Decarboxylative aldol reactions of allyl beta-keto esters via heterobimetallic catalysis

Mild and selective heterobimetallic-catalyzed decarboxylative aldol reactions involving allyl beta-keto esters have been developed. The reaction is promoted by Pd(0)- and Yb(III)-DIOP complexes at room temperature and involves the in situ formation of a ketone enolate from allyl beta-keto esters followed by addition of the enolate to aldehydes. The reaction is a new example of heterobimetallic catalysis in which the optimized reaction conditions require the addition of both metals.     

Optical properties of nanocrystalline Y2O3:Eu depending on its odd structure

The structure of nanocrystalline Y2O3:Eu prepared by a combustion reaction was analyzed by XRD and high-resolution electron microscopy. Compared with a large-scale particles, 5-nm Y2O3:Eu particles presented as distorted crystallite and rough surfaces. Luminescent and absorption properties of nano-Y2O3:Eu showed remarkably particle size effects. At Y2O3:Eu particle sizes smaller than 10 nm some new results were observed: (a) a red shift of the charge-transfer-state absorption; (b) new emission bands of Eu3+ in the 5D0 --> 7F2 region; (c) luminescent decay of energy level 5D0 of Eu3+ turning to a two-step exponential; and (d) a pronounced increase in quenching concentration and much lower phonon density compared with those of the bulk material. All these phenomena can be attributed to the effect of the softened lattice and surface state of the nanomaterial. The latter was confirmed by stronger excitation by the host absorption after the surface modification.     

Average peptide score: a useful parameter for identification of proteins derived from database searches of liquid chromatography/tandem mass spectrometry data

The quantity and variable quality of data that can be generated from liquid chromatography (LC)/mass spectrometry (MS)-based proteomics analyses creates many challenges in interpreting the spectra in terms of the actual proteins in a complex sample. In spite of improvements in algorithms that match putative peptide sequences to MS/MS spectra, the assembly of these lists of possible or probable peptides into a 'correct' set of proteins is still problematic. We have observed a trend in a simple relationship, derived from standard database search outputs, which can be useful in assessing the quality of a MS/MS-based protein identification. Specifically, the ratio of the protein score and number of non-redundant peptides, or average peptide score (APS), can facilitate initial filtering of database search results in addition to providing a useful measure of confidence for the proteins identified. This parameter has been applied to results from the analysis of multi-protein complexes derived from pull-down experiments analyzed using a two-dimensional LC/MS/MS workflow. In particular, the complex list of protein identifications derived from a drug affinity pull-down with immobilized ampicillin and an E. coli lysate was greatly simplified by applying the APS as a filter, allowing for facile identification of the penicillin-binding proteins known to interact with ampicillin. Furthermore, an APS threshold can be used for any data sets derived from electrospray ionization (ESI)- or matrix-assisted laser desorption/ionization (MALDI)-MS/MS experiments and is also not specific to any database search program.     

Mineralization mechanism of calcium phosphates under three kinds of Langmuir monolayers

Three kinds of Langmuir monolayers formed by dipalmitoylphosphatidylcholine (DPPC), arachidic acid (AA), and octadecylamine (ODA) were used as templates to study the initial stage of nucleation and crystallization of calcium phosphates. It was demonstrated that the combination of calcium ions (or phosphates) to the monolayer/subphase interface is a prerequisite for subsequent nucleation. It was found that calcium phosphate dihydrate (DPCD) formed at 25.0 degrees C for 12 h has a biphasic structure containing both amorphous and crystalline phases. These results showed that calcium phosphates were formed through a multistage assembly process, during which an initial amorphous phase DPCD was followed by a phase transformation into a crystalline phase and then the most stable hydroxyapatite (HAp). This provided new insights into the template-biomineral interaction and a mechanism for biomineralization.     

4,4′‐Bipyridyl N,N′‐dioxide–3‐hydroxy‐2‐naphthoic acid (1/2)

4,4′‐Bipyridyl N,N′‐dioxide crystallizes with 3‐hydr­oxy‐2‐naphthoic acid to give a centrosymmetric three‐component adduct, C₁₀H₈N₂O₂·2C₁₁H₈O₃, which is engineered into a two‐dimensional layer structure by two kinds of π–π inter­actions. Weak C—H⋯O inter­actions further link the two‐dimensional structure into a three‐dimensional structure.     

Two-Dimensional Supramolecular from the Self-Assembly of Dissymmetrical Oxamidato-Bridged Heterometallic Trinuclear Building Blocks: Synthesis, Crystal Structure, and Magnetic Properties

Two heterometallic trinuclear complexes {[Cu(oxbp)]₂Co(H₂O)₂}1.5DMF0.5H₂O (complex 1) and {[Cu(oxbm)]₂Co(H₂O)₂}2DMF (complex 2) were obtained from the self-organization of two new dissymmetrical oxamidato-bridged copper(II) building blocks [Cu(oxbp)]^– and [Cu(oxbm)]^–[H₃oxbp=N-benzoato-N'-(3-aminopropyl)oxamido, H₃oxbm=N-benzoato-N'-(2-amino-2-methylethyl)oxamido, DMF=dimethylformamide]. The crystal structure of complex 1 has been determined. Complex 1 crystallize in triclinic system, space group P-1, a=8.0609(16) Å, b=10.661(2) Å, c=22.279(5) Å, =85.32(3), =86.64(3), =70.90(3), and Z=1. The crystal structure of complex 1 consists of neutral trinuclear complex units, and hydrogen bond involved DMF and water molecules. Through the hydrogen bonds, weak coordination and CuCu weak interactions, complex 1 features a 2-D supramolecular structure. Magnetic susceptibility measurements (5–100 K) indicate that the central Co(II) and terminal copper metal ions are antiferromagnetically coupled with J=–28.09 and J=–29.70 cm^–1 for complex 1 and 2, respectively.     

环境监测实验室管理系统的开发与应用

基于2005版《计量认证/审查认可(验收)评审准则》要求,为满足环境监测实验室业务流程而设计开发了信息管理系统。该系统主要用于环境监测实验室的资源管理和日常自动化办公。系统采用B/S架构,实现全球化办公运作,能对监测样品的受理、分发、分析、原始记录、监测报告、数据三级审核、报告签发实现全程自动流转,并运用工作流和智能表单设计实现实验室程序文件中各类程序和日常办公事务流程的执行;原始记录和监测报告全部实现自动归档及智能查询;同时根据2005版准则中的要求,对人员、设备、材料、环境要素、记录、质量控制等所有要素全面实施网络化管理。     

A new chiral Rh(II) catalyst for enantioselective [2 + 1]-cycloaddition. mechanistic implications and applications

A novel chiral Rh(II) catalyst (1) is introduced for the [2 + 1]-cycloaddition of ethyl diazoacetate to terminal acetylenes and olefins with high enantioselectivity. The catalyst 1 consists of one acetate bridging group and three mono-N-triflyldiphenylimidazoline-2-one bidentate ligands (DPTI) spanning the Rh(II)-Rh(II) metallic center in a structure that was determined by single-crystal X-ray diffraction analysis. A rational mechanism is advanced that provides a straightforward explanation for the enantioselectivity and absolute stereochemical course of the [2 + 1]-cycloaddition reactions. A key element in this explanation is the cleavage of one of the Rh-O bonds of the bridging acetate group in the intermediate Rh-carbene complex to form a new pentacoordinate Rh carbene complex (formally 1.5 valent Rh) that can undergo [2 + 2]-cycloaddition with the C-C pi-bond of the acetylenic or olefinic substrate. Reductive elimination of the resulting adduct affords the cyclopropene or cyclopropane product. The C2-symmetry of the two DPTI ligands orthogonal to the bridging acetate also contributes to the high observed enantioselectivity and mechanistic clarity. The catalyst 1, which functions effectively at 0.5 mol %, can be recovered efficiently for reuse. Its ready availability, robustness, and effectiveness suggest it as a useful addition to the list of practical chiral Rh(II) catalysts for synthesis.     

不同孔径硅胶聚合物键合相对蛋白质分离的影响

介绍了不同孔径的硅胶聚合物键合相的合成，比较了其对蛋白质的分离特性。结果表明，大孔径的硅胶聚合物键合相比表面积小，易于获得生物大了分子的快速分离。