诱导效应指数与脂肪族胺、醇和醚的气相碱性

用烷基诱导效应指数I和RX分子中质子亲合原子X所带电荷qx及元素电负性XN与 脂肪胺，醇、醚的气相质子亲合PA进行关联，结果表明，脂肪胺，醇、醚的气相碱 性可以用下式定量描述：PA(kJ.mol^-1)-2732.0333-2457.1510∑I-1492.2351qx- 732.6277XN利用上式对64种化合物的气相碱性进行预测，平均相对误差为0．34％ ，预测值和实验值的偏差均在实验误差范围内。     

活性炭纤维对氙的动态吸附性能研究

采用动态吸附实验装置，研究了吸附温度、原料气浓度和原料气流量对活性炭纤维动态吸附氙性能的影响。结果表明：在低温条件下（≤273K)，随着温度的升高，活性炭纤维对氙的平衡吸附量明显下降／同时，活性炭纤维对氙的平衡吸附量分别随着原料气浓度及原料气流量的增大而增大。     

Vibronically resolved electronic circular dichroism spectra of (R)-(+)-3-methylcyclopentanone: a theoretical study

The vibrationally resolved electronic circular dichroism (ECD) spectra of the two dominant conformers of (R)-(+)-3-methylcyclopentanone in gas phase are computed by density functional response theory, with a full account of Franck-Condon and Herzberg-Teller vibrational contributions at the harmonic level. Proper inclusion of the latter contributions was made possible by the recent implementation of effective-scaling computations of vibrational overlaps and of analytical gradients of time dependent DFT. The Coulomb-attenuated Becke three parameters Lee-Yang-Parr (CAM-B3LYP) functional reproduces both the position and the intensity of the experimental peaks, providing a remarkable improvement over the spectra obtained with the popular hybrid B3LYP functional, and allowing a confident assignment of the CD fine vibrational structure. Franck-Condon and Herzberg-Teller contributions are discussed in detail. The computed decrease of the CD intensity in the gas phase upon increase of the temperature of the sample follows the trend observed experimentally in different solvents.     

Electrosynthesis of α-Amino Acids from NO and other NOx species over CoFe alloy-decorated Self-standing Carbon Fiber Membranes

The conversion of industrial exhaust gases of nitrogen oxides into high-value products is significantly meaningful for global environment and human health. And green synthesis of amino acids is vital for biomedical research and sustainable development of mankind. Herein, we demonstrate an innovative approach for converting nitric oxide (NO) to a series of α-amino acids (over 13 kinds) through electrosynthesis with α-keto acids over self-standing carbon fiber membrane with CoFe alloy. The essential leucine exhibits a high yield of 115.4 μmol h⁻¹ corresponding a Faradaic efficiency of 32.4 %, and gram yield of products can be obtained within 24 hours in lab as well as an ultra-long stability (>240 h) of the membrane catalyst, which could convert NO into NH₂OH rapidly attacking α-keto acid and subsequent hydrogenation to form amino acid. In addition, this method is also suitable for other nitrogen sources including gaseous NO₂ or liquidus NO₃⁻ and NO₂⁻. Therefore, this work not only presents promising prospects for converting nitrogen oxides from exhaust gas and nitrate-laden waste water into high-value products, but also has significant implications for synthetizing amino acids in biomedical and catalytic science.     

A new cycloartane glycoside from Camptosorus sibiricus Rupr

A new cycloartane glycoside was isolated from the dried aerial parts of Camptosorus sibiricus Rupr. By means of chemical and spectroscopic methods (IR, 1D and 2D NMR, ESI-MS), the structure was established as 3beta, 7beta, 24beta, 25, 30-pentahydroxycycloartane-3-O-beta-D-glucopyranoside-24-O-beta-D-glucopyranosyl(1 --> 2)-D-glucopyranoside (1).     

Structure and stability of X4Y4H4 (XY=CC,BN)

Ab initio calculations have been carried out to study the structures and relative stabilities of the planar eight‐membered ring B₄N₄H₄ and its isoelectronic species C₈H₄ at the HF/6‐31G*, MP2/6‐31G*, MP2/6‐311G**, and MP4SDQ/6‐31G* levels. The analyses of Milliken population, vibration frequencies, π‐molecular orbital components, and orbital energy levels were used to evaluate the relative stabilities of these two similar systems. The homodesmotic reactions were also taken to be a useful index of relative stability for X₄Y₄H₄ (XY=CC, BN) and gave the resonance energies with MP4SDQ/6‐31G* of C₈H₄ (?37.2 kcal/mol) < B₄N₄H₄ (?29.2 kcal/mol). Furthermore, we calculated the thermodynamic functions of these reactions to discuss the influence of temperature. It is concluded that B₄N₄H₄ may exist in theory and could be a little more stable than C₈H₄. © 2001 John Wiley & Sons, Inc. Int J Quant Chem 82: 293–298, 2001     

Synthesis of dihydroxyurea and its application to the U/Pu split in the PUREX process

Dihydroxyurea (DHU) was synthesized using tri-associated solid phosgene [bis(trichloromethyl) carbonate] dissolved in dioxane and hydroxylamine hydrochloride dissolved in potassium acetate solution. The reduction of Pu(IV) by DHU was investigated using UV-Vis spectrophotometry. The reduction back-extraction behavior of Pu(IV) in 30% tri-butyl phosphate/kerosene was firstly investigated under conditions of various temperature, various DHU and HNO₃ concentrations and various phase contact times. The results showed that Pu(IV) in the organic phase can be stripped rapidly to the aqueous phase by DHU. Simulating the 1B contactor of the PUREX process using a 0.1 M DHU in 0.36M nitric acid solution as the stripping agent, the separation factors of uranium/plutonium can reach 2.1·10⁴. This indicates that DHU is a promising salt free agent for uranium/plutonium separation.     

Complex Polypropionates from a South China Sea Photosynthetic Mollusk: Isolation and Biomimetic Synthesis Highlighting Novel Rearrangements

Placobranchus ocellatus is well known to produce diverse and complex γ‐pyrone polypropionates. In this study, the chemical investigation of P. ocellatus from the South China Sea led to the discovery and identification of ocellatusones A–D, a series of racemic non‐γ‐pyrone polyketides with novel skeletons, characterized by a bicyclo[3.2.1]octane ( 1 , 2 ), a bicyclo[3.3.1]nonane ( 3 ) or a mesitylene‐substituted dimethylfuran‐3(2H)‐one core ( 4 ). Extensive spectroscopic analysis, quantum chemical computation, chemical synthesis, and/or X‐ray diffraction analysis were used to determine the structure and absolute configuration of the new compounds, including each enantiomer of racemic compounds 1 – 4 after chiral HPLC resolution. An array of new and diversity‐generating rearrangements is proposed to explain the biosynthesis of these unusual compounds based on careful structural analysis and comparison with six known co‐occurring γ‐pyrones ( 5 – 10 ). Furthermore, the successful biomimetic semisynthesis of ocellatusone A ( 1 ) confirmed the proposed rearrangement through an unprecedented acid induced cascade reaction.     

Two New Diterpenoids from Isodon rubescens

In order to further study on minor diterpenoid constituents of lsodon rubescens, wereinvestigated this species, which was collected in Taibai mountain, Shaanxi Province.TWo new diterpenoids, taibairubescensins A (l) and B (2), were isolated. In this paper,we present the structure elucidation of these two new diterpenoids.Taibairubescensin A (l ), C,.H,#O, (FABMS m/z 435[M 11 ), an amorphous powder,showed UV and iR absorption bands for the existence of hydroxyl, acetoxyl and a fivemembe…     

A Stereoselective Synthetic Route To (E)-α,β-Unsaturated Thioesters

Terminal alkynes 1 react with Cp₂Zr(H)Cl (Cp = η⁵-C₅H₅) and CO to give acylzirconocene chloride derivatives 2, which are trapped with arylsulfenyl chlorides to afford (E)-α,β-unsaturated thioesters.