Characterisation of proanthocyanidin aglycones and glycosides from rose hips by high-performance liquid chromatography-mass spectrometry, and their rapid quantification together with vitamin C

Fifteen individual proanthocyanidin aglycones and 19 glycosides, together with a complex mixture of chromatographically non-separated tetra- to octameric proanthocyanidin glycosides were detected--the non-separated glycosides being novel natural products--and characterised from dog rose hips using high-performance liquid chromatography-electrospray ionisation mass spectrometry (HPLC-ESI-MS). Along with these phenolics, a 50% aqueous ethanol extract of rose hips was found to contain high levels of Vitamin C. A simple and rapid HPLC method assisted by diode array detection for the estimation of the total concentration of proanthocyanidin aglycones and glycosides, as well as Vitamin C, in rose hip extracts was developed.     

Long‐chain‐branched polyethene by the copolymerization of ethene and nonconjugated α,ω‐dienes

Ethene was copolymerized (1) with 1,5‐hexadiene with rac‐ethylenebis(indenyl)zirconium dichloride/methylaluminoxane (MAO) used as a catalyst and (2) with 1,7‐octadiene with bis(n‐butylcyclopentadienyl)zirconium dichloride/MAO and rac‐ethylenebis(indenyl)hafnium dichloride (Et[Ind]₂HfCl₂)/MAO used as catalysts at 80 °C in toluene. The copolymer microstructure and the influence of diene incorporation on the rheological properties were examined. Ethene and 1,5‐hexadiene formed a copolymer in which a major fraction of the 1,5‐hexadiene was incorporated into rings and a small fraction formed 1‐butenyl branches. The copolymerization of ethene with 1,7‐octadiene resulted in a higher selectivity toward branch formation. Some of the branches formed long‐chain‐branching (LCB) structures. The ring formation selectivity increased with decreasing ethene concentration in the polymerization reactor. Melt rheological properties of the diene copolymers resembled those of metallocene‐catalyzed LCB homopolyethenes and depended on the vinyl content, the catalyst, and the polymerization conditions. At high diene contents, all three catalysts produced crosslinked polyethene. This was especially pronounced with Et[Ind]₂HfCl₂, where only 0.2 mol % 1,7‐octadiene in the copolymer was required to achieve significantly modified rheological properties. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3805–3817, 2001     

Fractal characteristics of critical and localized states in incommensurate quantum systems

Incommensurate quantum systems with two competing periodicities exhibit metallic (with Bloch-type extended wave functions), insulating (with exponentially localized wave functions) as well ascritical (with fractal wave functions) phases. An exact renormalization method, which takes into account the inherent incommensurability, is used to obtain the phase diagram of various quantum models for the two-dimensional electron gas and for quantum spin chains in a magnetic field. In this approach, the scaling properties of the fractal eigenstates are characterized by a fixed point or a strange invariant set of the renormalization flow. One of our novel results is the existence of self-similar fluctuations in the localized states once the exponentially decaying envelope is factorized out. In almost all cases under investigation here, the universality classes can be broadly classified as those of the nearest-neighbor square or triangular lattices.     

A special method of deformational correction in N.M.R. of molecules dissolved in liquid crystals

A simple method of deformational correction for the N.M.R. spectral parameters of molecules dissolved in liquid crystals is described. The method is applicable to the different isotopically substituted derivatives of the molecules belonging to the cubic point groups. Its validity is verified for the dipolar and quadrupolar couplings observed in the molecules CH₄, CD₄ and CH₃D dissolved in the liquid crystals Merck Phase IV, Merck ZLI 1167 and their mixtures.     

An empirical constitutive model for complex glass-forming liquids using bitumen as a model material

While extensive research efforts have been devoted to understand the dynamics of chemically and structurally simple glass-forming liquids (SGFLs), the viscoelasticity of chemically and structurally complex glass-forming liquids (CGFLs) has received only little attention. This study explores the rheological properties of CGFLs in the vicinity of the glass transition. Bitumen is selected as the model material for CGFLs due to its extremely complex chemical composition and microstructure, fast physical aging and thermorheological simplicity, and abundant availability. A comprehensive rheological analysis reveals a significant broadening of the glass transition dynamics in bitumen as compared to SGFLs. In particular, the relaxation time spectrum of bitumen is characterized by a broad distribution of long relaxation modes. This observation leads to the development of a new constitutive equation, named the broadened power-law spectrum model. In this model, the wide distribution of long relaxation times is described by a power-law with positive exponent and a stretched exponential cut-off, with parameter β serving as a measure of the broadness of the distribution. This characteristic shape of the bitumen spectrum is attributed to the heterogeneous freezing of different molecular components of bitumen, i.e., to the coexistence of liquid and glassy micro-phases. Furthermore, as this type of heterogeneous glass transition behavior can be considered as a general feature of complex glass-forming systems, the broadened power-law spectrum model is expected to be valid for all types of CGFLs. Examples of the applicability of this model in various complex glass-forming systems are given.     

Xenon porometry at room temperature

Xenon porometry is a method in which porous material is immersed in a medium and the properties of the material are studied by means of 129Xe nuclear magnetic resonance (NMR) of xenon gas dissolved in the medium. For instance, the chemical shift of a particular signal (referred to as signal D) arising from xenon inside small pockets formed in the pores during the freezing of the confined medium is highly sensitive to the pore size. In the present study, we show that when naphthalene is used as the medium the pore size distribution of the material can be determined by measuring a single one-dimensional spectrum near room temperature and converting the chemical shift scale of signal D to the pore radius scale by using an experimentally determined correlation. A model has been developed that explains the curious behavior of the chemical shift of signal D as a function of pore radius. The other signals of the spectra measured at different temperatures have also been identified, and the influence of xenon pressure on the spectra has been studied. For comparison, 129Xe NMR spectra of pure xenon gas adsorbed to porous materials have been measured and analyzed.     

Formation of Aromatic and Other Unsaturated End Groups in Carboxymethyl Cellulose During Hot Alkaline Treatment

Carboxymethyl cellulose (CMC, DS 0.58) was treated in solutions of sodium hydroxide (0.001–1 M) at 95 °C. The treated (1–12 h) CMC samples were purified by dialysis and analyzed by UV spectroscopy and by UV resonance Raman spectroscopy (UVRRS) with excitation at 244 nm. A UV absorption maximum at 265 nm and a UVRR signal at 1650 cm⁻¹ were indicative of formation of -conjugated aldehyde end groups in CMC through -elimination. Another strong UVRR band at 1610 cm⁻¹ gave evidence on conversion of some of the -conjugated aldehyde end groups to alkali stable aromatic structures.     

Comparison of virtual high-throughput screening methods for the identification of phosphodiesterase-5 inhibitors

Reliable and effective virtual high-throughput screening (vHTS) methods are desperately needed to minimize the expenses involved in drug discovery projects. Here, we present an improvement to the negative image-based (NIB) screening: the shape, the electrostatics, and the solvation state of the target protein's ligand-binding site are included into the vHTS. Additionally, the initial vHTS results are postprocessed with molecular mechanics/generalized Born surface area (MMGBSA) calculations to estimate the favorability of ligand-protein interactions. The results show that docking produces very good early enrichment for phosphodiesterase-5 (PDE-5); however, in general, the NIB and the ligand-based screening performed better with or without the added electrostatics. Furthermore, the postprocessing of the NIB screening results using MMGBSA calculations improved the early enrichment for the PDE-5 considerably, thus, making hit discovery affordable.