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The time-dependent approach to electronic spectroscopy, as popularized by Heller and coworkers in the 1980's, is applied here in conjunction with linear-response, time-dependent density functional theory to study vibronic absorption, emission and resonance Raman spectra of several diamondoids. Two-state models, the harmonic and the Condon approximations, are used for the calculations, making them easily applicable to larger molecules. The method is applied to nine pristine lower and higher diamondoids: adamantane, diamantane, triamantane, and three isomers each of tetramantane and pentamantane. We also consider a hybrid species “Dia = Dia” – a shorthand notation for a recently synthesized molecule comprising two diamantane units connected by a C[double bond, length as m-dash]C double bond. We resolve and interpret trends in optical and vibrational properties of these molecules as a function of their size, shape, and symmetry, as well as effects of “blending” with sp2-hybridized C-atoms. Time-dependent correlation functions facilitate the computations and shed light on the vibrational dynamics following electronic transitions.
Through the reactions of 1-aminomethyl-2-naphthol and substituted 1-aminobenzyl-2-naphthols with 3,4-dihydroisoquinoline or 6,7-dimethoxy-3,4-dihydroisoquinoline under microwave conditions, naphth[1,2-e][1,3]oxazino[2,3-a]-isoquinoline derivatives were prepared in good yields. The latter reaction was extended by using 2-aminoarylmethyl-1-naphthols, leading to isomeric naphth-[2,1-e][1,3]oxazino[2,3-a] isoquinolines. Beside the detailed NMR spectroscopic and theoretical study of both stereochemistry and dynamic behaviour of these new conformational flexible heterocyclic ring systems an unexpected dynamic process between two diastereomers was observed in solution, studied by variable temperature H-1 NMR spectroscopy and the mechanism proved by theoretical DFT computations.
Transcriptome analysis through next-generation sequencing technologies allows the generation of detailed gene catalogs for non-model species, at the cost of new challenges with regards to computational requirements and bioinformatics expertise. Here, we present TRAPID, an online tool for the fast and efficient processing of assembled RNA-Seq transcriptome data, developed to mitigate these challenges. TRAPID offers high-throughput open reading frame detection, frameshift correction and includes a functional, comparative and phylogenetic toolbox, making use of 175 reference proteomes. Benchmarking and comparison against state-of-the-art transcript analysis tools reveals the efficiency and unique features of the TRAPID system.
Silver nanoparticles (SNPs) are among the most commercialized nanoparticles because of their antibacterial effects. Besides being employed, e. g. as a coatingmaterial for sterile surfaces in household articles and appliances, the particles are also used in a broad range of medical applications. Their antibacterial properties make SNPs especially useful for wound disinfection or as a coating material for prostheses and surgical instruments. Because of their optical characteristics, the particles are of increasing interest in biodetection as well. Despite the widespread use of SNPs, there is little knowledge of their toxicity. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) and laser post-ionization secondary neutral mass spectrometry (Laser-SNMS) were used to investigate the effects of SNPs on human macrophages derived from THP-1 cells in vitro. For this purpose, macrophages were exposed to SNPs. The SNP concentration ranges were chosen with regard to functional impairments of the macrophages. To optimize the analysis of the macrophages, a special silicon wafer sandwich preparation technique was employed; ToF-SIMS was employed to characterize fragments originating from macrophage cell membranes. With the use of this optimized sample preparation method, the SNP-exposed macrophages were analyzed with ToF-SIMS and with Laser-SNMS. With Laser-SNMS, the three-dimensional distribution of SNPs in cells could be readily detected with very high efficiency, sensitivity, and submicron lateral resolution. We found an accumulation of SNPs directly beneath the cell membrane in a nanoparticular state as well as agglomerations of SNPs inside the cells.
Silver nanoparticles (SNP) are among the most commercialized nanoparticles. Here, we show that peptide-coated SNP cause functional impairment of human macrophages. A dose-dependent inhibition of phagocytosis is observed after nanoparticle treatment, and pretreatment of cells with N-acetyl cysteine (NAC) can counteract the phagocytosis disturbances caused by SNP.
Using the surface-sensitive mode of time-of-flight secondary ion mass spectrometry, in combination with multivariate statistical methods, we studied the composition of cell membranes in human macrophages upon exposure to SNP with and without NAC preconditioning. This method revealed characteristic changes in the lipid pattern of the cellular membrane outer leaflet in those cells challenged by SNP. Statistical analyses resulted in 19 characteristic ions, which can be used to distinguish between NAC pretreated and untreated macrophages. The present study discusses the assignments of surface cell membrane phospholipids for the identified ions and the resulting changes in the phospholipid pattern of treated cells. We conclude that the adverse effects in human macrophages caused by SNP can be partially reversed through NAC administration. Some alterations, however, remained.
Thick poly(styrene-b-monomethoxydiethylenglycol-acrylate-b-styrene) [P(S-b-MDEGA-b-S)] films (thickness 5 mu m) are prepared from different solvents on flexible substrates by solution casting and investigated with small-angle X-ray scattering. As the solvents are either PS- or PMDEGA-selective, micelles with different core-shell micellar structures are formed. In PMDEGA-selective solvents, the PS block is the core and PMDEGA is the shell, whereas in PS-selective solvents, the order is reversed. After exposing the films to liquid D2O, the micellar structure inside the films prepared from PMDEGA-selective solvents remains unchanged and only the PMDEGA (shell part) swells. On the contrary, in the films prepared from PS-selective solvents, the micelles revert the core and the shell. This reversal causes more entanglements of the PMDEGA chains between the micelles. Moreover, the thermal collapse transition of the PMDEGA block in liquid D2O is significantly broadened. Irrespective of the solvent used for film preparation, the swollen PMDEGA shell does not show a prominent shrinkage when passing the phase transition, and the transition process occurs via compaction. The collapsed micelles have a tendency to densely pack above the transition temperature.
Despite the critical importance of the hydroxyl radical in major scientific fields, there are still open questions on the behavior of this species in the aqueous phase. In particular, there has been much debate on the existence of a hemibonded interaction between the hydroxyl radical and water molecules. While some reports indicate that the hemibonded radical might explain some experimental data, others have claimed that this interaction is simply a density functional theory (DFT) artifact. Here, we provide results from high level (basis set limit of coupled-cluster levels up to single, double, triple excitations (CCSD(T)) and beyond) ab initio calculations of different OH center dot(H2O)(n) clusters in the gas phase to accurately explore the existence of the hemibonded interaction and its energy difference with respect to other well-defined hydrogen bond interactions. Additional comparisons with second order perturbation theory (MP2) and DFT are also presented. Constrained molecular dynamics was applied to determine the free energy for the formation/disruption and ice systems. Overall, our findings confirm that the hemibond can be an alternative structure for the hydroxyl radical in the condensed phase when the formation of hydrogen bonds is impeded. These results will aid the understanding of theoretical and experimental data and help future experimental designs for the detection of this important species.
We present and discuss the results of crystallographic and electron paramagnetic resonance (EPR) spectroscopic analyses of five tetrachloridocuprate(II) complexes to supply a useful tool for the structural characterisation of the [CuCl4]2− moiety in the liquid state, for example in ionic liquids, or in solution. Bis(benzyltriethylammonium)-, bis(trimethylphenylammonium)-, bis(ethyltriphenylphosphonium)-, bis(benzyltriphenylphosphonium)-, and bis(tetraphenylarsonium)tetrachloridocuprate(II) were synthesised and characterised by elemental, IR, EPR and X-ray analyses. The results of the crystallographic analyses show distorted tetrahedral coordination geometry of all [CuCl4]2− anions in the five complexes and prove that all investigated complexes are stabilised by hydrogen bonds of different intensities. Despite the use of sterically demanding ammonium, phosphonium and arsonium cations to obtain the separation of the paramagnetic Cu(II) centres for EPR spectroscopy no hyperfine structure was observed in the EPR spectra but the principal values of the electron Zeeman tensor, g∥ and g⊥, could be determined. With these EPR data and the crystallographic parameters we were able to carry out a correlation study to anticipate the structural situation of tetrachloridocuprates in different physical states. This correlation is in good agreement with DFT calculations.
Tetrahalidocuprat(II)-komplexe : Untersuchungen zur Relation von Struktur- und EPR-Parametern
(2013)
A Co(II)–imidazolate-4-amide-5-imidate based MOF, IFP-5, is synthesized by using an imidazolate anion-based novel ionic liquid as a linker precursor under solvothermal conditions. IFP-5 shows significant amounts of gas (N2, CO2, CH4 and H2) uptake capacities. IFP-5 exhibits an independent high spin Co(II) centre and antiferromagnetic coupling.
Fluorescence probes consisting of well-established fluorophores in combination with rigid molecular rods based on spirane-type structures were investigated with respect to their fluorescence properties under different solvent conditions. The attachment of the dyes was accomplished by 1,3-dipolar cycloaddition between alkynes and azides (click' reaction) and is a prime example for a novel class of sensor constructs. Especially, the attachment of two (different) fluorophores on opposite sides of the molecular rods paves the way to new sensor systems with less bulky (compared to the conventional DNA- or protein-based concepts), nevertheless rigid spacer constructs, e.g., for FRET-based sensing applications. A detailed photophysical characterization was performed in MeOH (and in basic H2O/MeOH mixtures) for i) rod constructs containing carboxyfluorescein, ii) rod constructs containing carboxyrhodamine, iii) rod constructs containing both carboxyfluorescein and carboxyrhodamine, and iv) rod constructs containing both pyrene and perylene parts. For each dye (pair), two rod lengths with different numbers of spirane units were synthesized and investigated. The rod constructs were characterized in ensemble as well as single-molecule fluorescence experiments with respect to i) specific roddye and ii) dyedye interactions. In addition to MeOH and MeOH/NaOH, the rod constructs were also investigated in micellar systems, which were chosen as a simplified model for membranes.
In this work, thermosensitive hydrogels having tunable thermo-mechanical properties were synthesized. Generally the thermal transition of thermosensitive hydrogels is based on either a lower critical solution temperature (LCST) or critical micelle concentration/ temperature (CMC/ CMT). The temperature dependent transition from sol to gel with large volume change may be seen in the former type of thermosensitive hydrogels and is negligible in CMC/ CMT dependent systems. The change in volume leads to exclusion of water molecules, resulting in shrinking and stiffening of system above the transition temperature. The volume change can be undesired when cells are to be incorporated in the system. The gelation in the latter case is mainly driven by micelle formation above the transition temperature and further colloidal packing of micelles around the gelation temperature. As the gelation mainly depends on concentration of polymer, such a system could undergo fast dissolution upon addition of solvent. Here, it was envisioned to realize a thermosensitive gel based on two components, one responsible for a change in mechanical properties by formation of reversible netpoints upon heating without volume change, and second component conferring degradability on demand. As first component, an ABA triblockcopolymer (here: Poly(ethylene glycol)-b-poly(propylene glycol)-b-poly(ethylene glycol) (PEPE) with thermosensitive properties, whose sol-gel transition on the molecular level is based on micellization and colloidal jamming of the formed micelles was chosen, while for the additional macromolecular component crosslinking the formed micelles biopolymers were employed. The synthesis of the hydrogels was performed in two ways, either by physical mixing of compounds showing electrostatic interactions, or by covalent coupling of the components. Biopolymers (here: the polysaccharides hyaluronic acid, chondroitin sulphate, or pectin, as well as the protein gelatin) were employed as additional macromolecular crosslinker to simultaneously incorporate an enzyme responsiveness into the systems. In order to have strong ionic/electrostatic interactions between PEPE and polysaccharides, PEPE was aminated to yield predominantly mono- or di-substituted PEPEs. The systems based on aminated PEPE physically mixed with HA showed an enhancement in the mechanical properties such as, elastic modulus (G′) and viscous modulus (G′′) and a decrease of the gelation temperature (Tgel) compared to the PEPE at same concentration. Furthermore, by varying the amount of aminated PEPE in the composition, the Tgel of the system could be tailored to 27-36 °C. The physical mixtures of HA with di-amino PEPE (HA·di-PEPE) showed higher elastic moduli G′ and stability towards dissolution compared to the physical mixtures of HA with mono-amino PEPE (HA·mono-PEPE). This indicates a strong influence of electrostatic interaction between –COOH groups of HA and –NH2 groups of PEPE. The physical properties of HA with di-amino PEPE (HA·di-PEPE) compare beneficially with the physical properties of the human vitreous body, the systems are highly transparent, and have a comparable refractive index and viscosity. Therefore,this material was tested for a potential biological application and was shown to be non-cytotoxic in eluate and direct contact tests. The materials will in the future be investigated in further studies as vitreous body substitutes. In addition, enzymatic degradation of these hydrogels was performed using hyaluronidase to specifically degrade the HA. During the degradation of these hydrogels, increase in the Tgel was observed along with decrease in the mechanical properties. The aminated PEPE were further utilised in the covalent coupling to Pectin and chondroitin sulphate by using EDC as a coupling agent. Here, it was possible to adjust the Tgel (28-33 °C) by varying the grafting density of PEPE to the biopolymer. The grafting of PEPE to Pectin enhanced the thermal stability of the hydrogel. The Pec-g-PEPE hydrogels were degradable by enzymes with slight increase in Tgel and decrease in G′ during the degradation time. The covalent coupling of aminated PEPE to HA was performed by DMTMM as a coupling agent. This method of coupling was observed to be more efficient compared to EDC mediated coupling. Moreover, the purification of the final product was performed by ultrafiltration technique, which efficiently removed the unreacted PEPE from the final product, which was not sufficiently achieved by dialysis. Interestingly, the final products of these reaction were in a gel state and showed enhancement in the mechanical properties at very low concentrations (2.5 wt%) near body temperature. In these hydrogels the resulting increase in mechanical properties was due to the combined effect of micelle packing (physical interactions) by PEPE and covalent netpoints between PEPE and HA. PEPE alone or the physical mixtures of the same components were not able to show thermosensitive behavior at concentrations below 16 wt%. These thermosensitive hydrogels also showed on demand solubilisation by enzymatic degradation. The concept of thermosensitivity was introduced to 3D architectured porous hydrogels, by covalently grafting the PEPE to gelatin and crosslinking with LDI as a crosslinker. Here, the grafted PEPE resulted in a decrease in the helix formation in gelatin chains and after fixing the gelatin chains by crosslinking, the system showed an enhancement in the mechanical properties upon heating (34-42 °C) which was reversible upon cooling. A possible explanation of the reversible changes in mechanical properties is the strong physical interactions between micelles formed by PEPE being covalently linked to gelatin. Above the transition temperature, the local properties were evaluated by AFM indentation of pore walls in which an increase in elastic modulus (E) at higher temperature (37 °C) was observed. The water uptake of these thermosensitive architectured porous hydrogels was also influenced by PEPE and temperature (25 °C and 37 °C), showing lower water up take at higher temperature and vice versa. In addition, due to the lower water uptake at high temperature, the rate of hydrolytic degradation of these systems was found to be decreased when compared to pure gelatin architectured porous hydrogels. Such temperature sensitive architectured porous hydrogels could be important for e.g. stem cell culturing, cell differentiation and guided cell migration, etc. Altogether, it was possible to demonstrate that the crosslinking of micelles by a macromolecular crosslinker increased the shear moduli, viscosity, and stability towards dissolution of CMC-based gels. This effect could be likewise be realized by covalent or non-covalent mechanisms such as, micelle interactions, physical interactions of gelatin chains and physical interactions between gelatin chains and micelles. Moreover, the covalent grafting of PEPE will create additional net-points which also influence the mechanical properties of thermosensitive architectured porous hydrogels. Overall, the physical and chemical interactions and reversible physical interactions in such thermosensitive architectured porous hydrogels gave a control over the mechanical properties of such complex system. The hydrogels showing change of mechanical properties without a sol-gel transition or volume change are especially interesting for further study with cell proliferation and differentiation.
A rare example of in situ linker generation with the formation of soft porous Zn- and Co-MOFs (IFP-9 and -10, respectively) is reported. The flexible ethoxy groups of IFP-9 and -10 protrude into the 1D hexagonal channels. The gas-sorption behavior of both materials for H2, CO2 and CH4 showed wide hysteretic isotherms, typical for MOFs having a flexible substituent which can give rise to a gate effect.
A rare example of in situ linker generation with the formation of soft porous Zn- and Co-MOFs (IFP-9 and -10, respectively) is reported. The flexible ethoxy groups of IFP-9 and -10 protrude into the 1D hexagonal channels. The gas-sorption behavior of both materials for H-2, CO2 and CH4 showed wide hysteretic isotherms, typical for MOFs having a flexible substituent which can give rise to a gate effect.
The photochemistry as well as electrochemistry of novel donor-acceptor bis(morpholinothiazolyl)maleimides has been investigated. Proper substitution of these diarylethene-type molecular switches leads to the unique situation in which their ring-closure can only be accomplished electrochemically, while ring-opening can only be achieved photochemically. Hence, these switches operate with orthogonal stimuli, i.e. redox potential and light, respectively. The switch system could be optimized by introducing trifluoromethyl groups at the reactive carbon atoms in order to avoid by-product formation during oxidative ring closure. Both photochemical and electrochemical pathways were investigated for methylated, trifluoromethylated, and nonsymmetrical bis(morpholinothiazolyl) maleimides as well as the bis(morpholinothiazolyl) cyclopentene reference compound. With the aid of the nonsymmetrical "mixed" derivative, the mechanism of electrochemically driven ring closure could be elucidated and seems to proceed via a dicationic intermediate generated by two-fold oxidation. All experimental work has been complemented by density functional theory that provides detailed insights into the thermodynamics of the ring-open and closed forms, the nature of their excited states, and the reactivity of their neutral as well as ionized species in different electronic configurations. The particular diarylethene systems described herein could serve in multifunctional (logic) devices operated by different stimuli (inputs) and may pave the way to converting light into electrical energy via photoinduced "pumping" of redox-active meta-stable states.
The adsorption of boron (boric acid) from aqueous solutions on alumina has been investigated at pH 8.0, I=0.1M NaClO4, T=22 +/- 3 degrees C, and under normal atmospheric conditions. The characterization of the adsorbed species was performed by Raman spectroscopy and the spectroscopic speciation was assisted by theoretical DFT calculations. Evaluation of the spectroscopic data points to the formation of inner-sphere surface complexes and indicates the formation of two different types of adsorbed boron species. The theoretical calculations corroborate the spectroscopic data and indicate that at low boron concentration the monodentate surface species dominates, whereas increased boron concentration favors the formation of a bidentate surface species. Assuming low coverage, the conditional formation constant for the monodentate surface species has been evaluated to be log=4.1 +/- 0.1.
Nicotinamide (nia) has been employed as a supramolecular reagent in the synthesis of four copper(II) chloro- and dichlorobenzoate (Clbz/Cl(2)bz) complexes. The structures of the compounds [Cu(2-Clbz)(2) (nia)(2)(H2O)(2)] (1), icu(4-clbz)(2)(nia)(2)(H2O)(2)] (2), [Cu(3,5-Cl(2)bz)(2)(nia)(2)(H2O)(2)] (3), and [Cu(2,5-Cl(2)bz)(2) (nia)(2)(H2O)]center dot H2O (4) were determined. All the investigated compounds 1-4 reveal water molecules as coordinated. Their structures show distorted octahedral chromophores (CuN2O2O)-N-II'(2), though some are better described as square-planar or square-pyramid due to a large deviation of the axial ligand away from the octahedral z-axis along with different Cu center dot center dot center dot O (axial) lengths. The equatorial positions are occupied in all four cases by two nitrogen (nia-py) atoms and two carboxylate oxygen atoms of two Clbz/Cl(2)bz ligands, while the axial positions are occupied by water molecules. The EPR spectra reveal for all 1-4 compounds a spin state of S = 1/2, mostly with axial symmetry of the spectra. Their resolution is clearly dependant to the crystal symmetry related equivalence of the magnetic sites. The coordination molecules of all compounds are connected by N-H center dot center dot center dot O and O-H center dot center dot center dot O H-bonds from nicotinamide NH2 groups, carboxylate anions and/or water molecules, which create supramolecular chains or further H-bonded into 2D sheets. Steric hindering of the chlorine atoms of the Clbz/Cl(2)bz, especially seen at the coordination of the water molecules, demonstrates its role at the coordination sphere appearance. Despite this influence, the water molecules in 1-4 always assist at the similar supramolecular H-bonded network, almost at the same manner.
Trithiaazapentalene derivatives were prepared by the reaction of 2-alkylidene-4-oxothiazolidines with Lawesson's reagent. They are classified as two structurally different trithiaazapentalene compounds that have different contributions of monocyclic 1,2-dithiole and 1,2,4-dithiazole structures and degrees of aromaticity of the bicyclic trithiaazapentalene system. The electron-donating ability of substituents at the C(5) position of the trithiaazapentalene system is recognized as the main cause for changes in pi-Celectron distribution. This is the first complete study of substituent effects on the structure of trithiapentalenes. (C) 2013 Elsevier Ltd. All rights reserved.
We demonstrate new fluorophore-labelled materials based on acrylamide and on oligo(ethylene glycol) (OEG) bearing thermoresponsive polymers for sensing purposes and investigate their thermally induced solubility transitions. It is found that the emission properties of the polarity-sensitive (solvatochromic) naphthalimide derivative attached to three different thermoresponsive polymers are highly specific to the exact chemical structure of the macromolecule. While the dye emits very weakly below the LCST when incorporated into poly(N-isopropylacrylamide) (pNIPAm) or into a polyacrylate backbone bearing only short OEG side chains, it is strongly emissive in polymethacrylates with longer OEG side chains. Heating of the aqueous solutions above their cloud point provokes an abrupt increase of the fluorescence intensity of the labelled pNIPAm, whereas the emission properties of the dye are rather unaffected as OEG-based polyacrylates and methacrylates undergo phase transition. Correlated with laser light scattering studies, these findings are ascribed to the different degrees of pre-aggregation of the chains at low temperatures and to the extent of dehydration that the phase transition evokes. It is concluded that although the temperature-triggered changes in the macroscopic absorption characteristics, related to large-scale alterations of the polymer chain conformation and aggregation, are well detectable and similar for these LCST-type polymers, the micro-environment provided to the dye within each polymer network differs substantially. Considering sensing applications, this finding is of great importance since the temperature-regulated fluorescence response of the polymer depends more on the macromolecular architecture than the type of reporter fluorophore.
We demonstrate new fluorophore-labelled materials based on acrylamide and on oligo(ethylene glycol) (OEG) bearing thermoresponsive polymers for sensing purposes and investigate their thermally induced solubility transitions. It is found that the emission properties of the polarity-sensitive (solvatochromic) naphthalimide derivative attached to three different thermoresponsive polymers are highly specific to the exact chemical structure of the macromolecule. While the dye emits very weakly below the LCST when incorporated into poly(N-isopropylacrylamide) (pNIPAm) or into a polyacrylate backbone bearing only short OEG side chains, it is strongly emissive in polymethacrylates with longer OEG side chains. Heating of the aqueous solutions above their cloud point provokes an abrupt increase of the fluorescence intensity of the labelled pNIPAm, whereas the emission properties of the dye are rather unaffected as OEG-based polyacrylates and methacrylates undergo phase transition. Correlated with laser light scattering studies, these findings are ascribed to the different degrees of pre-aggregation of the chains at low temperatures and to the extent of dehydration that the phase transition evokes. It is concluded that although the temperature-triggered changes in the macroscopic absorption characteristics, related to large-scale alterations of the polymer chain conformation and aggregation, are well detectable and similar for these LCST-type polymers, the micro-environment provided to the dye within each polymer network differs substantially. Considering sensing applications, this finding is of great importance since the temperature-regulated fluorescence response of the polymer depends more on the macromolecular architecture than the type of reporter fluorophore.
Thin thermoresponsive films of the triblock copolymer polystyrene-block-poly(methoxydiethylene glycol acrylate)-block-polystyrene (P(S-b-MDEGA-b-S)) are investigated on silicon substrates. By spin coating, homogeneous and smooth films are prepared for a range of film thicknesses from 6 to 82 nm. Films are stable with respect to dewetting as investigated with optical microscopy and atomic force microscopy. P(S-b-MDEGA-b-S) films with a thickness of 39 nm exhibit a phase transition of the lower critical solution temperature (LCST) type at 36.5 degrees C. The swelling and the thermoresponsive behavior of the films with respect to a sudden thermal stimulus are probed with in-situ neutron reflectivity. In undersaturated water vapor swelling proceeds without thickness increase. The thermoresponse proceeds in three steps: First, the film rejects water as the temperature is above LCST. Next, it stays constant for 600 s, before the collapsed film takes up water again. With ATR-FTIR measurements, changes of bound water in the film caused by different thermal stimuli are studied. Hydrogen bonds only form between C=O and water in the swollen film. Above the LCST most hydrogen bonds with water are broken, but some amount of bound water remains inside the film in agreement with the neutron reflectivity data. Grazing-incidence small-angle X-ray scattering (GISAXS) shows that the inner lateral structure is not significantly influenced by the different thermal stimuli.
Molecular rods consisting of a hydrophobic backbone and terminally varying functional groups have been synthesized for applications for the functionalization of membranes. In the present study, we employ a spin-labeled analogue of a recently described new class of molecular rods to characterize their dynamic interactions with membranes. By using the different approaches of ESR and NMR spectroscopy, we show that the spin moiety of the membrane-embedded spin-labeled rod is localized in the upper chain/glycerol region of membranes of different compositions. The rod is embedded within the membrane in a tilted orientation to adjust for the varying hydrophobic thicknesses of these bilayers. This orientation does not perturb the membrane structure. The water solubility of the rod is increased significantly in the presence of certain cyclodextrins. These cyclodextrins also allow the rods to be extracted from the membrane and incorporated into preformed membranes. The latter will improve the future applications of these rods in cellular systems as stable membrane-associated anchors for the functionalization of membrane surfaces.
Stereoselective synthesis of dienyl phosphonates via extended tethered ring-closing metathesis
(2013)
Allylphosphonates of allylic alcohols were converted to conjugated dienyl phosphonates in a one-flask reaction, comprising a ring-closing metathesis (RCM), a base-induced ring-opening, and an alkylation. The ring-opening proceeds with very high diastereoselectivity, giving exclusively the (1Z,3E)-configured dienes. Single diastereomers and mixtures of diastereomers can be used as starting materials without noticeable effect on the diastereoselectivity of the sequence.
Standard quantum chemical methods are used for accurate calculation of thermochemical properties such as enthalpies of formation, entropies and Gibbs energies of formation. Equilibrium reactions are widely investigated and experimental measurements often lead to a range of reaction Gibbs energies and equilibrium constants. It is useful to calculate these equilibrium properties from quantum chemical methods in order to address the experimental differences. Furthermore, most standard calculation methods differ in accuracy and feasibility of the system size. Hence, asystematic comparison of equilibrium properties calculated with different numerical algorithms would provide a useful reference. We select two well-known gas phase equilibrium reactions with small molecules: covalent dimer formation of NO2 (2NO(2) reversible arrow N2O4) and the synthesis of NH3 (N-2 + 3 H-2 reversible arrow 2NH(3)). We test four quantum chemical methods denoted by G3B3, CBS-APNO, W1 and CCSD(T) with aug-cc-pVXZ basis sets (X = 2, 3, and 4), to obtain thermochemical data for NO2, N2O4, and NH3. The calculated standard formation Gibbs energies Delta(f)G degrees are used to calculate standard reaction Gibbs energies Delta(r)G degrees and standard equilibrium constants K-eq for the two reactions. Standard formation enthalpies Delta H-f degrees are calculated in a more reliable way using high-level methods such as W1 and CCSD(T). Standard entropies S degrees for the molecules are calculated well within the range of experiments for all methods, however, the values of standard formation Gibbs energies Delta(f)G degrees show some dependence on the choice of the method. High-level methods perform better for the calculation of molecular energies, however, simpler methods such as G3B3 and CBS-APNO perform quite well in the calculation of total reaction energies and equilibrium constants, provided that the chemical species involved do not exhibit molecular geometries that are difficult to handle by the applied method. The temperature dependence of standard reaction Gibbs energy Delta(r)G degrees for the NH3 reaction is discussed by using the calculated standard formation Gibbs energies Delta(f)G degrees of the reaction species at 298.15 K. The corresponding equilibrium constant K-eq as a function of temperature is found to be close to experimental values.
Six-color time-resolved forster resonance energy transfer for ultrasensitive multiplexed biosensing
(2013)
Simultaneous monitoring of multiple molecular interactions and multiplexed detection of several diagnostic biomarkers at very low concentrations have become important issues in advanced biological and chemical sensing. Here we present an optically multiplexed six-color Forster resonance energy transfer (FRET) biosensor for simultaneous monitoring of five different individual binding events. We combined simultaneous FRET from one Tb complex to five different organic dyes measured in a filter-based time-resolved detection format with a sophisticated spectral crosstalk correction, which results in very efficient background suppression. The advantages and robustness of the multiplexed FRET sensor were exemplified by analyzing a 15-component lung cancer immunoassay involving 10 different antibodies and five different tumor markers in a single 50 mu L human serum sample. The multiplexed biosensor offers clinically relevant detection limits in the low picomolar (ng/mL) concentration range for all five markers, thus providing an effective early screening tool for lung cancer with the possibility of distinguishing small-cell from non-small-cell lung carcinoma. This novel technology will open new doors for multiple biomarker diagnostics as well as multiplexed real-time imaging and spectroscopy.
In this paper, we report simulations of laser-driven many-electron dynamics by means of the time-dependent configuration interaction singles (TD-CIS) approach. Photoionization is included by a heuristic model within calculations employing standard Gaussian basis sets. Benzo[g]-N-methyl-quinolinium-7-hydroxylate (BMQ7H) serves as a test system to generate predefined wave packets, i.e. a superposition between the ground and fifth excited state, in a large molecule. For this molecule, these two states have a very similar geometry, which enables us to use the fixed nuclei approximation. Furthermore, this geometric stability would also prevent a dephasing of the electron wave packet due to nuclear dynamics in an experimental realization of our simulations. We also simulate the possible detection of such a wave packet by ultra short probe laser pulses, i.e. pump-probe spectra.
The thermally induced shape-memory effect of polymers is typically characterized by cyclic uniaxial thermomechanical tests. Here, a molecular-dynamics (MD) simulation approach of such a cyclic uniaxial thermomechanical test is presented for amorphous switching domains of poly(L-lactide) (PLLA). Uniaxial deformation of the constructed PLLA models is simulated with a Parinello-Rahman scheme, as well as a pragmatic geometrical approach. We are able to describe two subsequent test cycles using the presented simulation approach. The obtained simulated shape-memory properties in both test cycles are similar and independent of the applied deformation protocols. The simulated PLLA shows high shape fixity ratios (Rf 94%), but only a moderate shape recovery ratio is obtained (Rr 30%). Finally, the structural changes during the simulated test are characterized by analysis of the changes in the dihedral angle distributions.
Silacyclohexanes and silaheterocyclohexanes-why are they so different from other heterocyclohexanes?
(2013)
Stereochemical studies on silaheterocyclohexanes is a 'hot topic' as evidenced by the growing number of publications. During last 10 years a substantial number of substituted silacyclohexanes and heterocyclohexanes containing sulfur, oxygen or nitrogen as the second (or third) heteroatom have been synthesized and studied by variable temperature dynamic NMR spectroscopy, gas-phase electron diffraction, variable temperature IR, Raman, microwave spectroscopy with respect to thermodynamic (frozen conformational equilibria) and kinetic (barrier to ring inversion) information. As the stereochemistry of cyclohexane and its N-, O-, P-, S-hetero analogues is one of keystones of modern theoretical and synthetic organic and heterocyclic chemistry, the stereochemistry of silacyclohexane and its hetero analogs is an important element of theoretical and synthetic organosilicon chemistry. The various classes of saturated six-membered rings were critically compared and studied in detail with respect to differences in their stereochemistry and dynamic behavior.
4-Phenol diazonium salts undergo Pd-catalyzed Heck reactions with various styrenes to 4’-hydroxy stilbenes. In almost all cases higher yields and fewer side products were observed, compared to the analogous 4-methoxy benzene diazonium salts. In contrast, the reaction fails completely with 2- and 3-phenol diazonium salts. For these substitution patterns the methoxy-substituted derivatives are superior.
4-Phenol diazonium salts undergo Pd-catalyzed Heck reactions with various styrenes to 4'-hydroxy stilbenes. In almost all cases higher yields and fewer side products were observed, compared to the analogous 4-methoxy benzene diazonium salts. In contrast, the reaction fails completely with 2- and 3-phenol diazonium salts. For these substitution patterns the methoxy-substituted derivatives are superior.
A new sulfonated aniline-modified poly(vinyl alcohol)/K-feldspar (SAPK) composite was prepared. The cation-exchange capacity of the composite was found to be S times that of neat feldspar. The specific surface area and point of zero charge also changed significantly upon modification, from 15.6 +/- 0.1 m(2)/g and 2.20 (K-feldspar) to 73.6 +/- 0.3 m(2)/g and 1.91 (SAPK). Zn2+, Cd2+, and Pb2+ adsorption was found to be largely independent of pH, and the metal adsorption rate on SAPK was higher than that on neat feldspar. This particularly applies to the initial adsorption rates. The adsorption process involves both film and pore diffusion; film diffusion initially controls the adsorption. The Freundlich and Langmuir models were found to fit metal-ion adsorption on SAPK most accurately. Adsorption on neat feldspar was best fitted with a Langmuir model, indicating the formation of adsorbate monolayers. Both pure feldspar and SAPK showed better selectivity for Pb2+ than for Cd2+ or Zn2+.
The new N-heterocyclic carbene (NHC) precursors 4,5-dicyano-1, -dimesityl- (9) and 4, 5-dicyano-1, 3-dineopentyl-2-(pentafluorophenyl)imidazoline (14) were synthesized. 9 could be determined by X-ray crystallography. With the 2-pentafluorophenyl-substituted imidazolines 9 and 14, the [AgCl(NHC)], [RhCl(COD)(NHC)], and [RhCl(CO)(2)(NHC)] complexes [NHC = 4, 5-dicyano-1, 3-dimesitylimidazol-2-ylidene (3) and 4, 5-dicyano-1, 3-dineopentylimidazol-2-ylidene (4)] were obtained. Crystal structures of [AgCl(3)] (15), [RhCl(COD)(3)] (17), [RhCl(COD)(4)] (18), and [RhCl(CO)(2)(3)] (19) were solved and with the crystal data of 19, the percent buried volume (%V-bur) of 31.8(+/- 0.1)% was determined for NHC 3. Infrared spectra of the imidazolines 9 and 14 and of the complexes 15-20 were recorded and the CO stretching frequencies of complexes 19 and 20 were used to determine the 3 ( (-1)) and 4 ( (-1)), thus proving that 1, 3-substitution of maleonitrile-NHCs does not have a significant effect for the high -acceptor strength of these carbenes.
Shape-memory polymers (SMPs) are stimuli-sensitive materials capable of performing complex movements on demand, which makes them interesting candidates for various applications, for example, in biomedicine or aerospace. This trend article highlights current approaches in the chemistry of SMPs, such as tailored segment chemistry to integrate additional functions and novel synthetic routes toward permanent and temporary netpoints. Multiphase polymer networks and multimaterial systems illustrate that SMPs can be constructed as a modular system of different building blocks and netpoints. Future developments are aiming at multifunctional and multistimuli-sensitive SMPs.
We investigate the recombinative desorption of hydrogen and deuterium from a Ru(0001) surface initiated by femtosecond laser pulses. We adopt a quantum mechanical two-state model including three molecular degrees of freedom to describe the dynamics within the desorption induced by electronic transition (DIET) limit. The energy distributions as well as the state-resolved and ensemble properties of the desorbed molecules are analyzed in detail by using the time-energy method. Our results shed light on the experimentally observed 1) large isotopic effects regarding desorption yields and translational energies and 2) the nonequal energy partitioning into internal and translational modes. In particular, it is shown that a single temperature is sufficient to characterize the energy distributions for all degrees of freedom. Further, we confirm that quantization effects play an important role in the determination of the energy partitioning.
Push-pull allenes-conjugation, (anti)aromaticity and quantification of the push-pull character
(2013)
Structures, H-1/C-13 chemical shifts, and pi electron distribution/conjugation of an experimentally available and theoretically completed set of push-pull allenes Acc(2)C=C=CDon(2) (Acc=F, CHO, CF3, C N; Don=t-Bu, OMe, OEt, SMe, SEt, NCH2R) have been computed at the OFT level of theory. Both orthogonal linear and orthogonal bent structures have been obtained. In the latter case the push-pull character could be quantified by the quotient method. The C-13 chemical shift of the central allene carbon atom C-2 and chemical shift differences Delta delta(C-1, C-2) and Delta delta(C-2, C-3) of allene carbon atoms proved to be a quantitative alternative. TSNMRS of ring-closed push-pull allenes have been computed in addition and were employed to identify polar, carbene-like and carbone-like canonical structures of these molecules.
A homogeneous time-resolved luminescence resonance energy transfer (TR-LRET) assay has been developed to quantify proteins. The competitive assay is based on resonance energy transfer (RET) between two luminescent nanosized particles. Polystyrene nanoparticles loaded with Eu3+ chelates (EuNPs) act as donors, while protein-coated quantum dots (QDs), either CdSe/ZnS emitting at 655 nm (QD655-strep) or CdSeTe/ZnS with emission wavelength at 705 nm (QD705-strep), are acceptors. In the absence of analyte protein, in our case bovine serum albumin (BSA), the protein-coated QDs bind nonspecifically to the EuNPs, leading to RET. In the presence of analyte proteins, the binding of the QDs to the EuNPs is prevented and the RET signal decreases. RET from the EuNPs to the QDs was confirmed and characterized with steady-state and time-resolved luminescence spectroscopy. In accordance with the Forster theory, the approximate average donor acceptor distance is around 15 nm at RET efficiencies, equal to 15% for QD655 and 13% for QD705 acceptor, respectively. The limits of detection are below 10 ng of BSA with less than a 10% average coefficient of variation. The assay sensitivity is improved, when compared to the most sensitive commercial methods. The presented mix-and-measure method has potential to be implemented into routine protein quantification in biological laboratories.
We consider diffusion processes with a spatially varying diffusivity giving rise to anomalous diffusion. Such heterogeneous diffusion processes are analysed for the cases of exponential, power-law, and logarithmic dependencies of the diffusion coefficient on the particle position. Combining analytical approaches with stochastic simulations, we show that the functional form of the space-dependent diffusion coefficient and the initial conditions of the diffusing particles are vital for their statistical and ergodic properties. In all three cases a weak ergodicity breaking between the time and ensemble averaged mean squared displacements is observed. We also demonstrate a population splitting of the time averaged traces into fast and slow diffusers for the case of exponential variation of the diffusivity as well as a particle trapping in the case of the logarithmic diffusivity. Our analysis is complemented by the quantitative study of the space coverage, the diffusive spreading of the probability density, as well as the survival probability.
The present paper is related to interactions between strongly alternating polyampholytes, i.e., copolymers of N,N'-diallyl-N,N'-dimethylammonium chloride and maleamic acid derivatives, varying in hydrophobicity and excess charges and the oppositely charged anionic surfactant sodium dodecyl sulfate (SDS). Surface tension measurements have revealed a complex behavior with the formation of polyampholyte-SDS complexes at water air interfaces which depends on both the hydrophobic character of the polyampholyte and electrostatic attractive forces between the polyampholyte and the anionic surfactant in dependence on pH. Hereby, maleamic acid copolymers with additional carboxylic groups in the phenylic side chain show a significant lower surface tension at the critical association concentration (CAC) due to the formation of surface-active SDS complexes and multicomplexes. In the presence of only one carboxylic group in the p-position the CAC can be strongly shifted by varying the pH due to repulsive electrostatic interactions.
The chain length and end groups of linear PEG grafted on smooth surfaces is known to influence protein adsorption and thrombocyte adhesion. Here, it is explored whether established structure function relationships can be transferred to application relevant, rough surfaces. Functionalization of poly(ether imide) (PEI) membranes by grafting with monoamino PEG of different chain lengths (M-n=1kDa or 10kDa) and end groups (methoxy or hydroxyl) is proven by spectroscopy, changes of surface hydrophilicity, and surface shielding effects. The surface functionalization does lead to reduction of adsorption of BSA, but not of fibrinogen. The thrombocyte adhesion is increased compared to untreated PEI surfaces. Conclusively, rough instead of smooth polymer or gold surfaces should be investigated as relevant models.
We have used polarized confocal Raman microspectroscopy and scanning near-field optical microscopy with a resolution of 60 nm to characterize photoinscribed grating structures of azobenzene doped polymer films on a glass support. Polarized Raman microscopy allowed determining the reorientation of the chromophores as a function of the grating phase and penetration depth of the inscribing laser in three dimensions. We found periodic patterns, which are not restricted to the surface alone, but appear also well below the surface in the bulk of the material. Near-field optical microscopy with nanoscale resolution revealed lateral two-dimensional optical contrast, which is not observable by atomic force and Raman microscopy.
Solid surfaces are modified using photo-crosslinkable copolymers based on oligo(ethylene glycol) methacrylate (OEGMA) bearing 2-(4-benzoylphenoxy) ethyl methacrylate (BPEM) as a photosensitive crosslinking unit. Thin films of about 100 nm are formed by spin-coating these a priori highly biocompatible copolymers onto silicon substrates. Subsequent UV-irradiation assures immobilization and crosslinking of the hydrogel films. Their stability is controlled by the number of crosslinker units per chain and the molar mass of the copolymers. The swelling of the hydrogel layers, as investigated by ellipsometry, can be tuned by the crosslinker content in the copolymer. If films are built from the ternary copolymers of OEGMA, BPEM and 2-(2-methoxyethoxy) ethyl methacrylate (MEO(2)MA), the hydrogel films exhibit a swelling/deswelling transition of the lower critical solution temperature (LCST) type. The observed thermally induced hydrogel collapse is fully reversible and the onset temperature of the transition can be tuned at will by the copolymer composition. Different from analogously prepared thermo-responsive hydrogel films of photocrosslinked poly(N-isopropylacrylamide), the swelling-deswelling transition occurs more gradually, but shows no hysteresis.
Various 1,6- and 1,8-naphthalenophanes were synthesized by using the Photo-Dehydro-Diels-Alder (PDDA) reaction of bis-ynones. These compounds are easily accessible from omega-(3-iodophenyl)carboxylic acids in three steps. The obtained naphthalenophanes are axially chiral and the activation barrier for the atropisomerization could be determined in some cases by means of dynamic NMR (DNMR) and/or dynamic HPLC (DHPLC) experiments.
Various 1,6- and 1,8-naphthalenophanes were synthesized by using the Photo-Dehydro-Diels-Alder (PDDA) reaction of bis-ynones. These compounds are easily accessible from omega-(3-iodophenyl)carboxylic acids in three steps. The obtained naphthalenophanes are axially chiral and the activation barrier for the atropisomerization could be determined in some cases by means of dynamic NMR (DNMR) and/or dynamic HPLC (DHPLC) experiments.
With the present theoretical study of the photochemical switching of E-methylfurylfulgide we contribute an important step towards the understanding of the photochemical processes in furylfulgide-related molecules. We have carried out large-scale, full-dimensional direct semiempirical configuration-interaction surface-hopping dynamics of the photoinduced ring-closure reaction. Simulated static and dynamical UV/Vis-spectra show good agreement with experimental data of the same molecule. By a careful investigation of our dynamical data, we were able to identify marked differences to the dynamics of the previously studied E-isopropylfurylfulgide. With our simulations we can not only reproduce the experimentally observed quantum yield differences qualitatively but we can also pinpoint two reasons for them: kinematics and pre-orientation. With our analysis, we thus offer straightforward molecular explanations for the high sensitivity of the photodynamics towards seemingly minor changes in molecular constitution. Beyond the realm of furylfulgides, these insights provide additional guidance to the rational design of photochemically switchable molecules.
A new class of star-shaped, liquid crystalline, low-molecular weight compounds functionalized with photochromic azobenzene and mesogenic groups was investigated in terms of light-induced anisotropy. The behaviour of the materials under the action of light with simultaneous or subsequent thermal treatment was examined with respect to the induction of anisotropy. The unconventional UV light treatment prior to the irradiation with linearly polarized light allowed induction of very high values of anisotropy (D = 0.77) at room temperature. Moreover, the simultaneous action of light and temperature led to the induction of higher values of dichroism in comparison with anisotropy generated by the standard procedure. Subsequent thermal treatment led to dewetting and the formation of 3D macroscopic stripe- and dome-like structures for one of the investigated compounds. Despite photoinduction of anisotropy by a single beam, the formation of polarization and surface relief gratings by two-beam interference pattern was also investigated.
In the oxidative system (t-BuOCl+NaI) trifluoromethanesulfonamide is regio- and stereoselectively added to only one double bond of cyclopentadiene and 1,3-cyclohexadiene giving rise to 1,1,1-trifluoro-N-(5-iodocyclopent-2-en-1-yl)methanesulfonamide 7 and trans-N,N'-cyclohex-3-en-1,2-diylbis(1,1,1-trifluoromethanesulfonamide) 8. The structure of 7 and 8 was determined by X-ray, NMR, and MS. With 1,4-cyclohexadiene, addition to both double bonds occurs with the formation of N,N'-(4-chloro-5-iodocyclohexan-1,2-diyl)bis(1,1,1-trifluoromethanesulfonamide) 9. Under the action of sodium iodide in acetone, the latter product undergoes halogenophilic attack with the reduction of the CHI group and elimination of HCl to give trans-N,N'-cyclohex-4-en-1,2-diylbis(1,1,1-trifluoromethanesulfonamide) 10, whose structure was also determined by X-ray analysis. 1,3,5-Cycloheptatriene under these conditions is oxidized to benzaldehyde and does not react with trifluoromethanesulfonamide.
The role of electronic friction and, more generally, of nonadiabatic effects during dynamical processes at the gas/metal surface interface is still a matter of discussion. In particular, it is not clear if electronic nonadiabaticity has an effect under "mild" conditions, when molecules in low rovibrational states interact with a metal surface. In this paper, we investigate the role of electronic friction on the dissociative sticking and (inelastic) scattering of vibrationally and rotationally cold H-2 molecules at a Ru(0001) surface theoretically. For this purpose, classical molecular dynamics with electronic friction (MDEF) calculations are performed and compared to MD simulations without friction. The two H atoms move on a six-dimensional potential energy surface generated from gradient-corrected density functional theory (DFT), that is, all molecular degrees of freedom are accounted for. Electronic friction is included via atomic friction coefficients obtained from an embedded atom, free electron gas (FEG) model, with embedding densities taken from gradient-corrected DFT. We find that within this model, dissociative sticking probabilities as a function of impact kinetic energies and impact angles are hardly affected by nonadiabatic effects. If one accounts for a possibly enhanced electronic friction near the dissociation barrier, on the other hand, reduced sticking probabilities are observed, in particular, at high impact energies. Further, there is always an influence on inelastic scattering, in particular, as far as the translational and internal energy distribution of the reflected molecules is concerned. Additionally, our results shed light on the role played by the velocity distribution of the incident molecular beam for adsorption probabilities, where, in particular, at higher impact energies, large effects are found.
Various synthetic approaches were explored towards the preparation of poly(N-substituted glycine) homo/co-polymers (a.k.a. polypeptoids). In particular, monomers that would facilitate in the preparation of bio-relevant polymers via either chain- or step-growth polymerization were targeted. A 3-step synthetic approach towards N-substituted glycine N-carboxyanhydrides (NNCA) was implemented, or developed, and optimized allowing for an efficient gram scale preparation of the aforementioned monomer (chain-growth). After exploring several solvents and various conditions, a reproducible and efficient ring-opening polymerization (ROP) of NNCAs was developed in benzonitrile (PhCN). However, achieving molecular weights greater than 7 kDa required longer reaction times (>4 weeks) and sub-sequentially allowed for undesirable competing side reactions to occur (eg. zwitterion monomer mechanisms). A bulk-polymerization strategy provided molecular weights up to 11 kDa within 24 hours but suffered from low monomer conversions (ca. 25%). Likewise, a preliminary study towards alcohol promoted ROP of NNCAs suffered from impurities and a suspected alternative activated monomer mechanism (AAMM) providing poor inclusion of the initiator and leading to multi-modal dispersed polymeric systems. The post-modification of poly(N-allyl glycine) via thiol-ene photo-addition was observed to be quantitative, with the utilization of photo-initiators, and facilitated in the first glyco-peptoid prepared under environmentally benign conditions. Furthermore, poly(N-allyl glycine) demonstrated thermo-responsive behavior and could be prepared as a semi-crystalline bio-relevant polymer from solution (ie. annealing). Initial efforts in preparing these polymers via standard poly-condensation protocols were insufficient (step-growth). However, a thermally induced side-product, diallyl diketopiperazine (DKP), afforded the opportunity to explore photo-induced thiol-ene and acyclic diene metathesis (ADMET) polymerizations. Thiol-ene polymerization readily led to low molecular weight polymers (<2.5 kDa), that were insoluble in most solvents except heated amide solvents (ie. DMF), whereas ADMET polymerization, with diallyl DKP, was unsuccessful due to a suspected 6 member complexation/deactivation state of the catalyst. This understanding prompted the preparation of elongated DKPs most notably dibutenyl DKP. SEC data supports the aforementioned understanding but requires further optimization studies in both the preparation of the DKP monomers and following ADMET polymerization. This work was supported by NMR, GC-MS, FT-IR, SEC-IR, and MALDI-Tof MS characterization. Polymer properties were measured by UV-Vis, TGA, and DSC.
The ternary system composed of the ionic liquid surfactant (IL-S) 1-butyl-3-methylimidazolium dodecylsulfate ([Bmim][DodSO(4)]), the room temperature ionic liquid (RTIL) 1-ethyl-3-methylimidazolium ethylsulfate ([Emim][EtSO4]), and toluene has been investigated. Three major mechanisms guiding the structure of the isotropic phase were identified by means of conductometric experiments, which have been correlated to the presence of oil-in-IL, bicontinuous, and IL-in-oil microemulsions. IL-S forms micelles in toluene, which swell by adding RTIL as to be shown by dynamic light scattering (DLS) and small-angle X-ray scattering (SAXS) experiments. Therefore, it is possible to form water free IL-in-oil reverse microemulsions <= 10 nm in size as a new type of nanoreactor.
The polymer-controlled and bioinspired precipitation of inorganic minerals from aqueous solution at near-ambient or physiological conditions avoiding high temperatures or organic solvents is a key research area in materials science. Polymer-controlled mineralization has been studied as a model for biomineralization and for the synthesis of (bioinspired and biocompatible) hybrid materials for a virtually unlimited number of applications. Calcium phosphate mineralization is of particular interest for bone and dental repair. Numerous studies have therefore addressed the mineralization of calcium phosphate using a wide variety of low- and high-molecular-weight additives. In spite of the growing interest and increasing number of experimental and theoretical data, the mechanisms of polymer-controlled calcium phosphate mineralization are not entirely clear to date, although the field has made significant progress in the last years. A set of elegant experiments and calculations has shed light on some details of mineral formation, but it is currently not possible to preprogram a mineralization reaction to yield a desired product for a specific application. The current article therefore summarizes and discusses the influence of (macro)molecular entities such as polymers, peptides, proteins and gels on biomimetic calcium phosphate mineralization from aqueous solution. It focuses on strategies to tune the kinetics, morphologies, final dimensions and crystal phases of calcium phosphate, as well as on mechanistic considerations.
The nature of the major steric substituent constant scales for alkyl substituents, i.e. Omega(S), E-R and E-S' scales, was studied with the aid of the NBO and the natural steric (STERIC) analyses. Cyclohexyl esters R-3-CCOOC6H11 (R = alkyl or H) were used as the model compounds. Special emphasis was laid on the potential contribution of the polar component in these steric substituent parameters. In the light of our model the Omega(S) scale seems to be dominantly a steric substituent constant scale as is seen on the strengths of the good correlation between the Omega(S) constants of the CR3 group and the total steric exchange energy values E-TSEE for the model compounds. However, the Omega(S) values also seem to include a minor electronic component due to the varying electrostatic effect via the C alpha atom. On the other hand, E-R and E-S' parameters largely hinge on the size dependent polar effect of the CR3 alkyl group. By way of our model this repulsive interaction can be quantified by descriptor Delta q(OCO), the natural charge difference q(C)(C=O) - Sigma qO for the O-C(=O) functional group. Delta q(OCO) depends on the E-TSEE values, on qC alpha and on the polarization coefficients of the oxygen hybrid in the NBO of the pi(C=O) bond. The size sensitivity of the kinetic E-S' constants can be connected to variation of the Burgi-Dunitz angle in the transition state for the standard reaction used. A comparison is made for the q(C)(C=O) or Delta q(OCO) values computed on the one hand with the NBO formalism and on the other hand with the Hirshfeld formalism. A practical novel substituent constant q(C)(C=O) for the size of the alkyl groups is introduced.
We report on the influence of localized surface plasmon resonance excitation of Au@SiO2 core-shell nanoparticles on the amplified spontaneous emission of a semiconductor polymer composite (F8BT/MEH-PPV). Au@SiO2 nanoparticles are compatible with the donor-acceptor polymer matrix and get uniformly distributed within the whole polymer film. The plasmon resonance band of the nanoparticles correlates with both the emission and excitation spectra of the polymer composite, as well as with the donor emission and acceptor excitation spectra. We demonstrate that resonantly excited Au@SiO2 nanoparticles enhance the amplified spontaneous emission and the modal gain of the polymer films. The measurement of influential factors reveals that the emission is enhanced predominantly by the increase of acceptor excitation rate, which is accompanied by depletion of the FRET efficiency and increase of quantum yield. The enhancement factor is increased by both introducing a higher loading of plasmonic nanoparticles in the polymer film and increasing the excitation energy. This work shows that these plasmonic nanoantennas are able to enhance the stimulated emission of semiconductor polymers by improving the size mismatch between the excitation light and the emitting polymer.
An amphiphilic linear ternary block copolymer was synthesised in three consecutive steps via reversible addition-fragmentation chain transfer polymerisation. Oligo(ethylene glycol) monomethyl ether acrylate was engaged as a hydrophilic building block, while benzyl acrylate and 3-tris(trimethylsiloxy)silyl propyl acrylate served as hydrophobic building blocks. The resulting "triphilic" copolymer consists thus of a hydrophilic (A) and two mutually incompatible "soft" hydrophobic blocks, namely, a lipophilic (B) and a silicone-based (C) block, with all blocks having glass transition temperatures well below 0 A degrees C. The triphilic copolymer self-assembles into spherical multicompartment micellar aggregates in aqueous solution, where the two hydrophobic blocks undergo local phase separation into various ultrastructures as evidenced by cryogenic transmission electron microscopy. Thus, a silicone-based polymer block can replace the hitherto typically employed fluorocarbon-based hydrophobic blocks in triphilic block copolymers for inducing multicompartmentalisation.
Modifizierung von Silikonelastomeren mit organischen Dipolen für Dielektrische Elastomer Aktuatoren
(2013)
Ein Dielektrischer Elastomer Aktuator (DEA) ist ein dehnbarer Kondensator, der aus einem Elastomerfilm besteht, der sich zwischen zwei flexiblen Elektroden befindet. Bei Anlegen einer elektrischen Spannung, ziehen sich die Elektroden aufgrund elektrostatischer Wechselwirkungen an, wodurch das Elastomer in z-Richtung zusammengepresst wird und sich dementsprechend in der x-,y-Ebene ausdehnt. Hierdurch werden Aktuationsbewegungen erreicht, welche sehr präzise über die Spannung gesteuert werden können. Zusätzlich sind DEAs kostengünstig, leicht und aktuieren geräuschlos. DEAs können beispielsweise für Produkte im medizinischen Bereich oder für optischer Komponenten genutzt werden. Ebenso kann aus diesen Bauteilen Strom erzeugt werden. Das größte Hindernis für eine weite Implementierung dieser Materialien liegt in den erforderlichen hohen Spannungen zum Erzeugen der Aktuationsbewegung, welche sich tendenziell im Kilovolt-Bereich befinden. Dies macht die Elektronik teuer und die Bauteile unsicher für Anwender. Um geringere Betriebsspannungen für die DEAs zu erreichen, sind signifikante Materialverbesserungen - insbesondere des verwendeten Elastomers - erforderlich. Um dies zu erreichen, können die dielektrischen Eigenschaften (Permittivität) der Elastomere gesteigert und/oder deren Steifigkeit (Young-Modul) gesenkt werden. In der vorliegenden Arbeit konnte die Aktuationsleistung von Silikonfilmen durch die Addition organischer Dipole erheblich verbessert werden. Hierfür wurde ein Verfahren etabliert, um funktionalisierte Dipole kovalent an das Polymernetzwerk zu binden. Dieser als "One-Step-Verfahren" bezeichnete Ansatz ist einfach durchzuführen und es werden homogene Filme erhalten. Die Dipoladdition wurde anhand verschiedener Silikone erprobt, die sich hinsichtlich ihrer mechanischen Eigenschaften unterschieden. Bei maximalem Dipolgehalt verdoppelte sich die Permittivität aller untersuchten Silikone und die Filme wurden deutlich weicher. Hierbei war festzustellen, dass die Netzwerkstruktur der verwendeten Silikone einen erheblichen Einfluss auf die erreichte Aktuationsdehnung hat. Abhängig vom Netzwerk erfolgte eine enorme Steigerung der Aktuationsleistung im Bereich von 100 % bis zu 4000 %. Dadurch können die Betriebsspannungen in DEAs deutlich abgesenkt werden, so dass sie tendenziell bei Spannungen unterhalb von einem Kilovolt betrieben werden können.
A suitable vehicle for integration of bioactive plant constituents is proposed. It involves modification of proteins using phenolics and applying these for protection of labile constituents. It dissects the noncovalent and covalent interactions of beta-lactoglobulin with coffee-specific phenolics. Alkaline and polyphenol oxidase modulated covalent reactions were compared. Tryptic digestion combined with MALDI-TOF-MS provided tentative allocation of the modification type and site in the protein, and an in silico modeling of modified beta-lactoglobulin is proposed. The modification delivers proteins with enhanced antioxidative properties. Changed structural properties and differences in solubility, surface hydrophobicity, and emulsification were observed. The polyphenol oxidase modulated reaction provides a modified beta-lactoglobulin with a high antioxidative power, is thermally more stable, requires less energy to unfold, and, when emulsified with lutein esters, exhibits their higher stability against UV light. Thus, adaptation of this modification provides an innovative approach for functionalizing proteins and their uses in the food industry.
We have synthesized a set of new unsaturated macrocyclic dithioethers with an increasing number of flexible methylene units 1-7 (Scheme 2) to investigate the correlation between the ring size of these ligands, the chelation effect and the consequences for an efficient PdCl2 coordination. The dithioethers 1-7 and the complex [PdCl2(4)]center dot CHCl3 were characterized by X-ray diffraction analysis. The crystal structures of 1-7 show that 2-7 are better preorganized chelating ligands for an exocyclic PdCl2 coordination than 1. The chelation effect of 1-7, the orientation of the sulfur atoms and the S center dot center dot center dot S donor distances, are influenced by the flexibility of the methylene units. In this series the unsaturated macrocyclic ligands 5 and 6 are the best chelating ligands for an efficient PdCl2 coordination. Comparative solvent extraction experiments with mn-12S(2)O(2) (mn = maleonitrile) reveal that the low interface activity of the new ligands reduces the extraction rate. However, a comparison with open-chain dithiomaleonitriles shows the impact of the macrocyclic effect of 4 and 5 on the extraction yield.
Sugar-based molecules and polysaccharide biomass can be turned into porous functional carbonaceous products at comparably low temperatures of 400 °C under a nitrogen atmosphere in the presence of an ionic liquid (IL) or a poly(ionic liquid) (PIL). The IL and PIL act as “activation agents” with own structural contribution, and effectively promote the conversion and pore generation in the biomaterials even at a rather low doping ratio (7 wt%). In addition, this “induced carbonization” and pore forming phenomenon enables the preservation of the biotemplate shape to the highest extent and was employed to fabricate shaped porous carbonaceous materials from carbohydrate-based biotemplates, exemplified here with cellulose filter membranes, coffee filter paper and natural cotton. These carbonized hybrids exhibit comparably good mechanical properties, such as bendability of membranes or shape recovery of foams. Moreover, the nitrogen atoms incorporated in the final products from the IL/PIL precursors further improve the oxidation stability in the fire-retardant tests.
Sugar-based molecules and polysaccharide biomass can be turned into porous functional carbonaceous products at comparably low temperatures of 400 degrees C under a nitrogen atmosphere in the presence of an ionic liquid (IL) or a poly(ionic liquid) (PIL). The IL and PIL act as "activation agents" with own structural contribution, and effectively promote the conversion and pore generation in the biomaterials even at a rather low doping ratio (7 wt%). In addition, this "induced carbonization" and pore forming phenomenon enables the preservation of the biotemplate shape to the highest extent and was employed to fabricate shaped porous carbonaceous materials from carbohydrate-based biotemplates, exemplified here with cellulose filter membranes, coffee filter paper and natural cotton. These carbonized hybrids exhibit comparably good mechanical properties, such as bendability of membranes or shape recovery of foams. Moreover, the nitrogen atoms incorporated in the final products from the IL/PIL precursors further improve the oxidation stability in the fire-retardant tests.
Sugar-based molecules and polysaccharide biomass can be turned into porous functional carbonaceous products at comparably low temperatures of 400 °C under a nitrogen atmosphere in the presence of an ionic liquid (IL) or a poly(ionic liquid) (PIL). The IL and PIL act as "activation agents" with own structural contribution, and effectively promote the conversion and pore generation in the biomaterials even at a rather low doping ratio (7 wt%). In addition, this "induced carbonization" and pore forming phenomenon enables the preservation of the biotemplate shape to the highest extent and was employed to fabricate shaped porous carbonaceous materials from carbohydrate-based biotemplates, exemplified here with cellulose filter membranes, coffee filter paper and natural cotton. These carbonized hybrids exhibit comparably good mechanical properties, such as bendability of membranes or shape recovery of foams. Moreover, the nitrogen atoms incorporated in the final products from the IL/PIL precursors further improve the oxidation stability in the fire-retardant tests.
The detection of hydrogen sulfide (H2S) by 2 + 1 resonance-enhanced multi-photon ionization (REMPI) and the application of H2S as a laser dopant for the detection of polar compounds in laser ion mobility (IM) spectrometry at atmospheric pressure were investigated. Underlying ionization mechanisms were elucidated by additional studies employing a drift cell interfaced to a time-of-flight mass spectrometer. Depending on the pressure, the primary ions H2S+, HS+, S+, and secondary ions, such as H3S+, were observed. The 2 + 1 REMPI spectrum of H2S near lambda = 302.5 nm was recorded at atmospheric pressure. Furthermore, the limit of detection and the linear range were established. In the second part of the work, H2S was investigated as an H2O analogous laser dopant for the ionization of polar substances by proton transfer. H2S exhibits a proton affinity (PA) similar to that of H2O, but a significantly lower ionization energy facilitating laser ionization. Ion-molecule reactions (IMR) of H3S+ with a variety of polar substances with PA between 754.6 and 841.6 kJ/mol were investigated. Representatives of different compound classes, including alcohols, ketones, esters, and nitroaromatics were analyzed. The IM spectra resulting from IMR of H3S+ and H3O+ with these substances are similar in structure, i.e., protonated monomer and dimer ion peaks are found depending on the analyte concentration.
L-edge spectroscopy of 3d transition metals provides important electronic structure information and has been used in many fields. However, the use of this method for studying dilute aqueous systems, such as metalloenzymes, has not been prevalent because of severe radiation damage and the lack of suitable detection systems. Here we present spectra from a dilute Mn aqueous solution using a high-transmission zone-plate spectrometer at the Linac Coherent Light Source (LCLS). The spectrometer has been optimized for discriminating the Mn L-edge signal from the overwhelming 0 K-edge background that arises from water and protein itself, and the ultrashort LCLS X-ray pulses can outrun X-ray induced damage. We show that the deviations of the partial-fluorescence yield-detected spectra from the true absorption can be well modeled using the state-dependence of the fluorescence yield, and discuss implications for the application of our concept to biological samples.
A new phenylanthrone, named knipholone cyclooxanthrone and a dimeric anthraquinone, 10-methoxy-10,7'-(chrysophanol anthrone)-chrysophanol were isolated from the roots of Kniphofia foliosa together with the rare naphthalene glycoside, dianellin. The structures were determined by NMR and mass spectroscopic techniques. The compounds showed antiplasmodial activities against the chloroquine-resistant (W2) and chloroquine-sensitive (D6) strains of Plasmodium falciparum with 10-methoxy-10,7'-(chrysophanol anthrone)-chrysophanol being the most active with IC50 values of 1.17 +/- 0.12 and 4.07 +/- 1.54 mu g/ml, respectively.
In aqueous solution, symmetric triblock copolymers with a thermoresponsive middle block and hydrophobic end blocks form flower-like core-shell micelles which collapse and aggregate upon heating through the cloud point (CP). The collapse of the micellar shell and the intermicellar aggregation are followed in situ and in real-time using time-resolved small-angle neutron scattering (SANS), while heating micellar solutions of a poly((styrene-d(8))-b-(N-isopropyl acrylamide)-b-(styrene-d(8))) triblock copolymer in D2O rapidly through their CP. The influence of polymer concentration as well as of the start and target temperatures is addressed. In all cases, the micellar collapse is very fast. The collapsed micelles immediately form small clusters which contain voids. They densify which slows down or even stops their growth. For low concentrations and target temperatures just above the CP, i.e. shallow temperature jumps, the subsequent growth of the clusters is described by diffusion-limited aggregation. In contrast, for higher concentrations and/or higher target temperatures, i.e. deep temperature jumps, intermicellar bridges dominate the growth. Eventually, in all cases, the clusters coagulate which results in macroscopic phase separation. For shallow temperature jumps, the cluster surfaces stay rough; whereas for deep temperature jumps, a concentration gradient develops at late stages. These results are important for the development of conditions for thermal switching in applications, e.g. for the use of thermoresponsive micellar systems for transport and delivery purposes.
Kinetics and time-dependent Langmuir modeling of 4-nitrophenol adsorption onto Mansonia sawdust
(2013)
Often time's adsorption of large molecules onto untreated lignocellulosic materials is viewed as a two stage process and has frequently been characterized only by kinetic models while the rate limiting step of adsorption is determined only at various stages of the adsorption process. In this study the kinetics and the contribution of diffusion processes to 4-nitrophenol adsorption onto untreated sawdust was examined and the overall rate limiting step evaluated.
The adsorption profile showed an initial rapid uptake of 4-nitrophenol which decreased and became almost constant after 5 min of contact. Analysis of the adsorption profile with the intraparticle diffusion equation and fractional 4-nitrophenol uptake with time showed that the profile can be divided into three different stages. The rate determining step of 4-nitrophenol adsorption was then evaluated based on the activation energies of each processes along with their activation parameters (Delta G*, Delta H* and Delta S*). The results revealed that external mass transfer was the overall rate limiting step with activation parameters E-a = 21.11, Delta H* = 23.75 and Delta S* = 144.97. Time dependent Langmuir modeling was carried out to optimize process parameters. (c) 2013 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
Experimental results indicated the contact angles in the drops of Janus emulsions formed in a one-step mixing process to be invariant within a significant range the oil volume ratios, similar to the results from microfluidics emulsification. Since this result points to a connection between the kinetically formed emulsions and the local equilibrium topology of emulsion drops, the effect of interfacial tensions on the morphology of Janus emulsions was estimated from the equilibrium interfacial tensions at the line of contact. Realistic values of the tensions revealed the limited range of these to obtain Janus drops and also offered correlation between the equilibrium entities and the curvature of the interface between the two oils.
Ionogel fiber mats were made by electrospinning poly(methylmethacrylate) (PMMA) and the ionic liquid (IL) bis(1-butyl-3-methyl-imidazolium) tetrachloridocupraten, [Bmim](2)[CuCl4], from acetone. The morphology of the electrospun ionogels strongly depends on the spinning parameters. Dense and uniform fiber mats were only obtained at concentrations of 60 to 70 g of polymer and IL mass combined. Lower concentrations led to a low number of poorly defined fibers. High voltages of 20 to 25 kV led to well-defined and uniform fibers; voltages between 15 and 20 kV again led to less uniform and less dense fibers. At 10 kV and lower, no spinning could be induced. Finally, PMMA fibers electrospun without IL show a less well-defined morphology combining fibers and oblong droplets indicating that the IL has a beneficial effect on the electrospinning process. The resulting materials are prototypes for new functional materials, for example in sterile filtration.
Laser-based ion mobility (IM) spectrometry was used for the detection of neuroleptics and PAH. A gas chromatograph was connected to the IM spectrometer in order to investigate compounds with low vapour pressure. The substances were ionized by resonant two-photon ionization at the wavelengths lambda = 213 and 266 nm and pulse energies between 50 and 300 mu J. Ion mobilities, linear ranges, limits of detection and response factors are reported. Limits of detection for the substances are in the range of 1-50 fmol. Additionally, the mechanism of laser ionization at atmospheric pressure was investigated. First, the primary product ions were determined by a laser-based time-of-flight mass spectrometer with effusive sample introduction. Then, a combination of a laser-based IM spectrometer and an ion trap mass spectrometer was developed and characterized to elucidate secondary ion-molecule reactions that can occur at atmospheric pressure. Some substances, namely naphthalene, anthracene, promazine and thioridazine, could be detected as primary ions (radical cations), while other substances, in particular acridine, phenothiazine and chlorprothixene, are detected as secondary ions (protonated molecules). The results are interpreted on the basis of quantum chemical calculations, and an ionization mechanism is proposed.
In a systematic approach we synthesized a new series of fluorescent probes incorporating donoracceptor (D-A) substituted 1,2,3-triazoles as conjugative -linkers between the alkali metal ion receptor N-phenylaza-[18]crown-6 and different fluorophoric groups with different electron-acceptor properties (4-naphthalimide, meso-phenyl-BODIPY and 9-anthracene) and investigated their performance in organic and aqueous environments (physiological conditions). In the charge-transfer (CT) type probes 1, 2 and 7, the fluorescence is almost completely quenched by intramolecular CT (ICT) processes involving charge-separated states. In the presence of Na+ and K+ ICT is interrupted, which resulted in a lighting-up of the fluorescence in acetonitrile. Among the investigated fluoroionophores, compound 7, which contains a 9-anthracenyl moiety as the electron-accepting fluorophore, is the only probe which retains light-up features in water and works as a highly K+/Na+-selective probe under simulated physiological conditions. Virtually decoupled BODIPY-based 6 and photoinduced electron transfer (PET) type probes 35, where the 10-substituted anthracen-9-yl fluorophores are connected to the 1,2,3-triazole through a methylene spacer, show strong ion-induced fluorescence enhancement in acetonitrile, but not under physiological conditions. Electrochemical studies and theoretical calculations were used to assess and support the underlying mechanisms for the new ICT and PET 1,2,3-triazole fluoroionophores.
Industrial applications of photon density wave spectroscopy for in-line particle sizing [Invited]
(2013)
Optical spectroscopy in highly turbid liquid material is often restricted by simultaneous occurrence of absorption and scattering of light. Photon Density Wave (PDW) spectroscopy is one of the very few, yet widely unknown, technologies for the independent quantification of these two optical processes. Here, a concise overview about modern PDW spectroscopy is given, including all necessary equations concerning the optical description of the investigated material, dependent light scattering, particle sizing, and PDW spectroscopy itself. Additionally, it is shown how the ambiguity in particle sizing, arising from Mie theory, can be correctly solved. Due to its high temporal resolution, its applicability to highest particle concentrations, and its purely fiber-optical probe, PDW spectroscopy possesses all fundamental characteristics for optical in-line process analysis. Several application examples from the chemical industry are presented. (C) 2013 Optical Society of America
Here we report a new and simple synthetic pathway to form ordered, hollow carbon nitride structures, using a cyanuric acid melamine (CM) complex in ethanol as a starting product. A detailed analysis of the optical and photocatalytic properties shows that optimum hollow carbon nitride structures are formed after 8 h of condensation. For this condensation time, we find a significantly reduced fluorescence intensity and lifetime, indicating the formation of new, nonradiative deactivation pathways, probably involving charge-transfer processes. Enhanced charge transfer is seen as well from a drastic increase of the photocatalytic activity in the degradation of rhodamine B dye, which is shown to proceed via photoinduced hole transfer. Moreover, we show that various CM morphologies can be obtained using different solvents, which leads to diverse ordered carbon nitride architectures. In all cases, the CM-C3N4 structures exhibited superior photocatalytic activity compared to the bulk material. The utilization of CM hydrogen-bonded complexes opens new opportunities for the significant improvement of carbon nitride synthesis, structure, and optical properties toward an efficient photoactive material for catalysis.
Hydrothermal carbonisation
(2013)
The world’s appetite for energy is producing growing quantities of CO2, a pollutant that contributes to the warming of the planet and which currently cannot be removed or stored in any significant way. Other natural reserves are also being devoured at alarming rates and current assessments suggest that we will need to identify alternative sources in the near future. With the aid of materials chemistry it should be possible to create a world in which energy use needs not be limited and where usable energy can be produced and stored wherever it is needed, where we can minimize and remediate emissions as new consumer products are created, whilst healing the planet and preventing further disruptive and harmful depletion of valuable mineral assets. In achieving these aims, the creation of new and very importantly greener industries and new sustainable pathways are crucial. In all of the aforementioned applications, new materials based on carbon, ideally produced via inexpensive, low energy consumption methods, using renewable resources as precursors, with flexible morphologies, pore structures and functionalities, are increasingly viewed as ideal candidates to fulfill these goals. The resulting materials should be a feasible solution for the efficient storage of energy and gases. At the end of life, such materials ideally must act to improve soil quality and to act as potential CO2 storage sinks. This is exactly the subject of this habilitation thesis: an alternative technology to produce carbon materials from biomass in water using low carbonisation temperatures and self-generated pressures. This technology is called hydrothermal carbonisation. It has been developed during the past five years by a group of young and talented researchers working under the supervision of Dr. Titirici at the Max-Planck Institute of Colloids and Interfaces and it is now a well-recognised methodology to produce carbon materials with important application in our daily lives. These applications include electrodes for portable electronic devices, filters for water purification, catalysts for the production of important chemicals as well as drug delivery systems and sensors.
New hybrid clay adsorbent based on kaolinite clay and Carica papaya seeds with improved cation exchange capacity (CEC), rate of heavy metal ion uptake, and adsorption capacity for heavy metal ions were prepared. The CEC of the new material is ca. 75 meq/100 g in spite of the unexpectedly low surface area (approximate to 19 m(2)/g). Accordingly, the average particle size of the hybrid clay adsorbent decreased from over 200 to 100 pm. The hybrid clay adsorbent is a highly efficient adsorbent for heavy metals. With an initial metal concentration of 1 mg/L, the hybrid clay adsorbent reduces the Cd2+, Ni2+, and Pb2+ concentration in aqueous solution to <= 4, <= 7 and <= 20 mu g/L, respectively, from the first minute to over 300 min using a fixed bed containing 2 g of adsorbent and a flow rate of approximate to 7 mL/min. These values are (with the exception of Pb2+) in line with the WHO permissible limits for heavy metal ions. In a cocktail solution of Cd2+, and Ni2+, the hybrid clay shows a reduced rate of uptake but an increased adsorption capacity. The CEC data suggest that the adsorption of Pb2+, Cd2+, and Ni2+ on the hybrid clay adsorbent is essentially due to ion exchange. This hybrid clay adsorbent is prepared from materials that are abundant and by a simple means that is sustainable, easily recovered from aqueous solution, nonbiodegradable (unlike numerous biosorbent), and easily regenerated and is a highly efficient alternative to activated carbon for water treatment.
The supercapacitor is one of the most important energy storage devices as its construction allows for addressing many of the drawbacks related to batteries, but the low energy density of current systems is a major issue. In this doctoral dissertation, with a view to attaining high energy density supercapacitor systems that can be comparable to those for batteries, new heteroatom-containing carbons in the form of particles and three-dimensional films were investigated. A nitrogen-containing material, acrodam, was chosen as the carbon precursor due to the inexpensiveness, high carbonization yield, oligomerizability, etc. The carbon particles were prepared from acrodam together with caesium acetate as a meltable flux agent, and disclosed excellent properties in hydroquinone-loaded sulphuric acid electrolyte with high energy densities (up to 133.0 Wh kg–1) and sufficient cycle stabilities. These properties are already now comparable to those of batteries. Besides, conductive carbon three-dimensional films were fabricated using acrodam oligomer as the precursor by the inexpensive spin coating method. The films were found to be homogeneous, flat, void- and crack-free, and high conductivities (up to 334 S cm–1) could be obtained at the carbonization temperature of 1000 ºC. Furthermore, a porous carbon three-dimensional film could be formed using an organic template at the first attempt. This finding demonstrates the film’s potentiality for various applications such as supercapacitor electrode; the essential absence of contact resistance within the network should contribute to effective transportation of electron within the electrode. The progress made in this dissertation will open a new way to further enhancement of energy density for supercapacitor as well as other applications that exceeds the current properties.
A six-step synthesis of the antidepressant rolipram from the popular analgetic 4-acetamidophenol (paracetamol) is described. The steps include oxidative functionalization of the aromatic core, diazonium salt formation via deacetylation-diazotation, Matsuda-Heck reaction, conjugate addition of nitromethane, and hydrogenative cyclization.
Fluoreszenzfarbstoffe mit Dioxolobenzodioxol-Grundgerüst: Synthese, Untersuchungen und Anwendungen
(2013)
Fluorescent gold clusters synthesized in a poly(ethyleneimine) modified reverse microemulsion
(2013)
This paper is focused on the formation of gold clusters in a tailor-made polyelectrolyte-modified reverse microemulsion using poly(ethyleneimine) (PEI) as a cationic polyelectrolyte. PEI incorporated into a ternary w/o microemulsion consisting of water/heptanol/zwitterionic surfactant 3-(N,N-dimethyl-dodecylammonio)-propanesulfonate (SB) acts as a reducing and stabilizing agent and shows an additional template effect. The nanoparticle synthesis is performed by a simple mixing of two microemulsions, one containing the PEI and the other one containing the gold chloride precursor. UV-vis measurements in the microemulsion show two pronounced absorption maxima, one at 360 nm and the other one at 520 nm, indicating two particle fractions. The absorption maximum at 360 nm in combination to the unique fluorescence properties indicate the formation of gold clusters. After a complete solvent evaporation the redispersed nanoparticles have been characterized by using UV-vis and fluorescence spectroscopy, in combination to dynamic light scattering and transmission electron microscopy (TEM). In addition to the gold nanoparticle fraction (>5 nm) the fluorescent gold cluster fraction (<2 nm) can be redispersed without particle aggregation. By means of asymmetric flow field flow fractionation (AF-FFF) two different cluster fractions with particle diameter (<2 nm) can be identified.
We report on the fabrication, modeling, and experimental verification of the emission of fiber lenses fabricated on multimode fibers in different media. Concave fiber lenses with a radius of 150 mu m were fabricated onto a multimode silica fiber (100 mu m core) by grinding and polishing against a ruby sphere template. In our theoretical model we assume that the fiber guides light from a Lambertian light source and that the emission cone is governed solely by the range of permitted emission angles. We investigate concave and convex lenses at 532 nm with different radii and in a variety of surrounding media from air (n(0) = 1.00) to sapphire (n(0) = 1.77). It was found that noticeable focusing or defocusing effects of a silica fiber lens in ethanol (n(0) = 1.36) and dimethyl sulfoxide (DMSO) (n(0) = 1.48) are only observed when the fiber lens radius was less than the fiber diameter.
The equilibrium topology of an aqueous Janus emulsion of two oils, O1 and O2, with water, W, [(O1+O2)/W], is numerically evaluated with the following realistic interfacial tensions (): (O2/W)=5 mNm(-1), (O1/O2)=1 mNm(-1), and (O1/W) varies within the range 4-5 mNm(-1), which is the limiting range for stable Janus drop topology. The relative significance of the two independently pivotal factors for the topology is evaluated, that is, the local equilibrium at the line of contact between the three liquids and the volume fraction of the two dispersed liquids within the drop. The results reveal a dominant effect of the local equilibrium on the fraction of the O2 drop surface that is covered by O1. In contrast, for a constant volume of O2, the impact of the interfacial tension balance on the limit of the coverage is modest for an infinite volume of O1. Interestingly, when the O1 volume exceeds this value, an emulsion inversion occurs, and the O1 portion of the (O1+O2)/W topology becomes a continuous phase, generating a (W+O2)/O1 Janus configuration.