镍、钴超分子配合物的合成、晶体结构及理论计算

通过水热法合成了2个新的金属-有机超分子配合物[Ni(eoba)(phen)(H₂O)₂]·0.58H₂O(1)和[Co(eoba)(phen)]₂·H₂O(2)(H₂boba=4,4''-(乙烷-1,2-二氧基)-二苯甲酸,phen=菲咯啉),并对其进行了元素分析、红外光谱、热重和X射线单晶衍射测定。配合物1和2是同构的,每个配合物都是六配位的,菲咯啉分子上的2个氮原子、4,4''-(乙烷-1,2-二氧基)-二苯甲酸配体上的2个氧原子和2个配位水分子与金属配位。此外,还用高斯03程序PBE0/LANL2DZ方法对配合物1进行了自然键轨道(NBO)分析,计算结果表明配位原子与Ni原子之间存在着共价作用。     

Aggregation Effects in Visible‐Light Flavin Photocatalysts: Synthesis,Structure, and Catalytic Activity of 10‐Arylflavins

A series of 10‐arylflavins (10‐phenyl‐, 10‐(2′,6′‐dimethylphenyl)‐, 10‐(2′,6′‐diethylphenyl)‐, 10‐(2′,6′‐diisopropylphenyl)‐, 10‐(2′‐tert‐butylphenyl)‐, and 10‐(2′,6′‐dimethylphenyl)‐3‐methylisoalloxazine ( 2 a – f )) was prepared as potentially nonaggregating flavin photocatalysts. The investigation of their structures in the crystalline phase combined with ¹H‐DOSY NMR spectroscopic experiments in CD₃CN, CD₃CN/D₂O (1:1), and D₂O confirm the decreased ability of 10‐arylflavins 2 to form aggregates relative to tetra‐O‐acetyl riboflavin ( 1 ). 10‐Arylflavins 2 a – d do not interact by π–π interactions, which are restricted by the 10‐phenyl ring oriented perpendicularly to the isoalloxazine skeleton. On the other hand, N3? H???O hydrogen bonds were detected in their crystal structures. In the structure of 10‐aryl‐3‐methylflavin ( 2 f ) with a substituted N3 position, weak C? H???O bonds and weak π–π interactions were found. 10‐Arylflavins 2 were tested as photoredox catalysts for the aerial oxidation of 4‐methoxybenzyl alcohol to the corresponding aldehyde (model reaction), thus showing higher efficiency relative to 1 . The quantum yields of 4‐methoxybenzyl alcohol oxidation reactions mediated by arylflavins 2 were higher by almost one order of magnitude relative to values in the presence of 1 .     

Hydrogenation and double bond isomerization of hexenes over EUROPT-1

Hexenes give large amounts of hexane and isomeric hexenes over EUROPT-1. A constant hydrocarbon coverage can be assumed in the steady-state period of the reaction; the direction of reactions of these surface species depends on the hydrogen excess and also on the structure of starting hydrocarbon.

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EUROPT-1 , . , . , .

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Based on the diploma work of Mr. M. Räth and Ms. B. Brose.     

两个4-[(8-羟基-5-喹啉)偶氮]苯磺酸配合物的合成、结构及性质研究

以4-[(8-羟基-5-喹啉)偶氮]苯磺酸(H₂L)为配体,采用溶剂热合成法合成了两个配合物[CuL(en)]·0.5H₂O (1)和[CuL₂][Cu(en)₂]·2H₂O (2)(en=乙二胺),并采用单晶X-射线衍射、红外光谱、元素分析、X-射线粉末衍射和热重分析对其进行表征。化合物1和2通过氢键和π…π相互作用连接形成了三维超分子网格。此外,还研究了两个化合物的荧光性质。     

6, 6’-二硫二烟酸构筑的锌配位聚合物的合成、晶体结构和荧光性能

本文以6,6′-二硫二烟酸为主配体,通过水热法合成了新的配合物{[Zn(cpds)(dpa)]·H2O}n(1)(H2cpds=6,6′-dithiodinicotinic acid,dpa=dipyridin-2-ylamine)。用X-射线单晶衍射分析确定了配合物为三斜晶系,P1空间群,其晶体学参数为a=0.846 7(2),b=1.167 4(3),c=1.226 5(3)nm,α=73.605(3)°,β=78.656(3)°,γ=81.484(3)°,V=1.134 7(5)nm3,Dc=1.850 g·cm-3,Z=2。结构分析表明配合物1为一维链状结构,相邻一维链之间堆积形成三维超分子网络结构。本文还研究了配合物的热稳定性和荧光性质。     

Analysis by gas chromatography-mass spectrometry of the essential oil from the aerial parts of Pimpinella junoniae Ceb. & Ort., gathered in La Gomera, Canary Islands, Spain

The essential oil from the aerial parts of Pimpinella junoniae Ceb. & Ort., growing in La Gomera, Canary Islands, Spain, was studied by gas chromatography and gas chromatography-mass spectrometry, and 43 constituents were identified. The major components were found to be alpha-zingiberene (20.6%), alpha-pinene (17.9%), (E)-beta-farnesene (9.3%), ar-curcumene (7.4%), beta-phellandrene (7.0%), beta-bisabolene (6.1%) and epoxypseudoisoeugenyl 2-methylbutyrate (6.0%). The decomposition product of epoxypseudoisoeugenol derivatives, 5-methoxy-2-methylbenzofuran (5.7%), moderate amounts of other arylpropanoids with the pseudoisoeugenol skeleton (total percentage, 5.2%) and other compounds such as beta-sesquiphellandrene (3.0%), cis-beta-guaiene (1.5%), alpha-phellandrene (1.5%) and alpha-bisabolol (1.3%), were also found.     

Redox-Guest-Induced Multimode Photoluminescence Switch for Sequential Logic Gates in a Photoactive Coordination Cage

Molecular or supramolecular level photoluminescence (PL) modulation combining chemical and photonic input/output signals together in an integrated system can provide potential high-density data memorizing and process functions intended for miniaturized devices and machines. Herein, a PL-responsive supramolecular coordination cage has been demonstrated for complex interactions with redox-active guests. PL signals of the cage can be switched and modulated by adding or retracting Fc derivatives or converting TTF into different oxidation states through chemical or photochemical pathways. As a result, reversible or stepwise PL responses are displayed by these host–guest systems because of the occurrence of photoinduced electron-transfer (PET) or fluorescence resonance energy transfer (FREnT) processes, providing unique nanodevice models bearing off/on logic gates or memristor-like sequential memory and Boolean operation functions.     

A top-down LC-FTICR MS-based strategy for characterizing oxidized calmodulin in activated macrophages

A liquid chromatography-mass spectrometry (LC-MS)-based approach for characterizing the degree of nitration and oxidation of intact calmodulin (CaM) has been used to resolve ～250 CaM oxiforms using only 500 ng of protein. The analysis was based on high-resolution data of the intact CaM isoforms obtained by Fourier-transform ion cyclotron resonance mass spectrometry (FTICR MS) coupled with an on-line reversed-phase LC separation. Tentative identifications of post-translational modifications (PTMs), such as oxidation or nitration, have been assigned by matching observed protein mass to a database containing all theoretically predicted oxidation products of CaM and verified through a combination of tryptic peptide information (generated from bottom-up analyses) and on-line collisionally induced dissociation (CID) tandem mass spectrometry (MS/MS) at the intact protein level. The reduction in abundance and diversity of oxidatively modified CaM (i.e., nitrated tyrosines and oxidized methionines) induced by macrophage activation has been explored and semiquantified for different oxidation degrees (i.e., no oxidation, moderate, and high oxidation). This work demonstrates the power of the top-down approach to identify and quantify hundreds of combinations of PTMs for single protein target such as CaM and implicate competing repair and peptidase activities to modulate cellular metabolism in response to oxidative stress.     

A Rapid Method for Qualitative and Quantitative Analysis of Major Constituents in Dengzhanxixin Injection by LC-DAD-ESI–MSn

For the first time a rapid method for qualitative and quantitative analysis of constituents in Dengzhanxixin injection was established by liquid chromatography with electrospray ionization–tandem mass spectrometry. Eighteen compounds including flavonoids and phenolic acids were characterized or tentatively identified. Ten of these compounds, including 5-O-caffeoylquinic acid, caffeic acid, 1,3-O-dicaffeoylquinic acid, 6′-O-caffeoylerigeroside, scutellarin, 3,4-O-dicaffeoylquinic acid, 3,5-O-dicaffeoylquinic acid, erigoster B, apigenin-7-O-glucuronide and 4,5-O-dicaffeoylquinic acid, were further quantified as marker substances by LC-DAD using a C₁₈ column at 0.4 mL min^?1 within 37 min. The quantitative method was validated for ten interesting compounds, including linearity, accuracy, precisions, LOQ and LOD, which was proved to be sensitive, reproducible and accurate. The study might provide a comprehensive method for the quality assessment of dengzhanxixin injection.     

Combination of developed in-house method and application of Eichrom Sr resin to determine the radioactivity of <Superscript>90</Superscript>Sr in environmental sample

A method is described for the determination of ⁹⁰Sr in environmental samples using combination of developed in-house method, Eichrom Sr resin and Beta Counter. Strontium was efficiently, rapidly and simply separated from Ca and other interfering matrix components by Eichrom Sr resin. All the results in general showed good accuracy, high precision, reliable and in good agreement between these two measured and certified value of SRM (i.e. IAEA-375, IAEA-326, IAEA-152 and IAEA-414). As a whole, the procedure described in this work notably improves conventional methods in particular concerning the time needed, sample volume, safer and others. Thus, the introduced method was successfully performed and will be applied to actual sample for the determination of ⁹⁰Sr in different environmental materials such as soil, sediments, milk, biological sample, water etc.