Influence of the exchange‐correlation functional in all‐electron calculations of the vibrational frequencies of corundum (α‐Al2O3)

The equilibrium structural parameters, high‐ and low‐frequency dielectric tensors, Born effective charges, and Γ‐point vibrational frequencies of bulk Al₂O₃ corundum are calculated by using the periodic, ab initio program CRYSTAL, which adopts an all‐electron Gaussian‐type basis set. The effect of basis set and the performance of three different functionals, i.e., LDA, PW91, and B3LYP, are discussed. The mean absolute deviation from the measured frequencies is as small as 7 cm^?1 for both the LDA and B3LYP functionals, indicating that these functionals perform extremely well in this case. The mean absolute deviation increases to 18 cm^?1 when the PW91 functional is used. All three functionals reproduce the equilibrium geometry of corundum to a high level of accuracy, with LDA and B3LYP outperforming PW91 slightly. The comparison of the current all‐electron calculations with previous plane‐wave, pseudo‐potential calculations shows an overall similar performance. The results of isotopic substitution for both Al and O are also presented. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2006     

Lancifodilactone G: a unique nortriterpenoid isolated from Schisandra lancifolia and its anti-HIV activity

[structure: see text]. Lancifodilactone G (1), a novel, highly oxygenated nortriterpenoid featuring a partial enol structure and a spirocyclic moiety, was isolated from the medicinal plant Schisandra lancifolia. Its structure and stereochemistry were determined from extensive one- and two-dimensional NMR and mass spectral data, coupled with single-crystal X-ray analysis. Compound 1 exerted minimal cytotoxicity against C8166 cells (CC50 > 200 microg/mL) and showed anti-HIV activity with EC50 = 95.47 +/- 14.19 microg/mL and a selectivity index in the range of 1.82-2.46.     

A novel synthesis of allyl and propargyl selenides in aqueous media promoted by indium

Allylic and propargyl bromides react smoothly with diorganyl diselenides in aqueous media to give allylic and propargyl selenides in moderate to good yields. The reaction need not be carried out in inert atmosphere. The speed is quicker than the same reactions in organic media.     

用非等温TG、DTG曲线研究由邻香兰素衍生的Cu(Ⅱ)希夫碱配合物的热分解反应动力学

研究表明,许多过渡金属配合物具有抗癌抑菌性能,刃我们在以前工作基础上又合成了三种由邻香兰素衍生的新型希夫碱配合物,对他们进行了非等温热重分析,并采用积分法和微分法相结合的方法,推断出了它们的热分解反应机理.     

A New Brominated Phenylpropylaldehyde and its Dimethyl Acetal from Red Alga Rhodomela confervoides

A new brominated phenylpropylaldehyde and its dimethyl acetal together with a new natural brominated phenol were isolated from Rhodomela confervoides. Their structrues were elucidated as 2-methyl-3-(2,3-dibromo-4,5-dihydroxyphenyl)propylaldehyde, 2-methyl-3-(2,3-di-bromo-4,5-dihydroxyphenyl) propylaldehyde dimethyl acetal and 3-bromo-4,5-dihydroxybenzoic acid methyl ester by spectroscopic techniques including IR, HRFABMS, 1D and 2DNMR experiments.     

巯基葡聚糖凝胶分离富集光度法测定镉的研究

研究了在ＴｒｉｔｏｎＸ－１００存在下，新显色剂邻羧基苯基重氮氨基偶氮苯（ＣＤＡＡ）与镉的显色体系，在ｐＨ１０．６的Ｎａ２Ｂ４Ｏ７－ＮａＯＨ体系中，显色反应灵敏度很高。络合物的最大吸收位于５４５ｎｍ处，其摩尔吸光系数为２．２２×１０＾５Ｌ·ｍｏｌ＾－１·ｃｍ＾－１。镉含量在０￣１２μｇ／２５ｍＬ符合比耳定律。将该体系用于巯基葡聚糖凝胶分离富集－光度法测水样中微量镉，结果令人满意。     

Superabsorbent hydrogel composites

A new cost‐effective approach to enhance gel strength of superabsorbent hydrogels was invented. Superabsorbent hydrogel composites (SHCs) were prepared through an optimized rapid solution polymerization of concentrated partially neutralized acrylic acid in the presence of a crosslinking agent under normal atmospheric conditions. Kaolin was used as an inorganic component in the polymerization process to strengthen the hydrogel products. FT‐IR spectroscopy was used to confirm grafting of acrylic chains on to the surface of kaolin particles. Morphology of the products was studied by scanning electron microscopy (SEM). Compared with the kaolin‐free hydrogel (control), kaolin caused a reduced equilibrium swelling and swelling rate as low as 17–31% and 19–29%, respectively. Kaolin, however, resulted in enhanced gel strength as high as 21–35% compared to the control. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) were used to study thermal properties of the composites. The SHCs exhibited higher thermal stability than the control. Meanwhile, changes in certain thermal transitions reconfirmed the chemical interaction of the acrylic chain with kaolin. These thermostabilized strengthened superabsorbent hydrogels may be considered as good candidates for agricultural application to retain more water under soil pressure. Copyright © 2003 John Wiley & Sons, Ltd.     

STRUCTRE AND PROPERTIES OF COMPOSITE Ni/HARD CARBON FILMS PREPARED BY PLASMA DEPOSITION

IntroductionHardcarbonfilmsprcparcdb}'vari0usplasmaprocesscsareofc0nsidcrablcinterestbccauscofthcirunusualmcchanical-opticalandelcctricalpropertiesll~3l.Rccently,ithasReceive(IJl111c5,l9`)5;,.`,1iis()tI1ie)\tioII,1'ceil'edJtl1)'l4,l995*'I11isprojectiss[1pportcdh}tl1cNatiol1a1Nat[lntlScicl1ccI`()ul1dati()l1ofCl1il1aal1dtl1eI,aboraton'ofSolidI,ubricati()l1,l.al1/l10ulnstitutcofCl1cn1icalPh\'sics,111cChincscAcadcl11\'ofScicnccs.benfoundthattheinc0rporati0nofmetaIintocarbonfilmscangrcatl}'…     

Novel statistical approach for primary high-throughput screening hit selection

The standard activity threshold-based method (the "top X" approach), currently widely used in the high-throughput screening (HTS) data analysis, is ineffective at identifying good-quality hits. We have proposed a novel knowledge-based statistical approach, driven by the hidden structure-activity relationship (SAR) within a screening library, for primary hit selection. Application to an in-house ultrahigh-throughput screening (uHTS) campaign has demonstrated it can directly identify active scaffolds containing valuable SAR information with a greatly improved confirmation rate compared to the standard "top X" method (from 55% to 85%). This approach may help produce high-quality leads and expedite the hit-to-lead process in drug discovery.     

Carbon‐based Nanosensors for Salicylate Determination in Pharmaceutical Preparations

Thiourea derivative‐based carbon paste electrode (TUD1‐CPE) was constructed as a potentiometric sensor for the determination of salicylate anion in pharmaceutical formulations, Aspocid® and Aspirin®. The optimized CPE contained 45.5 % graphite, 0.5 % reduced graphene oxide (rGO), 46.0 % nitrophenyl octyl ether (NPOE) plasticizer, 5.0 % TUD1 ionophore, and 3.0 % tridodecylmethyl ammonium chloride as additive. The incorporation of NPOE of high dielectric constant, and rGO in electrode caused better performance of the sensor; Nernstian response of 59.0 mV decade^?1 in the concentration range of 10^?1–10^?5 mole L^?1, a detection limit of 1×10^?5 mole L^?1 in a very short response time of 6 seconds. The prepared sensor showed high selectivity against similar anions (i. e. , benzoate, I^?, SCN^?). Selectivity was confirmed by calculating the formation constant (K_β) using sandwich membrane method, where K_β for TUD1‐salicylate is 10^0.43. Theoretical calculations at DFT‐B3LY/6‐31G** level of theory were performed to find interaction mechanism, Energies of HOMO and LUMO orbitals, non‐linear optical (NLO) properties (the electronic dipole moment (μ), first‐order hyperpolarizability (β), the hyper‐Rayleigh scattering (β_HRS) and the depolarization ratio (DR)), and other global properties; these calculations showed lower values of β and DR, higher value of β_HRS, and the shortest lengths of the four N?H bonds between TUD1 and salicylate which confirm their strong complexation and salicylate‐selectivity. Also, all the studied anion‐TUD1 exhibited relatively high NLO properties, and these results were considered as a preliminary study for investigating new types of NLO bearing materials. The sensors were applied successfully for the determination of salicylate anion in Aspocid® and Aspirin®.