion nanoparticles (UCNP) with pure β crystal phase and Nd3+ ions as an additional sensitizer were studied in the temperature range of 288 K < T < 328 K. The results of this study showed that the complex interplay of different mechanisms and effects, causing the special temperature behavior of the UCNP can be developed into thermometry on the nanoscale, e.g. to be applied in biological systems on a cellular level. The performance was improved by the use of Nd3+ as an additional dopant utilizing the cascade sensitization mechanism in tri-doped UCNP.
Upconversion NaYF4:Yb:Er nanoparticles co-doped with Gd3+ and Nd3+ for thermometry on the nanoscale
(2015)
In the present work, the upconversion luminescence properties of oleic acid capped NaYF4:Gd3+:Yb3+:Er3+ upconversion nanoparticles (UCNP) with pure β crystal phase and Nd3+ ions as an additional sensitizer were studied in the temperature range of 288 K < T < 328 K. The results of this study showed that the complex interplay of different mechanisms and effects, causing the special temperature behavior of the UCNP can be developed into thermometry on the nanoscale, e.g. to be applied in biological systems on a cellular level. The performance was improved by the use of Nd3+ as an additional dopant utilizing the cascade sensitization mechanism in tri-doped UCNP.
Upconversion NaYF4:Yb:Er nanoparticles co-doped with Gd3+ and Nd3+ for thermometry on the nanoscale
(2015)
In the present work, the upconversion luminescence properties of oleic acid capped NaYF4:Gd3+:Yb3+:Er3+ upconversion nanoparticles (UCNP) with pure beta crystal phase and Nd3+ ions as an additional sensitizer were studied in the temperature range of 288 K < T < 328 K. The results of this study showed that the complex interplay of different mechanisms and effects, causing the special temperature behavior of the UCNP can be developed into thermometry on the nanoscale, e.g. to be applied in biological systems on a cellular level. The performance was improved by the use of Nd3+ as an additional dopant utilizing the cascade sensitization mechanism in tri-doped UCNP.
The temperature-dependent upconversion luminescence of NaYF4:Yb:Er nanoparticles (UCNP) containing different contents of Gd3+ as additional dopant was characterized. The UCNP were synthesized in a hydrothermal synthesis and stabilized with citrate in order to transfer them to the water phase. Basic characterization was carried out using TEM and DLS to determine the average size of the UCNP. The XRD technique was used to investigate the crystal lattice of the UCNP. It was found that due to the presence of Gd3+, an alteration of the lattice phase from a to beta was induced which was also reflected in the observed upconversion luminescence properties of the UCNP. A detailed analysis of the upconversion luminescence spectraespecially at ultralow temperaturesrevealed the different effects of phonon coupling between the host lattice and the sensitizer (Yb3+) as well as the activator (Er3+). Furthermore, the upconversion luminescence intensity reached a maximum between 15 and 250 K depending on Gd3+ content. In comparison to the very complex temperature behavior of the upconversion luminescence in the temperature range <273 K, the luminescence intensity ratio of H-2(11/2)-> I-4(15/2) to S-4(3/2)-> I-4(15/2) (R = G1/G2) in a higher temperature range can be described by an Arrhenius-type equation.
Hybrid materials are at the forefront of modern research and technology; hence a large number of publications on hybrid materials has already appeared in the scientific literature. This essay focuses on the specifics and peculiarities of hybrid materials based on two-dimensional (2D) building blocks and confinements, for two reasons: (1) 2D materials have a very broad field of application, but they also illustrate many of the scientific challenges the community faces, both on a fundamental and an application level; (2) all authors of this essay are involved in research on 2D materials, but their perspective and vision of how the field will develop in the future and how it is possible to benefit from these new developments are rooted in very different scientific subfields. The current article will thus present a personal, yet quite broad, account of how hybrid materials, specifically 2D hybrid materials, will provide means to aid modern societies in fields as different as healthcare and energy.
Cadmium(II) based 2D coordination polymer [Cd(L1)(2)(DMF)(2)] (1) (L1 = 4,5-dicyano-2-methylimidazolate, DMF = N,N'-dimethylformamide) and 2D cobalt(II)-imidazolate framework [Co(L3)(4)] (2) (L3 = 4,5-diamide-2-ethoxyimidazolate) were synthesized under solvothermal reaction conditions. The materials were characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, powder X-ray diffraction measurement (PXRD) and single-crystal X-ray diffraction. Compound 1 has hexacoordinate Cd-II ions and forms a zigzag chain-like coordination polymer structure, whereas compound 2 exhibits a 2D square grid type structure. The thermal stability analysis reveals that 2 showed an exceptional thermal stability up to 360 degrees C. Also, 2 maintained its fully crystalline integrity in boiling water as confirmed by PXRD. The solid state luminescent property of 1 was not observed at room temperature. Compound 2 showed an independent high spin central Co-II atom.
Langmuir polymers films (LPFs) frequently form non-equilibrium states which are manifested in a decay of the surface pressure with time when the system is allowed to relax. Monitoring and manipulating the temporal evolution of these relaxations experimentally helps to shed light on the associated molecular reorganization processes. We present a systematic study based on different compression protocols and show how these reorganization processes impact the morphology of LPFs of poly(gamma-benzyl-L-glutamate) (PBLG); visualized by means of atomic force microscopy. Upon continuous compression, a fibrillar morphology was formed with a surface decorated by squeezed-out islands. By contrast, stepwise compression promoted the formation of a fibrillar network with a bimodal distribution of fibril diameters, caused by merging of fibrils. Finally, isobaric compression induced in-plane compaction of the monolayer. We correlate these morphological observations with the kinetics of the corresponding relaxations, described best by a sum of two exponential functions with different time scales representing two molecular processes. We discuss the observed kinetics and the resulting morphologies in the context of nucleation and growth, characteristic for first-order phase transitions. Our results demonstrate that the preparation conditions of LPFs have tremendous impact on ordering of the molecules and hence various macroscopic properties of such films.
This article presents a simple and facile method to fabricate thermoresponsive polymer-grafted silica particles by direct surface-initiated photopolymerization of N-isopropylacrylamide (NIPAM). This method is based on silica particles bearing thiol functionalities, which are transformed into thiyl radicals by irradiation with UV light to initiate the polymerization of NIPAM in aqueous media at room temperature. The photopolymerization of NIPAM could be applied to smaller thiol-functionalized particles (approximate to 48 nm) as well as to larger particles (approximate to 692 nm). Hollow poly(NIPAM) capsules could be formed after etching away the silica cores from the composite particles. It is possible to produce tailor-made composite particles or capsules for particular applications by extending this approach to other vinyl monomers. (c) 2015 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 2015, 53, 1260-1267
As polypeptoids become increasingly popular, they present a more soluble and processable alternative to natural and synthetic polypeptides; the breadth of their potential functionality slowly comes into focus. This report analyzes the ability of an alkyne-functionalized polypeptoid, poly(N-propargyl glycine), to crosslink upon heating. The crosslinking process is analyzed by thermal analysis (differential scanning calorimetry and thermogravimetric analysis), Fourier-transform infrared, electron paramagnetic resonance, and solid-state NMR spectroscopy. While a precise mechanism cannot be confidently assigned, it is clear that the reaction proceeds by a radical mechanism that exclusively involves the alkyne functionality, which, upon crosslinking, yields alkene and aromatic products.
X-ray free-electron lasers (XFELs) may allow us to employ the single-particle imaging (SPI) method to determine the structure of macromolecules that do not form stable crystals. Ultrashort pulses of 10 fs and less allow us to outrun complete disintegration by Coulomb explosion and minimize radiation damage due to nuclear motion, but electronic damage is still present. The major contribution to the electronic damage comes from the plasma generated in the sample that is strongly dependent on the amount of Auger ionization. Since the Auger process has a characteristic time scale on the order of femtoseconds, one may expect that its contribution will be significantly reduced for attosecond pulses. Here we study the effect of electronic damage on the SPI at pulse durations from 0.1 to 10 fs and in a large range of XFEL fluences to determine optimal conditions for imaging of biological samples. We analyzed the contribution of different electronic excitation processes and found that at fluences higher than 1013-1015 photons/mu m(2) (depending on the photon energy and pulse duration) the diffracted signal saturates and does not increase further. A significant gain in the signal is obtained by reducing the pulse duration from 10 to 1 fs. Pulses below a duration of 1 fs do not give a significant gain in the scattering signal in comparison with 1-fs pulses. We also study the limits imposed on SPI by Compton scattering.
The Photoinduced E -> Z Isomerization of Bisazobenzenes: A Surface Hopping Molecular Dynamics Study
(2015)
The photoinduced E -> Z isomerization of azobenzene is a prototypical example of molecular switching. On the way toward rigid molecular rods such as those for opto-mechanical applications, multiazobenzene structures have been suggested in which several switching units are linked together within the same molecule (Bleger et al., J. Phys. Chem. B 2011, 115, 9930-9940). Large differences in the switching efficiency of multiazobenzenes have been observed, depending on whether the switching units are electronically decoupled or not. In this paper we study, on a time-resolved molecular level, the E -> Z isomerization of the simplest multiazobenzene, bisazobenzene (BAB). Two isomers (ortho- and para-BAB), differing only in the connectivity of two azo groups on a shared phenyl ring will be considered.To do so, nonadiabatic semiclassical dynamics after photo-excitation of the isomers are studied by employing an "on-the-fly", fewest switches surface hopping approach. States and couplings are calculated by Configuration Interaction (CI) based on a semiempirical (AM1) Hamiltonian (Persico and co-workers, Chem. Eur. J. 2004, 10, 2327-2341). In the case of para-BAB, computed quantum yields for photoswitching are drastically reduced compared to pristine azobenzene, due to electronic coupling of both switching units. A reason for this (apart from altered absorption spectra and reduced photochromicity) is the drastically reduced lifetimes of electronically excited states which are transiently populated. In contrast for meta-connected species, electronic subsystems are largely decoupled, and computed quantum yields are slightly higher than that for pristine azobenzene because of new isomerization channels. In this case we can also distinguish between single- and double-switch events and we find a cooperative effect: The isomerization of a single azo group is facilitated if the other azo group is already in the Z-configuration.
Polyether ether ketone (PEEK) as a high-performance, thermoplastic implant material entered the field of medical applications due to its structural function and commercial availability. In bone tissue engineering, the combination of mesenchymal stem cells (MSCs) with PEEK implants may accelerate the bone formation and promote the osseointegration between the implant and the adjacent bone tissue. In this concept the question how PEEK influences the behaviour and functions of MSCs is of great interest. Here the cellular response of human adipose-derived MSCs to PEEK was evaluated and compared to tissue culture plate (TCP) as the reference material. Viability and morphology of cells were not altered when cultured on the PEEK film. The cells on PEEK presented a high proliferation activity in spite of a relatively lower initial cell adhesion rate. There was no significant difference on cell apoptosis and senescence between the cells on PEEK and TCP. The inflammatory cytokines and VEGF secreted by the cells on these two surfaces were at similar levels. The cells on PEEK showed up-regulated BMP2 and down-regulated BMP4 and BMP6 gene expression, whereas no conspicuous differences were observed in the committed osteoblast markers (BGLAP, COL1A1 and Runx2). With osteoinduction the cells on PEEK and TCP exhibited a similar osteogenic differentiation potential. Our results demonstrate the biofunctionality of PEEK for human MSC cultivation and differentiation. Its clinical benefits in bone tissue engineering may be achieved by combining MSCs with PEEK implants. These data may also provide useful information for further modification of PEEK with chemical or physical methods to regulate the cellular processes of MSCs and to consequently improve the efficacy of MSC-PEEK based therapies.
Exposure to organic mercury compounds promotes primarily neurological effects. Although methylmercury is recognized as a potent neurotoxicant, its transfer into the central nervous system (CNS) is not fully evaluated. While methylmercury and thiomersal pass the blood–brain barrier, limited data are available regarding the second brain regulating interface, the blood–cerebrospinal fluid (CSF) barrier. This novel study was designed to investigate the effects of organic as well as inorganic mercury compounds on, and their transfer across, a porcine in vitro model of the blood–CSF barrier for the first time. The barrier system is significantly more sensitive towards organic Hg compounds as compared to inorganic compounds regarding the endpoints cytotoxicity and barrier integrity. Whereas there are low transfer rates from the blood side to the CSF side, our results strongly indicate an active transfer of the organic mercury compounds out of the CSF. These results are the first to demonstrate an efflux of organic mercury compounds regarding the CNS and provide a completely new approach in the understanding of mercury compounds specific transport.
Exposure to organic mercury compounds promotes primarily neurological effects. Although methylmercury is recognized as a potent neurotoxicant, its transfer into the central nervous system (CNS) is not fully evaluated. While methylmercury and thiomersal pass the blood–brain barrier, limited data are available regarding the second brain regulating interface, the blood–cerebrospinal fluid (CSF) barrier. This novel study was designed to investigate the effects of organic as well as inorganic mercury compounds on, and their transfer across, a porcine in vitro model of the blood–CSF barrier for the first time. The barrier system is significantly more sensitive towards organic Hg compounds as compared to inorganic compounds regarding the endpoints cytotoxicity and barrier integrity. Whereas there are low transfer rates from the blood side to the CSF side, our results strongly indicate an active transfer of the organic mercury compounds out of the CSF. These results are the first to demonstrate an efflux of organic mercury compounds regarding the CNS and provide a completely new approach in the understanding of mercury compounds specific transport.
Tetrahydrothiophene and Tetrahydrofuran, Computational and X-ray Studies in the Crystalline Phase
(2015)
Calculations at various levels of theory with different methods and respective evaluations confirm that the twist conformation (C-2) is preferred for tetrahydrothiophene (THT) in the gas phase. In the crystalline phase, achieved by a laser assisted crystallization device, THT has C-1 symmetry (slightly distorted C-2 symmetry) in the chiral space group P2(1)2(1)2(1). This is obviously a packing effect caused by the nonsymmetrical arrangement of neighboring molecules. The distortion from C-2 symmetry costs very little energy as confirmed by computational methods in the gas phase. Only one enantiomer of the chiral THT is found in the cell which requires spontaneous crystallization, which results in a racemic mixture of crystals, or a racemization occurs prior to/during nucleation or in the embryonic state. The racemization happens by a mechanism that can be described as a partial pseudo rotation within a five-membered mono-heterocycle with a C-2-C-S-C-2' transition (C-2 and C-2' are enantiomers) maintaining the heteroatom residing within the symmetry elements. While THT has the molecular symmetry of the gas phase almost also in the crystalline phase, THF has an envelope conformation (CS). This was also established by calculations at various levels of theory which agrees well with the previously experimentally found conformation by electron diffraction. However, in the X-ray crystal structure, previously determined by Luger & Buschmann, THF has C-2 symmetry in the centrosymmetric space group C2/c with the oxygen atom situated on the crystallographic C-2 polar axis, requesting a racemic crystal for the twisted conformers of the enantiomers. No solid-state phase transitions were detected within the experimental ranges for THT and THF. Following the stabilization by molecular clustering, and ending at the crystal lattice, we stepwise increased the number of molecules by calculation of the respective monomers, dimers, trimers, and tetramers for THF and THT. The starting point was taken from the arrangements as found in the respective crystal structures. Both conformational enantiomers are equal in energy. In such cases, a crystal may contain either a racemate of conformers or one of the conformational enantiomers only. The first case is observed in THF, the latter one in THT. It is quite likely that the selection of one enantiomeric conformer of THT from an equilibrium of conformers at the early stage of nucleation (embryonic stage) is responsible for the spontaneous crystallization. In order to check if THF could form a polymorph with the molecular packing of THT and vice versa, we first calculated THF and THT in their respective crystal lattices as determined by X-ray diffraction. Exchanging the compounds in the THT and THF crystal lattices (i.e., replacing O against S and vice versa) results in significantly worse lattice energies indicating that such a polymorph is not a probable option.
The protein corona, which forms on the nanoparticle's surface in most biological media, determines the nanoparticle's physicochemical characteristics. The formation of the protein corona has a significant impact on the biodistribution and clearance of nanoparticles in vivo. Therefore, the ability to influence the formation of the protein corona is essential to most biomedical applications, including drug delivery and imaging. In this study, we investigate the protein adsorption on nanoparticles with a hydrodynamic radius of 30 nm and a coating of thermoresponsive poly(2-isopropyl-2-oxazoline) in serum. Using multiangle dynamic light scattering (DLS) we demonstrate that heating of the nanoparticles above their phase separation temperature induces the formation of agglomerates, with a hydrodynamic radius of 1 mu m. In serum, noticeably stronger agglomeration occurs at lower temperatures compared to serum-free conditions. Cryogenic transmission electron microscopy (cryo-TEM) revealed a high packing density of agglomerates when serum was not present. In contrast, in the presence of serum, agglomerated nanoparticles were loosely packed, indicating that proteins are intercalated between them. Moreover, an increase in protein content is observed upon heating, confirming that protein adsorption is induced by the alteration of the surface during phase separation. After cooling and switching the surface back, most of the agglomerates were dissolved and the main fraction returned to the original size of approximately 30 nm as shown by asymmetrical flow-field flow fractionation (AF-FFF) and DLS. Furthermore, the amounts of adsorbed proteins are similar before and after heating the nanoparticles to above their phase-separation temperature. Overall, our results demonstrate that the thermoresponsivity of the polymer coating enables turning the corona formation on nanoparticles on and off in situ. As the local heating of body areas can be easily done in vivo, the thermoresponsive coating could potentially be used to induce the agglomeration of nanopartides and proteins and the accumulation of nanoparticles in a targeted body region.
Tandem Claisen Rearrangement/6-endo Cyclization Approach to Allylated and Prenylated Chromones
(2015)
Allyl, dimethylallyl and prenyl ethers derived from o-acyl-phenols reacted upon microwave irradiation to form C-allylated or -prenylated chromone derivatives, depending on the substitution pattern of the arene and the allyl substituent. The reaction proceeds through a tandem Claisen rearrangement and 6-endo-trig or 6-endo-dig cyclization sequence. For prenyl ethers, the tandem sequence can be extended by a Cope rearrangement to furnish 6-prenylchromones. The method is potentially useful for the synthesis of natural products and drugs.
Magnaldehydes B and E along with their 4'-methylated derivatives are naturally occurring 2,4'-biphenols that have been isolated from the Magnoliaceae. Herein, these natural products have been synthesized from a common intermediate, which was obtained by a microwave-promoted, hetero-geneously catalyzed, and protecting-group-free Suzuki-Miyaura coupling reaction in an aqueous medium. These reaction conditions were also successfully applied to a one-step synthesis of the slime mold metabolite dictyobiphenyl B.
Synthesis and Optical Properties of alpha,beta-Unsaturated Ketones Bearing a Benzofuran Moiety
(2015)
Five pi-expanded alpha,beta-unsaturated ketones have been prepared from a strongly electron-rich benzofuran derivative via Knoevenagel reaction and aldol condensation. The incorporation of two 6-didodecylaminobenzofuran-2-yl groups at the periphery of D-pi-A and D-pi-A-pi-D molecules resulted in dyes with excellent solubility in the majority of organic solvents. In contrast to the majority of alpha,beta-unsaturated ketones, these dyes emit relatively strongly in the red region with a fluorescence quantum yield up to 40%. They also display strong solvatofluorochromism with emission shifting from 570 nm in toluene to 670 nm in CHCl3. Depending on the chemical structure, they two-photon cross-sections (sigma(2)) are up to 1700 GM (1 GM=10(50) cm(4)s photon(-1)).
3-Methyl-3-silatetrahydropyran 1 was synthesized and its molecular structure and conformational behavior was studied by gas-phase electron diffraction (GED), FTIR, low temperature H-1 and C-13 NMR spectroscopy, and by theoretical calculations (DFT, MP2). Two conformers; 1-ax and 1-eq; were located on the potential energy Surface. In the gas phase; a slight predominance of the axial conformer was determined, with the ratio 1-ax:1-eq = 54(9):46(9) (from GED) or 53:47 or 61;39 (from IR). In solution, LT NMR spectroscopy at 103 K gives the ratio 1-ax:1-eq = 35:65 (-Delta G(103)degrees = 0.13 kcal/mol). Simulation of solvent effects using the PCM continuum model or by calculation of the corresponding solvent-solute complexes allowed us to rationalize the experimentally observed opposite conformational predominance of the conformers of 3-methyl-3-silatettahydropyran in the gas phase and in solution. Comparative analysis of the effect of heteroatom in 1-hetero-3-methyl-3-silacyclohexanes on the structure, stereoelectronic interactions, and relative energies of the conformers is done.
Swelling of Polyelectrolyte Multilayers: The Relation Between, Surface and Bulk Characteristics
(2015)
The odd even effect, i.e., the influence of the outermost layer of polyelectrolyte multilayers (PEMs) on their swelling behavior, is investigated. For that purpose poly(styrene sodium sulfonate) (PSS)/poly(diallyl-dimethylammonium chloride) (PDADMAC) polyelectrolyte multilayers are studied in air with 1% relative humidity (RH), 30% RH, 95% RH, and in liquid water by ellipsometry, atomic force microscopy (AFM), and X-ray reflectometry (XRR). Since the total amount of water uptake in swollen PEMs is divided into two fractions, the void water and the swelling water, a correct evaluation of the odd even effect is only possible if both fractions are examined separately. In order to allow measuring samples over a larger thickness regime the investigation of a larger amount of samples is required. Therefore, the concept of separating void water from swelling water using neutron reflectometry is for the first time transferred to ellipsometry. The subsequent analysis of swelling water, void water, and roughness revealed the existence of two types of odd even effects: an odd even effect which addresses only the surface of the PEM (surface-odd even effect) and an odd even effect which addresses also the bulk of the PEM (bulk-odd even effect). The appearance of both effects is dependent on the environment; the surface-odd even effect is only detectable in humid air while the bulk-odd even effect is only detectable in liquid water. The bulk-odd even effect is related to the osmotic pressure between the PEM and the surrounding water. A correlation between the amount of void water and both odd even effects is not found. The amount of void water is independent of the terminated layer and the thickness of PEMs.
In recent years, core/shell nanohybrids containing a nanoparticle core and a distinct surrounding shell of polymer brushes have received extensive attention in nanoelectronics, nanophotonics, catalysis, nanopatterning, drug delivery, biosensing, and many others. From the large variety of existing polymerization methods on the one hand and strategies for grafting onto nanoparticle surfaces on the other hand, the combination of grafting-from with controlled radical polymerization (CRP) techniques has turned out to be the best suited for synthesizing these well-defined core/shell nanohybrids and is known as surface-initiated CRP. Most common among these are surface-initiated atom transfer radical polymerization (ATRP), surface-initiated reversible addition-fragmentation chain transfer (RAFT) polymerization, and surface-initiated nitroxide-mediated polymerization (NMP). This review highlights the state of the art of growing polymers from nanoparticles using surface-initiated CRP techniques. We focus on mechanistic aspects, synthetic procedures, and the formation of complex architectures as well as novel properties. From the vast number of examples of nanoparticle/polymer hybrids formed by surface-initiated CRP techniques, we present nanohybrid formation from the particularly important and most studied silica nanoparticles, gold nanocrystals, and proteins which can be regarded as bionanoparticles.
In situ X-ray diffraction studies of structural evolution of colloidal crystal films formed by polystyrene spherical particles upon incremental heating are reported. The Bragg peak parameters, such as peak position, integrated intensity, and radial and azimuthal widths were analyzed as a function of temperature. A quantitative study of colloidal crystal lattice distortions and mosaic spread as a function of temperature was carried out using Williamson-Hall plots based on mosaic block model. The temperature dependence of the diameter of polystyrene particles was obtained from the analysis of Bragg peaks, and the form factor contribution extracted from the diffraction patterns. Four stages of structural evolution in a colloidal crystal upon heating were identified. Based on this analysis, a model of the heating and melting process in the colloidal crystal film is suggested.
Molecular structure and conformational behavior of 3-isopropoxy-3-methyl-3-oxasilinane is studied by low temperature C-13 NMR spectroscopy and theoretical calculations (DFT, MP2). Two conformers, 1-ROax and 1-ROeq, were found experimentally and located on the potential energy surface. LT C-13 NMR spectroscopy gives almost equal population of the two conformers at 98 K with Delta G(98K)degrees=0.02 kcal/mol in favor of 1-ROax and Delta G(98K)(#)=4.5 kcal/mol. The corresponding DFT calculated values (Delta G(98K)degrees=0.03 kcal/mol, Delta G(98K)(#)=5.1 kcal/mol) are in excellent agreement with the experiment. Detailed DFT and MP2 calculations of the solvent effect on the conformational equilibrium were performed and highlighted the leveling out of the two conformers when transferred from gas to solution. (C) 2015 Published by Elsevier Ltd.
Spatio-temporal control of cellular uptake achieved by photoswitchable cell-penetrating peptides
(2015)
The selective uptake of compounds into specific cells of interest is a major objective in cell biology and drug delivery. By incorporation of a novel, thermostable azobenzene moiety we generated peptides that can be switched optically between an inactive state and an active, cell-penetrating state with excellent spatio-temporal control.
Spatio-temporal control of cellular uptake achieved by photoswitchable cell-penetrating peptides
(2015)
The selective uptake of compounds into specific cells of interest is a major objective in cell biology and drug delivery. By incorporation of a novel, thermostable azobenzene moiety we generated peptides that can be switched optically between an inactive state and an active, cell-penetrating state with excellent spatio-temporal control.
A series of three dialkyl phosphate resins with a Merrifield resin support was used to extract platinum from acidic media. In column operations total capacities of 85-130 mg/g were gained. The presence of palladium and rhodium results in the order: Pt(IV) > Pd(II) >> Rh(III). From a leach liquor gained from spent automotive catalysts metals forming anionic chloro complexes are co-extracted only to a small extent. However, in order to separate and enrich platinum a selective back-extraction can be done with a sodium thiocyanate solution. A second elution step with acidic thiourea leads to a mixed solution of palladium and rhodium.
The simulation of the optical properties of supramolecular aggregates requires the development of methods, which are able to treat a large number of coupled chromophores interacting with the environment. Since it is currently not possible to treat large systems by quantum chemistry, the Frenkel exciton model is a valuable alternative. In this work we show how the Frenkel exciton model can be extended in order to explain the excitonic spectra of a specific double-walled tubular dye aggregate explicitly taking into account dispersive energy shifts of ground and excited states due to van der Waals interaction with all surrounding molecules. The experimentally observed splitting is well explained by the site-dependent energy shift of molecules placed at the inner or outer side of the double-walled tube, respectively. Therefore we can conclude that inclusion of the site-dependent dispersive effect in the theoretical description of optical properties of nanoscaled dye aggregates is mandatory.
The simulation of the optical properties of supramolecular aggregates requires the development of methods, which are able to treat a large number of coupled chromophores interacting with the environment. Since it is currently not possible to treat large systems by quantum chemistry, the Frenkel exciton model is a valuable alternative. In this work we show how the Frenkel exciton model can be extended in order to explain the excitonic spectra of a specific double-walled tubular dye aggregate explicitly taking into account dispersive energy shifts of ground and excited states due to van der Waals interaction with all surrounding molecules. The experimentally observed splitting is well explained by the site-dependent energy shift of molecules placed at the inner or outer side of the double-walled tube, respectively. Therefore we can conclude that inclusion of the site-dependent dispersive effect in the theoretical description of optical properties of nanoscaled dye aggregates is mandatory.
The simulation of the optical properties of supramolecular aggregates requires the development of methods, which are able to treat a large number of coupled chromophores interacting with the environment. Since it is currently not possible to treat large systems by quantum chemistry, the Frenkel exciton model is a valuable alternative. In this work we show how the Frenkel exciton model can be extended in order to explain the excitonic spectra of a specific double-walled tubular dye aggregate explicitly taking into account dispersive energy shifts of ground and excited states due to van der Waals interaction with all surrounding molecules. The experimentally observed splitting is well explained by the site-dependent energy shift of molecules placed at the inner or outer side of the double-walled tube, respectively. Therefore we can conclude that inclusion of the site-dependent dispersive effect in the theoretical description of optical properties of nanoscaled dye aggregates is mandatory.
In living cells, there are always a plethora of processes taking place at the same time. Their precise regulation is the basis of cellular functions, since small failures can lead to severe dysfunctions. For a comprehensive understanding of intracellular homeostasis, simultaneous multiparameter detection is a versatile tool for revealing the spatial and temporal interactions of intracellular parameters. Here, a recently developed time-correlated single-photon counting (TCSPC) board was evaluated for simultaneous fluorescence and phosphorescence lifetime imaging microscopy (FLIM/PLIM). Therefore, the metabolic activity in insect salivary glands was investigated by recording ns-decaying intrinsic cellular fluorescence, mainly related to oxidized flavin adenine dinucleotide (FAD) and the mu s-decaying phosphorescence of the oxygen-sensitive ruthenium-complex Kr341. Due to dopamine stimulation, the metabolic activity of salivary glands increased, causing a higher pericellular oxygen consumption and a resulting increase in Kr341 phosphorescence decay time. Furthermore, FAD fluorescence decay time decreased, presumably due to protein binding, thus inducing a quenching of FAD fluorescence decay time. Through application of the metabolic drugs antimycin and FCCP, the recorded signals could be assigned to a mitochondrial origin. The dopamine-induced changes could be observed in sequential FLIM and PLIM recordings, as well as in simultaneous FLIM/PLIM recordings using an intermediate TCSPC timing resolution.
In living cells, there are always a plethora of processes taking place at the same time. Their precise regulation is the basis of cellular functions, since small failures can lead to severe dysfunctions. For a comprehensive understanding of intracellular homeostasis, simultaneous multiparameter detection is a versatile tool for revealing the spatial and temporal interactions of intracellular parameters. Here, a recently developed time-correlated single-photon counting (TCSPC) board was evaluated for simultaneous fluorescence and phosphorescence lifetime imaging microscopy (FLIM/PLIM). Therefore, the metabolic activity in insect salivary glands was investigated by recording ns-decaying intrinsic cellular fluorescence, mainly related to oxidized flavin adenine dinucleotide (FAD) and the μs-decaying phosphorescence of the oxygen-sensitive ruthenium-complex Kr341. Due to dopamine stimulation, the metabolic activity of salivary glands increased, causing a higher pericellular oxygen consumption and a resulting increase in Kr341 phosphorescence decay time. Furthermore, FAD fluorescence decay time decreased, presumably due to protein binding, thus inducing a quenching of FAD fluorescence decay time. Through application of the metabolic drugs antimycin and FCCP, the recorded signals could be assigned to a mitochondrial origin. The dopamine-induced changes could be observed in sequential FLIM and PLIM recordings, as well as in simultaneous FLIM/PLIM recordings using an intermediate TCSPC timing resolution.
In living cells, there are always a plethora of processes taking place at the same time. Their precise regulation is the basis of cellular functions, since small failures can lead to severe dysfunctions. For a comprehensive understanding of intracellular homeostasis, simultaneous multiparameter detection is a versatile tool for revealing the spatial and temporal interactions of intracellular parameters. Here, a recently developed time-correlated single-photon counting (TCSPC) board was evaluated for simultaneous fluorescence and phosphorescence lifetime imaging microscopy (FLIM/PLIM). Therefore, the metabolic activity in insect salivary glands was investigated by recording ns-decaying intrinsic cellular fluorescence, mainly related to oxidized flavin adenine dinucleotide (FAD) and the μs-decaying phosphorescence of the oxygen-sensitive ruthenium-complex Kr341. Due to dopamine stimulation, the metabolic activity of salivary glands increased, causing a higher pericellular oxygen consumption and a resulting increase in Kr341 phosphorescence decay time. Furthermore, FAD fluorescence decay time decreased, presumably due to protein binding, thus inducing a quenching of FAD fluorescence decay time. Through application of the metabolic drugs antimycin and FCCP, the recorded signals could be assigned to a mitochondrial origin. The dopamine-induced changes could be observed in sequential FLIM and PLIM recordings, as well as in simultaneous FLIM/PLIM recordings using an intermediate TCSPC timing resolution.
Conformationally fixed carbohydrate analogues are promising small-molecule inhibitors for hydrolases like O-GlcNAcase (OGA); however, their synthesis usually requires many steps. Herein we describe cycloadditions of dichloroketene to various glycals and subsequent Beckmann rearrangements, which offer an easy and stereoselective entry to glycosamine derivatives in good yields. The reactions are applicable for hexoses, pentoses, and disaccharides, and transformations to the corresponding imidates proceed smoothly. First biological tests reveal that such imidates indeed inhibit human OGA.
Shape-Memory Capability of Copolyetheresterurethane Microparticles Prepared via Electrospraying
(2015)
Multifunctional thermo-responsive and degradable microparticles exhibiting a shapememory effect (SME) have attracted widespread interest in biomedicine as switchable delivery vehicles or microactuators. In this work almost spherical solid microparticles with an average diameter of 3.9 +/- 0.9 mm are prepared via electrospraying of a copolyetheresterurethane named PDC, which is composed of crystallizable oligo(p-dioxanone) (OPDO) hard and oligo(e-caprolactone) (OCL) switching segments. The PDC microparticles are programmed via compression at different pressures and their shapememory capability is explored by off-line and online heating experiments. When a low programming pressure of 0.2 MPa is applied a pronounced thermally-induced shape-memory effect is achieved with a shape recovery ratio about 80%, while a high programming pressure of 100 MPa resulted in a weak shape-memory performance. Finally, it is demonstrated that an array of PDC microparticles deposited on a polypropylene (PP) substrate can be successfully programmed into a smart temporary film, which disintegrates upon heating to 60 degrees C.
In this thesis we investigate the evaporation behaviour of sessile droplets of aqueous saline solutions on planar inert and metallic surfaces and characterise the corrosion phenomenon for iron surfaces. First we study the evaporation behaviour of sessile salty droplets on inert surfaces for a wide range of salt concentrations, relative humidities, droplet sizes and contact angles. Our study reveals the range of validity of the well-accepted diffusion-controlled evaporation model and highlights the impact of salt concentration (surface tension) gradients driven Marangoni flows on the evaporation behaviour and the subsequent salty deposit patterns. Furthermore we study the spatial-temporal evolution of sessile droplets from saline solutions on metallic surfaces. In contrast to the simple, generally accepted Evans droplet model, we show that the corrosion spreads ahead of the macroscopic contact line with a peripheral film. The three-phase contact line is destabilized by surface tension gradients induced by ionic composition changes during the course of the corrosion process and migration of cations towards the droplet perimeter. Finally we investigate the corrosion behaviour under drying salty sessile droplets on metallic surfaces. The corrosion process, in particular the location of anodic and cathodic activities over the footprint droplet area is correlated to the spatial distribution of the salt inside the drying droplet.
The present study deals with the adsorption performance of fixed bed columns using powdered sulphoxide modified poly(styrene-co-divinylbenzene) (d(10) < 13 mu m, d(50) < 30 mu m, d(90) < 50 mu m) for the separation of platinum and ruthenium from hydrochloric acidic solutions containing both metals (c(Pt) = 20 mg/L, c(Ru) = 10 mg/L). The influence of hydrochloric acid concentration, temperature, flow rate, flow direction, redox potential and bed height on the breakthrough characteristics was examined. Platinum was separately adsorbed mainly induced by hydrochloric acid concentration and redox potential keeping platinum as Pt-IV and ruthenium as Ru-III. Ruthenium was separately adsorbed to 90% essentially induced by hydrochloric acid concentration, temperature and redox potential keeping platinum as Pt-IV and ruthenium predominantly as Ru-IV. Experimental data at optimised separation conditions were fitted to different kinetic models (Thomas, Yoon-Nelson, Bohart-Adams, Wolborska) to characterise the fixed bed column behaviour. Adsorption of both metals was well described by Thomas and Yoon-Nelson model with correlation coefficients R-2 >= 0.95 whereas Bohart-Adams and Wolborska model were less suitable. (C) 2015 Elsevier B.V. All rights reserved.
Femtosecond-laser pulse driven non-adiabatic spectroscopy and dynamics in molecular and condensed phase systems continue to be a challenge for theoretical modelling. One of the main obstacles is the "curse of dimensionality" encountered in non-adiabatic, exact wavepacket propagation. A possible route towards treating complex molecular systems is via semiclassical surface-hopping schemes, in particular if they account not only for non-adiabatic post-excitation dynamics but also for the initial optical excitation. One such approach, based on initial condition filtering, will be put forward in what follows. As a simple test case which can be compared with exact wavepacket dynamics, we investigate the influence of the different parameters determining the shape of a laser pulse (e.g., its finite width and a possible chirp) on the predissociation dynamics of a NaI molecule, upon photoexcitation of the A(0(+)) state. The finite-pulse effects are mapped into the initial conditions for semiclassical surface-hopping simulations. The simulated surface-hopping diabatic populations are in qualitative agreement with the quantum mechanical results, especially concerning the subpicosend photoinduced dynamics, the main deviations being the relative delay of the non-adiabatic transitions in the semiclassical picture. Likewise, these differences in the time-dependent electronic populations calculated via the semiclassical and the quantum methods are found to have a mild influence on the overall probability density distribution. As a result, the branching ratios between the bound and the dissociative reaction channels and the time-evolution of the molecular wavepacket predicted by the semiclassical method agree with those computed using quantum wavepacket propagation. Implications for more challenging molecular systems are given. (C) 2015 AIP Publishing LLC.
In order to understand the timing of leaf wax synthesis in higher plants, we analysed the variability in leaf wax n-alkane concentration, composition (expressed as average chain length (ACL)), and delta H-2(wax) values as well as plant source water delta H-2 values (xylem and leaf water) in the evergreen tree Quercus agrifolia over a period of 9 months, beginning with leaf flush. We identified three distinct periods of leaf development with the first month following leaf flush being characterized by de novo synthesis and possibly removal of n-alkanes. During the following 3 months, n-alkane concentrations increased sevenfold and delta H-2(wax) and ACL values increased, suggesting this period was the major leaf wax n-alkane formation period. During the remaining 4 months of the experiment, stable values suggest cessation of leaf wax n-alkane formation. We find that n-alkane synthesis in Q. agrifolia takes place over 4 months, substantially longer than that observed for deciduous trees.
It is demonstrated that the orientation of striped patterns can be reversibly switched between two perpendicular in-plane orientations upon exposure to electric fields. The results on thin films of symmetric polystyrene-block-poly(2-vinyl pyridine) polymer in the intermediate segregation regime disclose two types of reorientation mechanisms from perpendicular to parallel relative to the electric field orientation. Domains orient via grain rotation and via formation of defects such as stretched undulations and temporal phase transitions. The contribution of additional fields to the structural evolution is also addressed to elucidate the generality of the observed phenomena. In particular solvent effects are considered. This study reveals the stabilization of the meta-stable in-plane oriented lamella due to sequential swelling and quenching of the film. Further, the reorientation behavior of lamella domains blended with selective nanoparticles is addressed, which affect the interfacial tensions of the blocks and hence introduce another internal field to the studied system. Switching the orientation of aligned block copolymer patterns between two orthogonal directions may open new applications of nanomaterials as switchable electric nanowires or optical gratings.
Incorporating photochromic molecules into organic/inorganic hybrid materials may lead to photoresponsive systems. In such systems, the second-order nonlinear properties can be controlled via external stimulation with light at an appropriate wavelength. By creating photochromic molecular switches containing self-assembled monolayers on Si(111), we can demonstrate efficient reversible switching, which is accompanied by a pronounced modulation of the nonlinear optical (NLO) response of the system. The concept of utilizing functionalized photoswitchable Si surfaces could be a way for the generation of two-dimensional NLO switching materials, which are promising for applications in photonic and optoelectronic devices.
Dual responsive inverse opal hydrogels were designed as autonomous sensor systems for (bio)macromolecules, exploiting the analyte-induced modulation of the opal's structural color. The systems that are based on oligo(ethylene glycol) macromonomers additionally incorporate comonomers with various recognition units. They combine a coil-to-globule collapse transition of the LCST type with sensitivity of the transition temperature toward molecular recognition processes. This enables the specific detection of macromolecular analytes, such as glycopolymers and proteins, by simple optical methods. While the inverse opal structure assists the effective diffusion even of large analytes into the photonic crystal, the stimulus responsiveness gives rise to strong shifts of the optical Bragg peak of more than 100nm upon analyte binding at a given temperature. The systems' design provides a versatile platform for the development of easy-to-use, fast, and low-cost sensors for pathogens.
Fully renewable pyridinium ionic liquids were synthesised via the hydrothermal decarboxylation of pyridinium zwitterions derived from furfural and amino acids in flow. The functionality of the resulting ionic liquid (IL) can be tuned by choice of different amino acids as well as different natural carboxylic acids as the counterions. A representative member of this new class of ionic liquids was successfully used for the synthesis of ionogels and as a solvent for the Heck coupling.
Fully renewable pyridinium ionic liquids were synthesised via the hydrothermal decarboxylation of pyridinium zwitterions derived from furfural and amino acids in flow. The functionality of the resulting ionic liquid (IL) can be tuned by choice of different amino acids as well as different natural carboxylic acids as the counter-ions. A representative member of this new class of ionic liquids was successfully used for the synthesis of ionogels and as a solvent for the Heck coupling.
Fully renewable pyridinium ionic liquids were synthesised via the hydrothermal decarboxylation of pyridinium zwitterions derived from furfural and amino acids in flow. The functionality of the resulting ionic liquid (IL) can be tuned by choice of different amino acids as well as different natural carboxylic acids as the counterions. A representative member of this new class of ionic liquids was successfully used for the synthesis of ionogels and as a solvent for the Heck coupling.
The rehydration of thermoresponsive poly(monomethoxydiethylene glycol acrylate) (PMDEGA) films exhibiting a lower critical solution temperature (LCST) type demixing phase transition in aqueous environments, induced by a decrease in temperature, is investigated in situ with real-time neutron reflectivity. Two different starting conditions (collapsed versus partially swollen chain conformation) are compared. In one experiment, the temperature is reduced from above the demixing temperature to well below the demixing temperature. In a second experiment, the starting temperature is below the demixing temperature, but within the transition regime, and reduced to the same final temperature. In both cases, the observed rehydration process can be divided into three stages: first condensation of water from the surrounding atmosphere, then absorption of water by the PMDEGA film and evaporation of excess water, and finally, rearrangement of the PMDEGA chains. The final rehydrated film is thicker and contains more absorbed water as compared with the initially swollen film at the same temperature well below the demixing temperature.
This study presents a novel and easily applicable approach to recruit sulfhydryl-containing biomolecules to membranes by using a palmitic acid which is functionalized with a maleimide group. Notably, this strategy can also be employed with preformed (biological) membranes. The applicability of the assay is demonstrated by characterizing the binding of a Rhodamine-labeled peptide to lipid and cellular membranes using methods of fluorescence spectroscopy, lifetime measurement, and microscopy. Our approach offers new possibilities for preparing biologically active liposomes and manipulating living cells.
The importance of carbohydrate chemistry in biological and medicinal chemistry has led to enormous developments in the synthesis of carbohydrate mimics. In this context, the synthesis of branched sugars in general and of 2-C-branched carbohydrates in particular, as well as the synthesis of 1,2-annulated sugars, have received immense attention. They serve not only as carbohydrate mimics in the form of stand-alone molecules, but also as useful intermediates in the synthesis of many natural products, their analogues, and glycosidase inhibitors. This microreview covers the recent synthetic efforts in this area and puts the subject matter into proper perspective for future developments.
Brownianmotion is ergodic in the Boltzmann–Khinchin sense that long time averages of physical observables such as the mean squared displacement provide the same information as the corresponding ensemble average, even at out-of-equilibrium conditions. This property is the fundamental prerequisite for single particle tracking and its analysis in simple liquids. We study analytically and by event-driven molecular dynamics simulations the dynamics of force-free cooling granular gases and reveal a violation of ergodicity in this Boltzmann–
Khinchin sense as well as distinct ageing of the system. Such granular gases comprise materials such as dilute gases of stones, sand, various types of powders, or large molecules, and their mixtures are ubiquitous in Nature and technology, in particular in Space. We treat—depending on the physical-chemical properties of the inter-particle interaction upon their pair collisions—both a constant and a velocity-dependent (viscoelastic) restitution coefficient e. Moreover we compare the granular gas dynamics with an effective single particle stochastic model based on an underdamped Langevin equation with time dependent diffusivity. We find that both models share the same behaviour of the ensemble mean squared displacement (MSD) and the velocity correlations in the limit of weak dissipation. Qualitatively, the reported non-ergodic behaviour is generic for granular gases with any realistic dependence of e on the impact velocity of particles.
Brownianmotion is ergodic in the Boltzmann–Khinchin sense that long time averages of physical observables such as the mean squared displacement provide the same information as the corresponding ensemble average, even at out-of-equilibrium conditions. This property is the fundamental prerequisite for single particle tracking and its analysis in simple liquids. We study analytically and by event-driven molecular dynamics simulations the dynamics of force-free cooling granular gases and reveal a violation of ergodicity in this Boltzmann-Khinchin sense as well as distinct ageing of the system. Such granular gases comprise materials such as dilute gases of stones, sand, various types of powders, or large molecules, and their mixtures are ubiquitous in Nature and technology, in particular in Space. We treat—depending on the physical-chemical properties of the inter-particle interaction upon their pair collisions—both a constant and a velocity-dependent
(viscoelastic) restitution coefficient e. Moreover we compare the granular gas dynamics with an effective single particle stochastic model based on an underdamped Langevin equation with time dependent diffusivity. We find that both models share the same behaviour of the ensemble mean squared displacement (MSD) and the velocity correlations in the limit of weak dissipation. Qualitatively, the reported non-ergodic behaviour is generic for granular gases with any realistic dependence of e on the impact velocity of particles.
Organosilanes are used routinely to functionalize various support materials for further modifications. Nevertheless, reliable quantitative information about surface functional group densities after layer formation is rarely available. Here, we present the analysis of thin organic nanolayers made from nitrogen containing silane molecules on naturally oxidized silicon wafers with reference-free total reflection X-ray fluorescence (TXR.F) and X-ray photoelectron spectroscopy (XPS). An areic density of 2-4 silane molecules per nm(2) was calculated from the layer's nitrogen mass deposition per area unit obtained by reference-free TXRF. Complementary energy and angle-resolved XPS (ER/AR-XPS) in the Si 2p core-level region was used to analyze the outermost surface region of the organic (silane layer)-inorganic (silicon wafer) interface. Different coexisting silicon species as silicon, native silicon oxide, and silane were identified and quantified. As a result of the presented proof-of-concept, absolute and traceable values for the areic density of silanes containing nitrogen as intrinsic marker are obtained by calibration of the XPS methods with reference-free TXRF. Furthermore, ER/AR-XPS is shown to facilitate the determination of areic densities in (mono)layers made from silanes having no heteroatomic marker other than silicon. After calibration with reference-free TXRF, these areic densities of silane molecules can be determined when using the XPS component intensity of the silane's silicon atom.
In this work, gold nanostars (AuNSs) with size around 90 nm were prepared through an easy one-step method. They show excellent catalytic activity and large surface-enhanced Raman scattering (SERS) activity at the same time. Surprisingly, they exhibited different catalytic performance on the reduction of aromatic nitro compounds with different substituents on the para position. To understand such a difference, the SERS spectra were recorded, showing that the molecular orientation of reactants on the gold surface were different. We anticipate that this research will help to understand the relationship of the molecular orientation with the catalytic activity of gold nanoparticles.
Aims: 1-Methyl-4-phenyl-tetrahydropyridine (MPTP) is among the most widely used neurotoxins for inducing experimental parkinsonism. MPTP causes parkinsonian symptoms in mice, primates, and humans by killing a subpopulation of dopaminergic neurons. Extrapolations of data obtained using MPTP-based parkinsonism models to human disease are common; however, the precise mechanism by which MPTP is converted into its active neurotoxic metabolite, 1-methyl-4-phenyl-pyridinium (MPP+), has not been fully elucidated. In this study, we aimed to address two unanswered questions related to MPTP toxicology: (1) Why are MPTP-converting astrocytes largely spared from toxicity? (2) How does MPP+ reach the extracellular space? Results: In MPTP-treated astrocytes, we discovered that the membrane-impermeable MPP+, which is generally assumed to be formed inside astrocytes, is almost exclusively detected outside of these cells. Instead of a transporter-mediated export, we found that the intermediate, 1-methyl-4-phenyl-2,3-dihydropyridinium (MPDP+), and/or its uncharged conjugate base passively diffused across cell membranes and that MPP+ was formed predominately by the extracellular oxidation of MPDP+ into MPP+. This nonenzymatic extracellular conversion of MPDP+ was promoted by O-2, a more alkaline pH, and dopamine autoxidation products. Innovation and Conclusion: Our data indicate that MPTP metabolism is compartmentalized between intracellular and extracellular environments, explain the absence of toxicity in MPTP-converting astrocytes, and provide a rationale for the preferential formation of MPP+ in the extracellular space. The mechanism of transporter-independent extracellular MPP+ formation described here indicates that extracellular genesis of MPP+ from MPDP is a necessary prerequisite for the selective uptake of this toxin by catecholaminergic neurons.
Porphyrin substituent regiochemistry, conformation and packing - the case of 5,10-diphenylporphyrin
(2015)
5,10-Disubstituted porphyrins are more recent additions to the family of meso-substituted porphyrins. A crystallographic comparison of 5,10-diphenylporphyrin with the regioisomeric 5,15-disubstituted system reveals striking differences in their conformation. In the free base porphyrins the former uses mainly out-of-plane distortion to alleviate steric strain while in-plane core elongation predominates in the latter. In contrast, the structure of the Cu(II) complex is planar and forms strong p-p aggregates with very small lateral shifts. Macroscopically, the packing is similar to that of porphyrin sponges of the 5,10,15,20-tetraphenylporphyrin type.
A concentrated solution of a symmetric triblock copolymer with a thermoresponsive poly(methoxy diethylene glycol acrylate) (PMDEGA) middle block and short hydrophobic, fully deuterated polystyrene end blocks is investigated in D2O where it undergoes a lower critical solution temperature-type phase transition at ca. 36 A degrees C. Small-angle neutron scattering (SANS) in a wide temperature range (15-50 A degrees C) is used to characterize the size and inner structure of the micelles as well as the correlation between the micelles and the formation of aggregates by the micelles above the cloud point (CP). A model featuring spherical core-shell micelles, which are correlated by a hard-sphere potential or a sticky hard-sphere potential together with a Guinier form factor describing aggregates formed by the micelles above the CP, fits the SANS curves well in the entire temperature range. The thickness of the thermoresponsive micellar PMDEGA shell as well as the hard-sphere radius increase slightly already below the cloud point. Whereas the thickness of the thermoresponsive micellar shell hardly shrinks when heating through the CP and up to 50 A degrees C, the hard-sphere radius decreases within 3.5 K at the CP. The volume fraction decreases already significantly below the CP, which may be at the origin of the previously observed gel-sol transition far below the CP (Miasnikova et al., Langmuir 28: 4479-4490, 2012). Above the CP, small, and at higher temperatures, large aggregates are formed by the micelles.
Dendritic cells (DC) contribute to immunity by presenting antigens to T cells and shape the immune response by the secretion of cytokines. Due to their immune stimulatory potential DC-based therapies are promising approaches to overcome tolerance e.g. against tumors. In order to enforce the immunogenicity of DCs, they have to be matured and activated in vitro, which requires an appropriate cell culture substrate, supporting their survival expansion and activation.
Since most cell culture devices are not optimized for DC growth, it is hypothesized that polymers with certain physicochemical properties can positively influence the DC cultures. With the aim to evaluate the effects that polymers with different chemical compositions have on the survival, the activation status, and the cytokine/chemokine secretion profile of DC, their interaction with polystyrene (PS), polycarbonate (PC), poly(ether imide) (PEI), and poly(styrene-co-acrylonitrile) (PSAN)-based cell culture inserts was investigated. By using this insert system, which fits exactly into 24 well cell culture plates, effects induced from the culture dish material can be excluded. The viability of untreated DC after incubation with the different inserts was not influenced by the different inserts, whereas LPS-activatedDCshowed an increased survival after cultivation on PC, PS, and PSAN compared to tissue culture polystyrene (TCP). The activation status of DC estimated by the expression of CD40, CD80, CD83, CD86 and HLA-DR expression was not altered by the different inserts in untreated DC but slightly reduced when LPS-activated DC were cultivated on PC, PS, PSAN, and PEI compared to TCP. For each polymeric cell culture insert a distinct cytokine profile could be observed.
Since inserts with different chemical compositions of the inserts did not substantially alter the behavior of DC all insert systems could be considered as alternative substrate. The observed increased survival on some polymers, which showed in contrast to TCP a hydrophobic surface, could be beneficial for certain applications such as T cell expansion and activation.
Poly(Ionic Liquid)s
(2015)
The main focus of the present thesis was to investigate the stabilization ability of poly(ionic liquid)s (PILs) in several examples as well as develop novel chemical structures and synthetic routes of PILs. The performed research can be specifically divided into three parts that include synthesis and application of hybrid material composed of PIL and cellulose nanofibers (CNFs), thiazolium-containing PILs, and main-chain imidazolium-type PILs.
In the first chapter, a vinylimidazolium-type IL was polymerized in water in the presence of CNFs resulting in the in situ electrostatic grafting of polymeric chains onto the surface of CNFs. The synthesized hybrid material merged advantages of its two components, that is, superior mechanical strength of CNFs and anion dependent solution properties of PILs. In contrast to unmodified CNFs, the hybrid could be stabilized and processed in organic solvents enabling its application as reinforcing agent for porous polyelectrolyte membranes.
In the second part, PILs and ionic polymers containing two types of thiazolium repeating units were synthesized. Such polymers displayed counterion dependent thermal stability and solubility in organic solvents of various dielectric constants. This new class of PILs was tested as stabilizers and phase transfer agents for carbon nanotubes in aqueous and organic media, and as binder materials to disperse electroactive powders and carbon additives in solid electrode in lithium-ion batteries. The incorporation of S and N atoms into the polymeric structures make such PILs also potential precursors for S, N - co-doped carbons.
In the last chapter, reactants originating from biomass were successfully harnessed to synthesize main-chain imidazolium-type PILs. An imidazolium-type diester IL obtained via a modified Debus-Radziszewski reaction underwent transesterification with diol in a polycondensation reaction. This yielded a polyester-type PIL which CO2 sorption properties were investigated. In the next step, the modified Debus-Radziszewski reaction was further applied to synthesize main-chain PILs according to a convenient, one-step protocol, using water as a green solvent and simple organic molecules as reagents. Depending on the structure of the employed diamine, the synthesized PILs after anion exchange showed superior thermal stability with unusually high carbonization yields.
Overall, the outcome of these studies will actively contribute to the current research on PILs by introducing novel PIL chemical structures, improved synthetic routes, and new examples of stabilized materials. The synthesis of main-chain imidazolium-type PILs by a modified Debus-Radziszewski reaction is of a special interest for the future work on porous ionic liquid networks as well as colloidal PIL nanoparticles.
The present article is among the first reports on the effects of poly(ampholyte)s and poly(betaine)s on the biomimetic formation of calcium phosphate. We have synthesized a series of di- and triblock copolymers based on a non-ionic poly(ethylene oxide) block and several charged methacrylate monomers, 2-(trimethylammonium)ethyl methacrylate chloride, 2-((3-cyanopropyl)-dimethylammonium)ethyl methacrylate chloride, 3-sulfopropyl methacrylate potassium salt, and [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide. The resulting copolymers are either positively charged, ampholytic, or betaine block copolymers. All the polymers have very high molecular weights of over 106 g mol−1. All polymers are water-soluble and show a strong effect on the precipitation and dissolution of calcium phosphate. The strongest effects are observed with triblock copolymers based on a large poly(ethylene oxide) middle block (nominal Mn = 100 000 g mol−1). Surprisingly, the data show that there is a need for positive charges in the polymers to exert tight control over mineralization and dissolution, but that the exact position of the charge in the polymer is of minor importance for both calcium phosphate precipitation and dissolution.
The present article is among the first reports on the effects of poly(ampholyte)s and poly(betaine) s on the biomimetic formation of calcium phosphate. We have synthesized a series of di- and triblock copolymers based on a non-ionic poly(ethylene oxide) block and several charged methacrylate monomers, 2-(trimethylammonium) ethyl methacrylate chloride, 2-((3-cyanopropyl)-dimethylammonium)ethyl methacrylate chloride, 3-sulfopropyl methacrylate potassium salt, and [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl) ammonium hydroxide. The resulting copolymers are either positively charged, ampholytic, or betaine block copolymers. All the polymers have very high molecular weights of over 10(6) g mol(-1). All polymers are water-soluble and show a strong effect on the precipitation and dissolution of calcium phosphate. The strongest effects are observed with triblock copolymers based on a large poly(ethylene oxide) middle block (nominal M-n = 100 000 g mol(-1)). Surprisingly, the data show that there is a need for positive charges in the polymers to exert tight control over mineralization and dissolution, but that the exact position of the charge in the polymer is of minor importance for both calcium phosphate precipitation and dissolution.
The present article is among the first reports on the effects of poly(ampholyte)s and poly(betaine)s on the biomimetic formation of calcium phosphate. We have synthesized a series of di- and triblock copolymers based on a non-ionic poly(ethylene oxide) block and several charged methacrylate monomers, 2-(trimethylammonium)ethyl methacrylate chloride, 2-((3-cyanopropyl)-dimethylammonium)ethyl methacrylate chloride, 3-sulfopropyl methacrylate potassium salt, and [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide. The resulting copolymers are either positively charged, ampholytic, or betaine block copolymers. All the polymers have very high molecular weights of over 106 g mol−1. All polymers are water-soluble and show a strong effect on the precipitation and dissolution of calcium phosphate. The strongest effects are observed with triblock copolymers based on a large poly(ethylene oxide) middle block (nominal Mn = 100 000 g mol−1). Surprisingly, the data show that there is a need for positive charges in the polymers to exert tight control over mineralization and dissolution, but that the exact position of the charge in the polymer is of minor importance for both calcium phosphate precipitation and dissolution.
Polypeptoids have been of great interest in the polymer science community since the early half of the last century; however, they had been basically forgotten materials until the last decades in which they have enjoyed an exciting revival. In this mini-review, we focus on the recent developments in polypeptoid chemistry, with particular focus on polymers synthesized by the ring-opening polymerization (ROP) of amino acid N-carboxyanhydrides (NCAs). Specifically, we will review traditional monomer synthesis (such as Leuchs, Katchalski, and Kricheldorf) and recent advances in polymerization methods to yield both linear, cyclic, and functional polymers, solution and bulk thermal properties, and preliminary results on the use of polypeptoids as biomaterials (i.e immunogenicity, biodistribution, degradability, and drug delivery).
Previously unknown, vertically linked heterocycles comprised of benzofuran and iminocoumarin moieties have been synthesized directly from 1,5-dibenzoyloxyanthraquinone and arylacetonitriles via double Knoevenagel condensation followed by formal HCN elimination. The structural assembly of fully conjugated, electron-rich benzofuran and electron-deficient iminocoumarin is responsible for the strongly polarized nature of these heterocycles which translates into their polarity-sensitive fluorescence.
The approach of deriving new photoresponsive active supramolecular azopolymers based on the hydrogen bonds is described. Polymers with imide rings, i.e., poly(esterimide)s and poly(etherimide)s, with phenolic hydroxyl or carboxylic groups were applied as matrixes for the polymer dye supramolecular systems. Supramolecular films were built on the basis of the hydrogen bonds between the functional groups of the polymers and various azochromophores, that is, 4-phenylazophenol, 4-[4-(6-hydroxyhexy loxy)phenylazo]benzene, 4[4-(6-hexadecaneoxy)phenylazo]pyridine and 4-(4-hydroxyphenylazo)-pyridine. The hydrogen bonding interaction in azo-systems were studied by Fourier transform infrared spectroscopy and for selected assembles by H-1 NMR technique. The obtained polyimide azo-assembles were characterized by X-ray diffraction and DSC measurements. H-bonds allow attaching a chromophore to each repeating unit of the polymer, thereby suppressing the macroscopic phase separation except for the systems based on 4-[4-(6-hydroxyhexyloxy)phenylazo]benzene. H-bonds systems were amorphous and revealed glass transition temperatures lower than for the polyimide matrixes (170-260 degrees C). The photoresponsive behavior of the azo-assemblies was tasted in holographic recording experiment. (C) 2015 Elsevier B.V. All rights reserved.
The polymer architecture of telechelic or associative polymers has a large impact on the bridging of self-assembled structures. This Work presents: the phase behavior, small angle neutron scattering (SANS), dynamic light scattering (DLS), and fluorescence correlation spectroscopy (FCS) of a nonionic oil-in-water (O/W) microemulsion with hydrophobically end-capped multiarm polymers With functionalities f = 2, 3, and 4. For high polymer concentrations and large average interdroplet distance relative to the end-to-end distance of the polymer, d/R-ee; the system phase separates into a dense, highly connected droplet network phase, in equilibrium with a dilute phase. The extent of the two-phase region is larger for polymers With similar length but higher f. The Interaction potential between the droplets in the presence of polymer has both a repulsive and an attractive contribution as a result of the counterbalancing effects of the exclusion by polymer chains and bridging between droplets. This study experimentally demonstrates that higher polymer functionalities induce a stronger attractive force between droplets, which is responsible for a more extended phase separation region., and correlate with lower Collective droplet diffusivities and higher amplitude of the second relaxation time in DLS. The viscosity and the droplet self-diffusion obtained from FCS, however, are dominated by the end-capped chain concentration.
The PEPPSI (Pyridine Enhanced Precatalyst Preparation, Stabilization and Initiation) complexes 12-15 with the structure [PdCl2{(CN)(2)IMes}(3-R-py)] (12: R = H; 13: R = Cl; 14: R = Br; 15: R = CN) bearing the maleonitrile-based N-heterocyclic carbene (NHC) (CN)(2)IMes ({(CN)(2)IMes}: 4,5-dicyano-1,3-dimesitylimidazol-2-ylidene) were prepared. Solid state structures of 14 and 15 were obtained. Complexes 14 and 15 adopt a slightly distorted square-planar coordination geometry in the solid state with the substituted pyridine ligand trans to the NHC. Catalytic activities of precatalysts 12-15 were studied and subsequently compared to complexes [PdCl2{(CN)(2)IMes}(PPh3)] (4) and [PdCl(dmba){(CN)(2)IMes}] (5) recently reported by our group in the Suzuki-Miyaura reaction of various aryl halides and phenylboronic acid. Reactions using previously reported [PdCl2(IMes)(py)] (IMes: 1,3-dimesitylimidazol-2-ylidene) (1) were also carried out and their results contrasted to those involving 12-15, 4 and 5. Differences in initiation rates and the catalytically active species related to the seven complexes in regards to the throw away ligand were investigated. Poisoning experiments with mercury show that palladium nanoparticles are responsible for the catalytic activity.
Oxide/water interfaces are ubiquitous in a wide variety of applications and the environment. Despite this ubiquity, and attendant decades of study, gaining molecular level insight into water/oxide interaction has proven challenging. In part, this challenge springs from a lack of tools to concurrently characterize changes in surface structure (i.e., water/oxide interaction from the perspective of the solid) and O-H population and local environment (i.e., water/oxide interaction from the water perspective). Here, we demonstrate the application of surface specific vibrational spectroscopy to the characterization of the interaction of the paradigmatic alpha-Al2O3(0001) surface and water. By probing both the interfacial Al-O (surface phonon) and O-H spectral response, we characterize this interaction from both perspectives. Through electronic structure calculation, we assign the interfacial Al-O response and rationalize its changes on surface dehydroxylation and reconstruction. Because our technique is all-optical and interface specific, it is equally applicable to oxide surfaces in vacuum, ambient atmospheres and at the solid/liquid interface. Application of this approach to additional alumina surfaces and other oxides thus seems likely to significantly expand our understanding of how water meets oxide surfaces and thus the wide variety of phenomena this interaction controls. (C) 2015 AIP Publishing LLC.
In turbid biogenic liquid material, like blood or milk, quantitative optical analysis is often strongly hindered by multiple light scattering resulting from cells, particles, or droplets. Here, optical attenuation is caused by losses due to absorption as well as scattering of light. Fiber-based Photon Density Wave (PDW) spectroscopy is a very promising method for the precise measurement of the optical properties of such materials. They are expressed as absorption and reduced scattering coefficients (mu (a) and mu (s)', respectively) and are linked to the chemical composition and physical properties of the sample. As a process analytical technology, PDW spectroscopy can sense chemical and/or physical processes within such turbid biogenic liquids, providing new scientific insight and process understanding. Here, for the first time, several bioprocesses are analyzed by PDW spectroscopy and the resulting optical coefficients are discussed with respect to established mechanistic models of the chosen processes. As model systems, enzymatic casein coagulation in milk, temperature-induced starch hydrolysis in beer mash, and oxy- as well as deoxygenation of human donor blood were investigated by PDW spectroscopy. The findings indicate that also for very complex biomaterials (i.e., not well-defined model materials like monodisperse polymer dispersions), obtained optical coefficients allow for the assessment of a structure/process relationship and thus for a new analytical access to biogenic liquid material. This is of special relevance as PDW spectroscopy data are obtained without any dilution or calibration, as often found in conventional spectroscopic approaches.
Nonlinear optical response of photochromic azobenzene-functionalized self-assembled monolayers
(2015)
The combination of photochromic and nonlinear optical (NLO) properties of azobenzene-functionalized self-assembled monolayers (SAMs) constitutes an intriguing step towards novel photonic and optoelectronic devices. By utilizing the second-order NLO process of second harmonic generation (SHG), supported by density-functional theory and correlated wave function method calculations, we demonstrate that the photochromic interface provides the necessary prerequisites en route towards possible future technical applications: we find a high NLO contrast on the order of 16% between the switching states. These are furthermore accessible reversibly and with high efficiencies in terms of cross sections on the order of 10−18 cm2 for both photoisomerization reactions, i.e., drivable by means of low-power LED light sources. Finally, both photostationary states (PSSs) are thermally stable at ambient conditions.
Nonlinear optical response of photochromic azobenzene-functionalized self-assembled monolayers
(2015)
The combination of photochromic and nonlinear optical (NLO) properties of azobenzene-functionalized self-assembled monolayers (SAMs) constitutes an intriguing step towards novel photonic and optoelectronic devices. By utilizing the second-order NLO process of second harmonic generation (SHG), supported by density-functional theory and correlated wave function method calculations, we demonstrate that the photochromic interface provides the necessary prerequisites en route towards possible future technical applications: we find a high NLO contrast on the order of 16% between the switching states. These are furthermore accessible reversibly and with high efficiencies in terms of cross sections on the order of 10(-18) cm(2) for both photoisomerization reactions, i.e., drivable by means of low-power LED light sources. Finally, both photostationary states (PSSs) are thermally stable at ambient conditions.
Nonlinear optical response of photochromic azobenzene-functionalized self-assembled monolayers
(2015)
The combination of photochromic and nonlinear optical (NLO) properties of azobenzene-functionalized self-assembled monolayers (SAMs) constitutes an intriguing step towards novel photonic and optoelectronic devices. By utilizing the second-order NLO process of second harmonic generation (SHG), supported by density-functional theory and correlated wave function method calculations, we demonstrate that the photochromic interface provides the necessary prerequisites en route towards possible future technical applications: we find a high NLO contrast on the order of 16% between the switching states. These are furthermore accessible reversibly and with high efficiencies in terms of cross sections on the order of 10−18 cm2 for both photoisomerization reactions, i.e., drivable by means of low-power LED light sources. Finally, both photostationary states (PSSs) are thermally stable at ambient conditions.
Ni-based materials for the catalytic conversion of lignocellulosic biomass into valuable products
(2015)
Singlet oxygen donors are of current interest for medical applications, but suffer from a short half-life leading to low singlet oxygen yields and problems with storage. We have synthesized more than 25new singlet oxygen donors based on differently substituted naphthalenes in only a few steps. The influence of functional groups on the reaction rate of the photooxygenations, thermolysis, half-life, and singlet oxygen yield has been thoroughly studied. We determined various thermodynamic data and compared them with density functional calculations. Interestingly, remarkable stabilities of functional groups during the photooxygenations and stabilizing effects for some endoperoxides during the thermolysis have been found. Furthermore, we give evidence for a partly concerted and partly stepwise thermolysis mechanism leading to singlet and triplet oxygen, respectively. Our results might be interesting for dark oxygenations and future applications in medicine.
Ziel dieser Arbeit war die Synthese und Charakterisierung von neuartigen fluoreszierenden Copolymeren zur Analytdetektion in wässrigen Systemen. Das Detektionssystem sollte ein einfaches Schalten der Fluoreszenz bei Analytbindung „Aus“ bzw. Verdrängung „An“ ermöglichen. Dafür wurde die Synthese eines funktionalisierten Monomers so geplant, dass sich Fluorophor und Analyt innerhalb derselben Monomereinheit in direkter Nachbarschaft zueinander befinden. So sollten bei Erkennung des Analyten durch eine mit einem Fluoreszenzlöscher funktionalisierte Erkennungsstruktur Fluorophor und Löscher in einen vorgegebenen Abstand zueinander gezwungen und die Fluoreszenz des Fluorophors effizient gelöscht werden. Bei anschließender Verdrängung der Erkennungseinheit durch einen stärker bindenden Analyten sollte die Fluoreszenz wieder „angeschaltet“ werden. Eine weitere Zielstellung für das Detektionssystem war eine hohe Löslichkeit und Fluoreszenzintensität in Wasser. Da die Anwendung solcher Sensoren besonders in der Medizin und Biologie, z.B. für Schnellerkennungstest von Pathogenen, von Interesse ist, ist die Kompatibilität mit wässrigen Medien essentiell. Die funktionalisierten Monomere wurden frei radikalisch mit N Vinyl-pyrrolidon bzw. N Vinyl¬caprolactam zu wasserlöslichen, fluoreszierenden Copolymeren umgesetzt. In den N-Vinyl¬pyrrolidon-Polymeren (PNVP) wurde RhodaminB, in den thermoresponsiven N Vinyl¬caprolactam-Polymeren (PNVCL) ein Naphthalsäureimid als Fluorophor verwendet. Während Rhodamine eine hohe Fluoreszenzintensität, gute Quantenausbeuten und hohen Extinktionskoeffizienten in Wasser zeigen, sind Naphthalsäure¬imide umgebungssensitive Chromophore, die bei Änderung ihrer Lösungsmittelumgebung, wie z.B. beim Kollaps eines thermoresponsiven Polymers in Wasser, ihre Fluoreszenzintensität und Quantenausbeute drastisch ändern können. Der Vorteil der hier verwendeten Strategie der Monomersynthese liegt darin, dass bei jeder spezifischen Analytdetektion durch eine Erkennungseinheit die Fluoreszenz effizient gelöscht bzw. bei Verdrängung durch einen stärker bindenden Analyten wieder „angeschaltet“ wird. Dieses Prinzip wird bereits vielfach in der Biologie in sogenannten „Molecular Beacons“ ausgenutzt, wobei ein Fluorophor und ein Löscher durch spezifische DNA Basenpaarung in einen vorgegebenen Abstand zueinander gezwungen werden und so ein „Schalten“ der Fluoreszenz ermöglichen. Aufgrund der vorgegebenen Struktur der DNA Basensequenzen ist es jedoch nicht direkt auf andere Erkennungsreaktionen übertragbar. Daher wurde ein Modellsystem entwickelt, welches die Möglichkeit bietet Analyt, Erkennungseinheit und Signalgeber variabel, je nach Anforderungen des Systems, auszutauschen. So soll es möglich sein, den Sensor a priori für jede Erkennungs¬reaktion zu verwenden. Als Modell Bindungs¬paare wurden ß Cyclodextrin/Adamantan und Con¬cana¬valinA/Mannose ausgewählt. Adamantan bzw. Mannose wurde als Analyt zusammen mit dem Fluorophor in das Polymer eingebunden. ß Cyclo¬dextrin (ß CD) bzw. ConcanavalinA (ConA) wurde als Erkennungsstruktur an einem Fluoreszenzlöscher immobilisiert. Polymer-basierte Fluoreszenzsensoren sind in der Fachliteratur gut dokumentiert. In der Regel sind Signalgeber und Analyt jedoch statistisch im Polymer verteilt, da sie sich entweder in unterschiedlichen Monomereinheiten befinden oder die Funktionalisierung durch eine polymeranaloge Umsetzung erfolgt. Der gewählte Ansatz Fluorophor und Analyt innerhalb derselben Monomereinheit einzubinden, soll bei jeder Erkennungsreaktion des Analyten zu einer Änderung der Signalintensität des Fluorophors führen. Eine hohe Signalintensität bei Analytdetektion ist wünschenswert, insbesondere für Erkennungsreaktionen, die mit möglichst geringem apparativem Aufwand, am besten mit dem bloßen Auge zu verfolgen sein sollen. Des Weiteren ist es möglich den Fluorophorgehalt im Polymer genau einzustellen und so Selbstlöschung zu vermeiden. Die synthetisierten Polymere haben einen Fluorophorgehalt von 0,01 mol% bis 0,5 mol%. Für die RhodaminB haltigen Polymere zeigte sich, dass ein Fluorophorgehalt unterhalb 0,1 mol% im Polymer die höchsten Ausbeuten, Molmassen und Quantenausbeuten liefert. Für die Naphthalsäureimid haltigen Polymere hingegen wurden auch für einen Fluorophorgehalt von bis zu 1 mol% hohe Ausbeuten und Molmassen erreicht. Die Naphthalsäureimid haltigen Polymere haben jedoch in wässriger Lösungsmittelumgebung nur geringe Quantenausbeuten. Als Fluoreszenzlöscher wurden Goldnanopartikel synthetisiert, die mit den entsprechenden Erkennungsstrukturen (ß-CD oder ConA) für den verwendeten Analyten funktionalisiert wurden. Goldnanopartikel als Löscher bieten den Vorteil, dass ihre Dispergierbarkeit in einem Lösemittel durch Funktionalisierung ihrer Hülle gezielt gesteuert werden kann. Durch die hohe Affinität von Goldnanopartikeln zu Thiolen und Aminen konnten sie mit Hilfe einfacher Syntheseschritte mit Thio ß CD Derivaten bzw. ConA funktionalisiert werden. In der hier vorgelegten Arbeit sollte ein Modellsystem für einen solches fluoreszenz-basiertes Detektionssystem in Wasser entwickelt werden. Nachfolgend werden die zu erfüllenden strukturellen Voraussetzungen für die Synthese eines solchen Sensors nochmals zusammengefasst:
1. Verwendung eines Fluorophors, der eine hohe Signalintensität zeigt.
2. Analyt bzw. Erkennungseinheit soll sich im Abstand von wenigen Nanometern zum Signalgeber befinden, um bei jeder Detektionsreaktion die Signalintensität des Signalgebers beeinflussen zu können.
3. Die Detektionseinheit benötigt eine funktionelle Gruppe zur Immobilisierung. Immobilisierung kann z.B. durch Einbindung in ein Polymer erfolgen.
4. Der Fluorophor soll bei Änderung seiner lokalen Umgebung, durch Binden eines Löschers oder Änderung seiner Lösemittelumgebung seine Fluoreszenzeigenschaften drastisch ändern.
5. Die Reaktion sollte schnell und mit möglichst geringem apparativem Aufwand, am besten mit bloßem Auge zu verfolgen sein.
Für das ß-CD/Adamantan Modellsystem wurde ein Fluoreszenz Aus/An Sensor entwickelt, der bei Binden ß CD funktionalisierter Goldnanopartikel an das polymergebundene Adamantan die Fluoreszenz des RhodaminB Fluorophors effizient löscht und bei Verdrängung der Goldnanopartikel wieder zurück gewinnt. Dies konnte auch mit bloßem Auge verfolgt werden.
Für die Naphthalsäureimid Monomere, die mit NVCL copolymerisiert wurden, wurde abhängig von der lokalen Umgebung des Fluorophors eine unterschiedliche Verstärkung der Fluoreszenzintensität bei Überschreiten des Trübungspunktes des Polymers gefunden. Dabei zeigte sich, dass die Einführung eines Abstandshalters zwischen Polymerrückgrat und Fluorophor zu einer großen Fluoreszenz¬verstärkung führt, während sich ohne Abstandshalter die Fluoreszenzintensität bei Über¬schreiten des Trübungspunktes kaum ändert.
Temperature-memory polymers remember the temperature, where they were deformed recently, enabled by broad thermal transitions. In this study, we explored a series of crosslinked poly[ethylene-co-(vinyl acetate)] networks (cPEVAs) comprising crystallizable polyethylene (PE) controlling units exhibiting a pronounced temperature-memory effect (TME) between 16 and 99 °C related to a broad melting transition (∼100 °C). The nanostructural changes in such cPEVAs during programming and activation of the TME were analyzed via in situ X-ray scattering and specific annealing experiments. Different contributions to the mechanism of memorizing high or low deformation temperatures (Tdeform) were observed in cPEVA, which can be associated to the average PE crystal sizes. At high deformation temperatures (>50 °C), newly formed PE crystals, which are established during cooling when fixing the temporary shape, dominated the TME mechanism. In contrast, at low Tdeform (<50 °C), corresponding to a cold drawing scenario, the deformation led preferably to a disruption of existing large crystals into smaller ones, which then fix the temporary shape upon cooling. The observed mechanism of memorizing a deformation temperature might enable the prediction of the TME behavior and the knowledge based design of other TMPs with crystallizable controlling units.
Temperature-memory polymers remember the temperature, where they were deformed recently, enabled by broad thermal transitions. In this study, we explored a series of crosslinked poly[ethylene-co-(vinyl acetate)] networks (cPEVAs) comprising crystallizable polyethylene (PE) controlling units exhibiting a pronounced temperature-memory effect (TME) between 16 and 99 °C related to a broad melting transition (∼100 °C). The nanostructural changes in such cPEVAs during programming and activation of the TME were analyzed via in situ X-ray scattering and specific annealing experiments. Different contributions to the mechanism of memorizing high or low deformation temperatures (Tdeform) were observed in cPEVA, which can be associated to the average PE crystal sizes. At high deformation temperatures (>50 °C), newly formed PE crystals, which are established during cooling when fixing the temporary shape, dominated the TME mechanism. In contrast, at low Tdeform (<50 °C), corresponding to a cold drawing scenario, the deformation led preferably to a disruption of existing large crystals into smaller ones, which then fix the temporary shape upon cooling. The observed mechanism of memorizing a deformation temperature might enable the prediction of the TME behavior and the knowledge based design of other TMPs with crystallizable controlling units.
Temperature-memory polymers remember the temperature, where they were deformed recently, enabled by broad thermal transitions. In this study, we explored a series of crosslinked poly[ethylene-co-(vinyl acetate)] networks (cPEVAs) comprising crystallizable polyethylene (PE) controlling units exhibiting a pronounced temperature-memory effect (TME) between 16 and 99 degrees C related to a broad melting transition (similar to 100 degrees C). The nanostructural changes in such cPEVAs during programming and activation of the TME were analyzed via in situ X-ray scattering and specific annealing experiments. Different contributions to the mechanism of memorizing high or low deformation temperatures (T-deform) were observed in cPEVA, which can be associated to the average PE crystal sizes. At high deformation temperatures (>50 degrees C), newly formed PE crystals, which are established during cooling when fixing the temporary shape, dominated the TME mechanism. In contrast, at low T-deform (<50 degrees C), corresponding to a cold drawing scenario, the deformation led preferably to a disruption of existing large crystals into smaller ones, which then fix the temporary shape upon cooling. The observed mechanism of memorizing a deformation temperature might enable the prediction of the TME behavior and the knowledge based design of other TMPs with crystallizable controlling units.
By dropping a NaH2PO4 center dot H2O precursor solution to a CaCl2 solution at 90 degrees C under continuous stirring in presence of two biopolymers, i.e. gelatin (G) and chitosan (C), supramolecular calcium phosphate (CP) card house structures are formed. Light microscopic investigations in combination with scanning electron microscopy show that the GC-based flower-like structure is constructed from very thin CP platelets. Titration experiments indicate that H-bonding between both biopolymers is responsible for the synergistic effect in presence of both polymers. Gelatin chitosan water complexes play an important role with regard to supramolecular ordering. FTIR spectra in combination with powder X-ray diffraction show that after burning off all organic components (heating up >600 degrees C) dicalcium and tricalcium phosphate crystallites are formed. From high resolution transmission electron microscopy (HR-TEM) it is obvious to conclude, that individual crystal platelets are dicalcium phosphates, which build up ball-like supramolecular structures. The results reveal that the GC guided crystal growth leads to nano-porous supramolecular structures, potentially attractive candidates for bone repair. (c) 2015 Elsevier B.V. All rights reserved.