Quantum mechanical calculations of NMR J coupling values in the determination of relative configuration in organic compounds

[structure: see text] An approach relying on quantum mechanical calculations of proton-proton and proton-carbon J coupling values is proposed as a tool for assigning the relative configuration on chiral organic compounds. The method is suitable for carbon frameworks containing several adjacent stereogenic centers and may allow significant advances in the extensive use of spin-spin couplings in structural elucidation.     

Fibrillar Networks of Glycyrrhizic Acid for Hybrid Nanomaterials with Catalytic Features

Self‐assembly of the naturally occurring sweetening agent, glycyrrhizic acid (GA) in water is studied by small‐angle X‐ray scattering and microscopic techniques. Statistical analysis on atomic force microscopy images reveals the formation of ultralong GA fibrils with uniform thickness of 2.5 nm and right‐handed twist with a pitch of 9 nm, independently of GA concentration. Transparent nematic GA hydrogels are exploited to create functional hybrid materials. Two‐fold and three‐fold hybrids are developed by introducing graphene oxide (GO) and in situ‐synthesized gold nanoparticles (Au NPs) in the hydrogel matrix for catalysis applications. In the presence of GO, the catalytic efficiency of Au NPs in the reduction of p‐nitrophenol to p‐aminophenol is enhanced by 2.5 times. Gold microplate single crystals are further synthesized in the GA hydrogel, expanding the scope of these hybrids and demonstrating their versatility in materials design.     

Phase Behavior of a Designed Cyclopropyl Analogue of Monoolein: Implications for Low‐Temperature Membrane Protein Crystallization

Lipidic cubic phases (LCPs) are used in areas ranging from membrane biology to biodevices. Because some membrane proteins are notoriously unstable at room temperature, and available LCPs undergo transformation to lamellar phases at low temperatures, development of stable low‐temperature LCPs for biophysical studies of membrane proteins is called for. Monodihydrosterculin (MDS) is a designer lipid based on monoolein (MO) with a configurationally restricted cyclopropyl ring replacing the olefin. Small‐angle X‐ray scattering (SAXS) analyses revealed a phase diagram for MDS lacking the high‐temperature, highly curved reverse hexagonal phase typical for MO, and extending the cubic phase boundary to lower temperature, thereby establishing the relationship between lipid molecular structure and mesophase behavior. The use of MDS as a new material for LCP‐based membrane protein crystallization at low temperature was demonstrated by crystallizing bacteriorhodopsin at 20 °C as well as 4 °C.     

Synthesis and optical properties of a poly(2′,5′-dioctyloxy-4,4′,4″- terphenylenevinylene) with high content of (Z) vinylene units

Poly(2′,5′-dioctyloxy-4,4′,4″-terphenylenevinylene) with (E) configuration of the vinylene double bonds was prepared by Suzuki-Miyaura polymerization of (E)-4,4′-dibromostilbene and 2,5-dioctyloxy-1,4-benzenediboronic acid. Attempts to extend this simple procedure to the synthesis of the polymer with (Z) configuration, starting from (Z)-4,4′-dibromostilbene, were unsuccessful. However, the use of (Z)-4,4′-diiodostilbene and a careful choice of Pd catalyst and experimental conditions, lead to a material with a >95/<5 (Z)/(E) ratio of vinylene units. The investigation of optical properties of both the (E) and (Z) polymers evidenced that (Z) linkages act as defects which reduce the effective conjugation length in the polymer backbone.     

Car-Parrinello MD simulations for the Na+ -phenylalanine complex in aqueous solution

Car-Parrinello molecular dynamics (CPMD) calculations are presented for a Na (+)(Phe) complex in aqueous solution and for various stable Na (+)(Phe) complexes and Na (+)(H 2O) n clusters in the gas phase (with up to six water molecules). The CPMD results are compared to available experimental and ab initio reference data, to DFT results obtained with various combinations of density functionals and basis sets, and to previous classical mechanics MD simulations. The agreement with the reference data in the gas phase validates the CPMD method, showing that it is a valid approach for studying these systems and that it describes correctly the competing Na (+)-Phe and Na (+)-H 2O interactions. Analysis of MD trajectories reveals that the Na (+)(Phe) complex in aqueous solution maintains a stable configuration in which the Na (+) cation hovers above the phenyl ring, at an average distance of 3.85 A from the ring center, while remaining strongly bound to one of the carboxylic oxygens of Phe. Constrained MD simulations indicate that the free energy barrier opposing dissociation of the complex exceeds 5.5 kcal/mol. We thus confirm that "cation- pi" interactions between alcali cations and the pi ring, combined with other kinds of interactions, may allow aromatic amino acids to overcome the competition with water in binding a cation.     

Perturbative calculation of Franck-Condon integrals: new hints for a rational implementation

Perturbative approaches to the mode mixing effects in the calculation of Franck-Condon integrals are analyzed and discussed. The zero order multidimensional Franck-Condon integrals are factorized into products of one-dimensional ones, so that recurrence relations can be used without need of storing a huge number of data. Calculations on model systems show that at the second order of perturbation, the method gives results in very good agreement with the exact ones, even in the case of significantly large Duschinsky effect. The accuracy of the results can be substantially improved by grouping together all those modes which are strongly mixed with each other, usually a few ones, for which Franck-Condon integrals can be computed exactly, and using the perturbative approach for treating the smaller mixing between all the other modes.     

Maltodextrin as stabilizer for emulsion polymerization: Adsorption and grafting behavior

Emulsion polymerization of the three-monomer system butyl acrylate–styrene–methacrylic acid was performed in batch using a commercial maltodextrin derived from starch degradation as stabilizer. Stable latexes with narrow particle size distributions were obtained in all examined cases. A method was developed to analyze and quantify the partitioning of the maltodextrin between the continuous phase (supernatant) and the particle phase. Significant differences between the polysaccharides adsorbed onto particles with or without emulsion polymerization reaction were observed. The possible reactions of maltodextrin in presence of a radical initiator were studied in aqueous phase, thus confirming maltodextrin degradation. The formation of copolymers involving the original monomers and the stabilizer according to two different reactive pathways was also confirmed. In terms of adsorbed maltodextrin, two different contributions were observed: maltodextrin physically adsorbed and maltodextrin chemically grafted and/or physically incorporated into the polymer.     

Coordination properties of 6-deoxy-6-[1-(2-amino) ethylamino]-β-cyclodextrin and the ability of its copper(II) complex to recognize and separate amino acid enantiomeric pairs

The functionalized cyclodextrin 6-deoxy-6-[1-(2-amino)ethylamino]--cyclodextrin was synthesized, and an NMR, EPR, pH-metric, and calorimetric investigation was carried out in aqueous solution in order to ascertain its behaviour towards protonation and copper(II) complex formation. The thermodynamic parameters of the ternary complex formation with alanine, phenylalanine and tryptophan enantiomeric pairs were also determined (25° C andI=0.1 mol dm^–3). No thermodynamic enantioselectivity was observed in these systems, while a chiral, though poor, discrimination was observed in LEC: c.d. spectra also show enantiomeric stereoselectivity. The results of the present investigation, compared with previously reported results, suggest the occurence of acis-complex trans-complex equilibrium in such systems.     

Liquid-crystalline polymers from cationic dendronized polymer-anionic lipid complexes

The use of cationic dendronized polymers as a polyelectrolytic system for templating thermotropic liquid-crystalline phases (LC) via complexation and self-assembly with counter-charged ionic lipids is described. The topology of the LC phases resulting from the self-assembly process, their lattice parameter, and the interpenetration of lipid chains is discussed via birefringency analysis and small-angle X-ray scattering. Depending on the generation of the dendronized polymer and the length of the alkyl chains, amorphous, lamellar, and columnar tetragonal phases are observed. A structural model is proposed which accounts for the systematic variations of alkyl chain length as well as polymer generation. Owing to the reversible nature of the ionic complexation, this process proves high relevance for nanoporous channels, biomimetic, transport, and nanotemplating applications.     

Amyloid-mediated synthesis of giant, fluorescent, gold single crystals and their hybrid sandwiched composites driven by liquid crystalline interactions

We report for the first time on the templating effect of β-lactoglobulin amyloid-like fibrils to synthesize gold single crystals of several decades of μm in dimensions. The gold single crystals were produced by reducing an aqueous solution of chloroauric acid by β-lactoglobulin amyloid protein fibrils. Atomic force microscopy, conventional and scanning transmission electron microscopy, electron diffraction and optical microscopy techniques were combined to characterize the structure of the gold crystals. The single-crystalline features of these macroscopic gold crystals are witnessed by their distinctive hexagonal and triangular shape and are confirmed by selected area electron diffraction (SAED). UV-vis absorption spectrum, recorded after a reaction time of 6h at the heating temperature of 55°C showed a surface plasmon resonance peak at 540 nm. With the increase of reaction time to 24h, the absorption spectrum peaks shift to a very broad and higher wavelength region extending up to near infrared region. Remarkably, these single crystalline gold crystals show auto fluorescence when illuminated to UV lamp. Further increase in β-lactoglobulin amyloid fibrils concentration above the isotropic-nematic transition, drives the formation of gold single crystals microplates stacking together and self-assembling into new hierarchical, layered protein-gold hybrid composites.