Professor Cristofor I. Simionescu on His 70th Birthday

Professor Cristofor I. Simionescu was born on July 17, 1920, in Dumbraveni-Suceava. His father was a high school teacher, and young Simionescu went to elementary school in his home town. After completing elementary school he went to Jassy and attended the prestigious “National Lyceum,” the roots of which stem from the “Michailean Academy.” He then began studies at the Polytechnic Institute of Jassy at the Faculty of Chemical Engineering. As a young student he was known for his enthusiasm and was recognized as an excellent young scientist. In 1944 Cristofor Simionescu graduated mugna cum lade from the Polytechnic Institute in Jassy. He obtained his first scientific degree in organic technology, i.e., Doctor of Technical Sciences, in 1948, and became Associate Professor at the Polytechnic Institute. In 1951 he was promoted to Full Professor and was appointed to the Chair of Natural and Synthetic Macromolecules. From 1953 until 1976 Professor Simionescu was Rector of the Polytechnic Institute of Jassy.     

Improving Liquid Chromatography-Mass Spectrometry Sensitivity Using a Subambient Pressure Ionization with Nanoelectrospray (SPIN) Interface

In this work, the subambient pressure ionization with nanoelectrospray (SPIN) ion source and interface, which operates at ~15–30 Torr, is demonstrated to be compatible with gradient reversed-phase liquid chromatography-MS applications, exemplified here with the analysis of complex samples (a protein tryptic digest and a whole cell lysate). A low liquid chromatographic flow rate (100–400 nL/min) allowed stable electrospray to be established while avoiding electrical breakdown. Efforts to increase the operating pressure of the SPIN source relative to previously reported designs prevented solvent freezing and enhanced charged cluster/droplet desolvation. A 5- to 12-fold improvement in sensitivity relative to a conventional atmospheric pressure nanoelectrospray ionization (ESI) source was obtained for detected peptides.     

Heat transfer over a stretching surface with variable heat flux in micropolar fluids

Heat transfer over a stretching surface with uniform or variable heat flux in micropolar fluids is investigated in this Letter. The boundary layer equations are transformed into ordinary differential equations, and then they are solved numerically by a finite-difference method. The effects of the material parameter K, Prandtl number Pr, velocity exponent parameter m, and heat flux exponent parameter n on the heat transfer characteristics are studied. It is found that the local Nusselt number is higher for micropolar fluids compared to Newtonian fluids.     

Why Ortho- and Para-Hydroxy Metabolites Can Scavenge Free Radicals That the Parent Atorvastatin Cannot? Important Pharmacologic Insight from Quantum Chemistry

The pharmaceutical success of atorvastatin (ATV), a widely employed drug against the “bad” cholesterol (LDL) and cardiovascular diseases, traces back to its ability to scavenge free radicals. Unfortunately, information on its antioxidant properties is missing or unreliable. Here, we report detailed quantum chemical results for ATV and its ortho- and para-hydroxy metabolites (o-ATV, p-ATV) in the methanolic phase. They comprise global reactivity indices, bond order indices, and spin densities as well as all relevant enthalpies of reaction (bond dissociation BDE, ionization IP and electron attachment EA, proton detachment PDE and proton affinity PA, and electron transfer ETE). With these properties in hand, we can provide the first theoretical explanation of the experimental finding that, due to their free radical scavenging activity, ATV hydroxy metabolites rather than the parent ATV, have substantial inhibitory effect on LDL and the like. Surprisingly (because it is contrary to the most cases currently known), we unambiguously found that HAT (direct hydrogen atom transfer) rather than SPLET (sequential proton loss electron transfer) or SET-PT (stepwise electron transfer proton transfer) is the thermodynamically preferred pathway by which o-ATV and p-ATV in methanolic phase can scavenge DPPH• (1,1-diphenyl-2-picrylhydrazyl) radicals. From a quantum chemical perspective, the ATV’s species investigated are surprising because of the nontrivial correlations between bond dissociation energies, bond lengths, bond order indices and pertaining stretching frequencies, which do not fit the framework of naive chemical intuition.     

Influence of Convective and Vacuum-Type Drying on Quality,Microstructural, Antioxidant and Thermal Properties of Pretreated Boletus edulis Mushrooms

Freshly harvested Boletus edulis mushrooms are subjected to rapid loss of quality due to the high moisture content and enzymatic activity. Drying time, quality characteristics, microstructural and thermal properties were studied in mushrooms ground to puree subjected to hot air drying (HAD), freeze drying (FD) and centrifugal vacuum drying (CVD). The influence of hot water blanching and UV-C pretreatments was additionally investigated. The rehydration ability of mushroom powders was improved by FD, especially without pretreatment or combined to UV-C exposure. The HAD and CVD, with no pretreatment or combined to UV-C, ensured good preservation of phenolics and antioxidant activity of dried mushrooms. The total difference in color of mushroom pigments extracted in acetone was lower in samples dried by CVD and higher in ones by FD. Blanching before HAD produced whiter product probably due to the reduced polyphenoloxidase activity. Scanning Electron Microscopy (SEM) analysis showed fewer physical changes in FD-samples. Heat-induced structural changes were noticed by Differential Scanning Calorimetry (DSC), Thermogravimetry (TG) and Derivative Thermogravimetry (DTG) analysis, in particular of biopolymers, confirmed by ATR-FTIR analysis. Based on our complex approach, the UV pretreatment of mushrooms could be a better alternative to water blanching. Centrifugal vacuum emerged as a new efficient drying method in terms of bioactive compounds, color and thermal stability, while FD led to better rehydration ability and microstructure.     

ChemInform Abstract: Beyond the Icosahedron: A Density Functional Theory Study of 14‐Atom Germanium Clusters.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.     

Structural studies of tetrazoles. Crystal and molecular structure and ab initio calculations of 1-phenyl-1H-tetrazole-5-thiolate,as its [diaqua(18-crown-6)sodium] salt: An anionic tetrazole free of direct metal interactions

The structure of the anionic heterocycle obtained by deprotonation of 1-phenyl-1H-tetrazole-5-thione was determined by X-ray diffractometry. The counterion is [Na(18-crown-6)(H₂O)₂]⁺. There are no direct interactions between the metal and the tetrazole, while hydrogen bonds between sodium ion coordinated water molecules and neighboring azole anions give cohesion to the crystal. The thiotetrazolato ion displays extensive π-delocalization, with all members of the ring and the exocyclic sulfur contributing to it; however, no interannular conjugation between the phenyl and azole rings is found. The structure of the heterocycle is best described as a resonance hybrid. The geometric parameters of the metal-free tetrazole could be used as the input of ab initio MO calculations at the 6-31G*//3-21G* level, which supported the proposal that the negative charge is mainly concentrated on the N₄-C₅-S portion of the tetrazolate. Some small but significant and consistent bond length differences are found in the uncoordinated tetrazole with respect to metal-bonded analogues. The coordination behavior of the crown ether, with five oxygens bonded to sodium in the complex cation, is rare. © 1997 John Wiley & Sons, Inc.     

Multipolymers with Fischer-Tropsch olefins

Multipolymers consisting of ethylene, 1-heptene, 3-methylpentene and 4-methylpentene were prepared with a heterogeneous Ziegler-Natta catalyst. The polymers were prepared in such a way that the molar fraction of the comonomers remained the same. Copolymers of ethylene/1-heptene and ethylene/4-methylpentene were prepared in order to study the changes in polymer characteristics as one moves from an ethylene/linear alpha olefin copolymer through ethylene multipolymers to an ethylene/4-methylpentene copolymer. The mechanical, rheological and application properties showed expected trends.     

Fast Augmented Lagrangian Method in the convex regime with convergence guarantees for the iterates

Mathematical Programming - We present a trust-region steepest descent method for dynamic optimal control problems with binary-valued integrable control functions. Our method interprets the control...     

Heats of formation of organic molecules by ab initio methods: Thiaalkanes

The bond energy scheme for calculating heats of formation of organic molecules from ab initio data (6–31G*) has been extended to include 24 compounds containing sulfur in the sulfide oxidation state. The rms deviation from the experimental values for these compounds is 0.54 kcal/mol, which is approximately experimental error.