Tellurium in organic synthesis: a general approach to buteno- and butanolides

The naturally occurring butanolides (?)-blastmycinolactol, (+)-blastmycinone, (?)-NFX-2, (+)-antimycinone as well as the four stereoisomers of the butenolide Acaterin were prepared in high enantiomeric purity using hydroxy-vinyl tellurides as starting materials.     

Group 4 metal complexes bearing new tridentate (NNO) ligands: Benzyl migration and formation of unusual C-C coupled products

Group 4 metal complexes bearing new phenoxy(benzimidazolyl)-imine, -amine and -amide ligands have been synthesized. A series of metal chloride derivatives has been prepared via treatment of MCl₄(THF)₂ (M = Ti, Zr, Hf) with the in situ generated sodium salt of the (benzimidazolyl)imine phenol 1. Reaction of the pro-ligand 2 with TiCl₄(THF)₂ afforded the corresponding complex 8 in which the amine proton remains bound to the nitrogen donor. Benzyl complexes of zirconium and hafnium were synthesized via treatment of pro-ligands 1 and 2 with M(CH₂Ph)₄ precursors. The complexes [NNO]M(CH₂Ph)₃ (6 M = Zr, 7 M = Hf) were found to undergo benzyl migration from the metal centre to the imine carbon of the ligand backbone giving complexes 11 and 12; the migration follows first order kinetics. The reaction of 1 with Ti(NMe₂)₄ led to the formation of an unusual C-C coupled product in which a new piperazine ring has formed. Complexes 11 and 12 undergo related transformations, leading to analogous C-C coupled products which were characterized by X-ray crystallography. Deuterium labelling experiments were carried out to determine the mechanistic pathway of the reactions. Chloride and benzyl complexes 3-12 were screened as pre-catalysts for olefin polymerization.     

基于压力传感器的汽车重心实时监测力学模型

介绍了传统车辆重心测定的方法，提出了基于压力传感器的汽车重心实时监测机理的力学模型．利用该模型能实时监测汽车的整车重量、重心位置，提供安全装载和安全车速监测与报警，可为汽车安全系统提供可靠的重心计算力学模型，为研制汽车重心实时监测系统提供了必要参数与依据．     

Tomographic reconstruction of atmospheric turbulence with the use of time-dependent stochastic inversion

Acoustic travel-time tomography allows one to reconstruct temperature and wind velocity fields in the atmosphere. In a recently published paper [S. Vecherin et al., J. Acoust. Soc. Am. 119, 2579 (2006)], a time-dependent stochastic inversion (TDSI) was developed for the reconstruction of these fields from travel times of sound propagation between sources and receivers in a tomography array. TDSI accounts for the correlation of temperature and wind velocity fluctuations both in space and time and therefore yields more accurate reconstruction of these fields in comparison with algebraic techniques and regular stochastic inversion. To use TDSI, one needs to estimate spatial-temporal covariance functions of temperature and wind velocity fluctuations. In this paper, these spatial-temporal covariance functions are derived for locally frozen turbulence which is a more general concept than a widely used hypothesis of frozen turbulence. The developed theory is applied to reconstruction of temperature and wind velocity fields in the acoustic tomography experiment carried out by University of Leipzig, Germany. The reconstructed temperature and velocity fields are presented and errors in reconstruction of these fields are studied.     

Preparation and evaluation of rigid porous polyacrylamide-based strong cation-exchange monolithic columns for capillary electrochromatography

A CEC monolithic column with strong cation-exchange (SCX) stationary phase based on hydrophilic monomers was prepared by in situ polymerization of acrylamide, methylenebisacrylamide, and 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) in a complete organic binary porogenic solvent consisting of DMSO and dodecanol. The sulfonic groups provided by the monomer AMPS on the surface of the stationary phase generate an EOF from anode to cathode, and serve as an SCX stationary phase at the same time. The monolithic stationary phase exhibited normal-phase chromatographic behavior for neutral analytes. For charged analytes, electrostatic interaction/repulsion with the monolith was observed. The strong SCX monolithic column has been successfully employed in the electrochromatographic separation of basic drugs, peptides, and alkaloids extracted from natural products.     

Stereoelectronic interactions: A booster for 4JHF transmission

Long-range proton-fluorine coupling constants (ⁿJ_HF) are helpful for the structure elucidation of fluorinated molecules. However, their magnitude and sign can change with the relative position of coupled nuclei and the presence of substituents. Here, trans-4-tert-butyl-2-fluorocyclohexanone was used as a model compound for the study of the transmission of ⁴J_HF. In this compound, the ⁴J_H6axF was measured to be +5.1 Hz, which is five times larger than the remaining ⁴J_HF in the same molecule (⁴J_H4F = +1.0 Hz and ⁴J_H6eqF = +1.0 Hz). Through a combination of experimental data, natural bond orbital (NBO) and natural J-coupling (NJC) analyses, we observed that stereoelectronic interactions involving the π system of the carbonyl group are involved in the transmission pathway for the ⁴J_H6axF. Interactions containing the π system as an electron acceptor (e.g., σ_{C6 H6ax} → π^*_C═O and σ_{C F} → π^*_C═O) increase the value of the ⁴J_H6axF, while the interaction of the π system as an electron donor (e.g., π_C═O → σ^*_{C F}) decreases it. Additionally, the carbonyl group was shown not to be part of the transmission pathway of the diequatorial ⁴J_H6eqF coupling in cis-4-tert-butyl-2-fluorocyclohexanone, revealing that there is a crucial symmetry requirement that must be fulfilled for the π system to influence the value of the ⁴J_HF in these systems.     

Counterintuitive deshielding on the 13C NMR chemical shift for the trifluoromethyl anion

The trifluoromethyl anion (CF₃⁻) displays ¹³C NMR chemical shift (175.0 ppm) surprisingly larger than neutral (CHF₃, 122.2 ppm) and cation (CF₃⁺, 150.7 ppm) compounds. This unexpected deshielding effect for a carbanion is investigated by density functional theory calculations and decomposition analyses of the ¹³C shielding tensor into localized molecular orbital contributions. The present work determines the shielding mechanisms involved in the observed behaviour of the fluorinated anion species, shedding light on the experimental NMR data and demystify the classical correlation between electron density and NMR chemical shift. The presence of fluorine atoms induces the carbon lone pair to create a paramagnetic shielding on the carbon nucleus.     

Competitive Reactivity of Tautomers in the Degradation of Organophosphates by Imidazole Derivatives

The harmful impact caused by pesticides on human health and the environment necessitates the development of efficient degradation processes and control of prohibited stocks of such substances. Organophosphates (OPs) are among the most used agrochemicals in the world and their degradation can proceed through several possible pathways. Investigating the reactivity of OPs with nucleophilic species allows one to propose new and efficient catalyst scaffolds for use in detoxification. In light of the remarkable catalytic activity of imidazole (IMZ) at promoting dephosphorylation processes of OPs, the reactivity of 4(5)-hydroxymethylimidazole (HMZ) with diethyl-2,4-dinitrophenylphosphate (DEDNPP) and Paraoxon are evaluated by combining experimental and theoretical approaches. It is observed that HMZ is an efficient and regiospecific catalyst with reactivity modulated by competing tautomers. To propose an optimal IMZ-based catalyst, quantum chemical calculations were performed for monosubstituted 4(5)IMZ derivatives that might cleave DEDNPP. Both inductive effects and hydrogen bonding by the substituents are shown to influence barriers and mechanisms.     

Temperature dependence on phase evolution in the BaTiO3 polytypes studied using ab initio calculations

Identifying the forces that drive a temperature-induced phase transition is always challenging in the prospect of the first-principles methods. Herein, we perform a first-principles study of the temperature effects on structural, energetic, electronic, and vibrational properties of four BaTiO₃ polymorphs using quasi-harmonic approximations. Study of the stability between these four phases, which we break into contributions arising from the vibration of the lattice, electronic structure, and volume expansion/contraction, is helpful to confirm the sequence of phase transitions as cubic → tetragonal → orthorhombic → rhombohedral, as well as its transition temperatures. A general mechanism was proposed based on the combination between structural distortions at [TiO₆] clusters, vibrational characteristics, and electronic structure. These findings confirm the power of quasi-harmonic approximations to disclose the main fingerprints associated with both thermic and mechanical phase transitions, serving as a guide for further theoretical studies.