Comparison of localization and delocalization indices obtained with Hartree-Fock and conventional correlated methods: effect of Coulomb correlation

Atomic populations and localization [lambda(A)] and delocalization [delta(A,B)] indices (LIs and DIs) are calculated for a large set of molecules at the Hartree-Fock (HF), MP2, MP4(SDQ), CISD, and QCISD levels with the 6-311++G(2d,2p) basis set. The HF method and the conventional correlation methods [MP2, MP4(SDQ), CISD, and QCISD] yield distinct sets of LIs and DIs. Yet, within the four conventional correlation methods the differences in atomic populations and LIs and DIs are small. Relative to HF, the conventional correlation methods [MP2, MP4(SDQ), CISD, QCISD] yield virtually the same LIs and DIs for molecules with large charge separations while LIs and DIs that differ significantly from the HF values--the LIs are increased and DIs decreased--are obtained for bonds with no or small charge separations. Such is the case in the archetypal homopolar molecules HC(triple bond)CH, H2C=CH2, CH3-CH3, and "protonated cyclopropane" C(3)H(7) (+), in which case the bonding may be atypical. Relative to HF, the typical effect of the conventional correlation methods is to decrease the DI between atoms.     

Simultaneous isolation and determination of esculin and rutin in natural materials using SPE and HPLC

Summary Esculin (ESC) and rutin (RUT) have been simultaneously isolated from pharmaceutical natural materials by solid phase extraction (SPE). Determination of both substances was performed by reversed phase high performance liquid chromatography (RPHPLC) with UV detection. Optimization of the separation conditions showed that simultaneous isolation and determination of rutin and esculin from pharmaceutical material was possible. The recovery obtained was not lower than 95±2%.     

中医药抗衰老与微量元素的相关性

重点讨论了各类抗衰老中药和微量元素的相关性，探讨了中医中药衰老和现代微量元素的关系，为人类健康防病抗衰、益寿延年做出新的贡献。     

Use of Two-Dimensional Liquid Chromatography Combined with Diode-Array and Mass Spectrometric Detection for Analysis of Compounds in Flos Lonicera

Comprehensive two-dimensional liquid chromatographic separation by means of a combination of ion-exchange chromatography (IEC) and reversed-phase liquid chromatography (RPLC) has been realized and applied to the analysis of components of a traditional Chinese medicine Flos Lonicera. In the first dimension the components of a Flos Lonicera extract is separated on strong anion-exchange (SAX) column according to the charge-exchange properties of the components. In the second dimension the components are further fractionated by reversed-phase liquid chromatography (on ODS) on the basis of their hydrophobicity. The RPLC effluent is desalted and split and the components are identified on-line by use of both diode-array detection and mass spectrometry with atmospheric pressure chemical ionization (APCI–MS). In this way, the extract of Flos Lonicera can be rapidly separated, desalted, and analyzed, with determination of molecular weight. More than 58 components of an extract of Flos Lonicera were well resolved and six were tentatively identified from their UV and mass spectra.     

Characterisation of Sol-Gel TiO2 Films by Etching

This article describes the SmartKom Companion, one of three demonstrators developed within the SmartKom project whose goal has been to provide an intuitive and intelligent interface for non-expert users to everyday computer-based applications in different scenarios of use. Conceived for the SmartKom Mobile scenario, the Companion allows intuitive multimodal interaction for drivers and pedestrians. The development of the SmartKom prototypes was constantly accompanied by Wizard-of-Oz experiments as well as system evaluations at different stages of the project. Some usability evaluation results relative to the SmartKom Companion will also be presented.     

微乳液增敏光度法测定中草药中微量硒

研究了在非离子微乳液介质中,硫氰酸盐罗丹明B 明胶体系分光光度法测定微量硒的方法。实验表明,当微乳液组成为V(OP乳化剂) +V(正戊醇) +V(正庚烷) +V(水) =1 5 0 +0 1 1+0 41 +97 98时,体系的表观摩尔吸收系数达1 3 0 1×1 0 6 L·mol- 1·cm- 1,灵敏度比在OP溶液中有显著提高,使该法成为少有的超高灵敏度测定硒的光度法之一。Se (Ⅳ)含量在0～0 0 5 μg·mL- 1范围内符合比耳定律,对0 0 2 μg·mL- 1Se(Ⅳ)平行测定1 1次,测得相对标准偏差为0 945 %。应用于中草药中微量硒的测定结果令人满意     

Relativistic atomic natural orbital type basis sets for the alkaline and alkaline-earth atoms applied to the ground-state potentials for the corresponding dimers

New basis sets of the atomic natural orbital (ANO) type have been developed for the atoms Li–Fr and Be–Ra. The ANOs have been obtained from the average density matrix of the ground states and the lowest excited states of the atom, the positive ion, and the dimer at its equilibirium geometry. Scalar realtivisitc effects are included through the use of a Douglas–Kroll Hamiltonian. Multiconfigurational wave functions have been used with dynamic correlation included using second-order perturbation theory (CASSCF/CASPT2). The basis sets are applied in calculations of the ground-state potentials for the dimers. Computed bond energies are accurate to within 0.05 eV for the alkaline dimers and 0.02 eV for the alkaline-earth dimers (except for Be₂).Acknowledgments.ensp;B.O.R. would like to express his gratitude to Prof. Jacopo Tomasi for all the inspiration that his scientific work has given him through the years and continues to do in particular through the work on solvent effects on molecular properties. This work has been supported by a grant from the Swedish Science Research Council, VR.Contribution to the Jacopo Tomasi Honorary Issue     

Synthesis of Obyanamide, a Marine Cytotoxic Cyclic Depsipeptide

Obyanamide 1 is a cyclic depsipeptide that was recently isolated from the marine cyanobacterium Lyngbya confervoides by Moore and co-workers1. This compound displayed a potent inhibitory effect on both KB and LoVo cells in vitro. Several structural analog…     

Metabolomic-based investigation of Yinlan alleviating hyperlipidemia by inhibiting blood stasis and phlegm turbidity through the PXR-CYP3A4-ABCB1-FXR pathway

Yinlan lipid regulatory capsule (YL) is a composite traditional Chinese medicine (TCM) new drug to alleviate hyperlipidemia, while its therapeutic mechanism in vivo was not clarified with nontargeted metabolomics investigation. An animal model was established in rats fed a high-fat diet, and their body weights, body mass index (BMI) and blood cholesterol levels were measured. Serum, liver and kidney tissue samples were also extracted for PXR-CYP3A4-ABCB1-FXR signaling pathway research using PCR and UHPLC–MS. The obtained plasma samples were analyzed by UHPLC-Q-TOF-MS metabolomic investigation, which revealed PXR-CYP3A4-related metabolites and changes induced by YL. Finally, the key metabolites were chosen as index components, and their levels in the serum, liver, small intestine and bile were used for simultaneous UHPLC–MS-MS determination. The results indicated that YL was effective in rebalancing blood TG and TC levels (compared to controls). With respect to the PXR-CYP3A4-ABCB1 pathway, as a result of YL’s effect, gene expression or activity of the two targets decreased significantly in both the liver and kidney. The same trend was observed in the serum samples mentioned above. Metabolomics screening and data revealed that 44 metabolites can be regarded as biomarkers related to hyperlipidemia, fatty acids synthesis, and body energy consumption, as well as synthesis, transportation and exertion of cholesterol. YL’s treatment focused on 26 of them, primarily bile acids, indicating that the antihyperlipidemic effect of this drug lies in its inhibitory activity of cholesterol metabolism. Subsequent analysis of those in vivo components revealed that significant increases (compared to the model group) occurred in the blood, liver, small intestine and bile in groups that received medium and high doses of YL (while the low dose was relatively unchanged). Those target components exhibit a close relationship with PXR and/or CYP3A4. The use of YL repressed PXR expression and subsequently decreased CYP3A4 activity. As a result, synthesis of related bile acids increased, while cholesterol levels decreased, consequently leading to the attenuation of hyperlipidemia. This study comprehensively investigated the antihyperlipidemia mechanism of YL based on its repression of PXR-CYP3A4 activity and related metabolite yield, establishing an accurate method for evaluating the therapeutic effect of YL.     

微量元素与中医辩证分型

通过对两间小学639名学生进行微量元素检测及体格检查，并进行中医辩证分型，发现广州市部份小学生体内微量元素缺乏较严重，占体检总人数的62．3％，同时也存在营养不良，贫血、佝偻病，急慢性上呼吸道炎等、按中医辩证分型有肝热、脾气虚弱、肝血不足、肾气虚等，本文试从微量元素缺乏与中医辩证中找出两者之间的联系，以便于指导治疗，提高小学生的健康水平，增强体质和智力。