Insertion of CO2 into a palladium allyl bond and a Pd(II) catalysed carboxylation of allyl stannanes

The complex 2,6-bis[(di-t-butylphosphino)methyl]phenyl allyl palladium (PCP(tBu)Pd-allyl, 3) reacts with CO(2) in a very fast insertion reaction to give the corresponding butenoate complex. The reaction is thought to occur via a cyclic six-membered transition state (7), where the gamma-carbon of the allyl group is linked up with the CO(2)-carbon. A group of related PCP complexes were investigated as catalysts for the carboxylation of tributyl(allyl)stannane. A catalytic cycle is proposed for this reaction where the rate determining step is the transmetallation between tin and palladium. The carboxylation reaction is faster using less sterically crowded catalysts whereas the electron richness of the palladium complexes seems less important for reactivity. Thus, there was no apparent difference in reactivity between 2,6-bis[(di-phenylphosphino)methyl]phenyl palladium triflouroacetate (13) and resorcinolbis(diphenyl)phosphinite palladium triflouroacetate (10). Both of these complexes give high turnovers for the carboxylation of tributyl(allyl)stannane (80% in 16 h using a ca. 5% catalyst loading and 4 atm CO(2) pressure). On the other hand complex 3 was inactive in the catalytic carboxylation reaction.     

Dissociative electron attachment to gas phase glycine: exploring the decomposition pathways by mass separation of isobaric fragment anions

Dissociative electron attachment to gas phase glycine generates a number of fragment ions, among them ions observed at the mass numbers 15, 16 and 26 amu. From stoichiometry they can be assigned to the chemically rather different species NH(-)/CH(3)(-)(15 amu), O(-)/NH(2)(-)(16 amu) and CN(-)/C(2)H(2)(-)(26 amu). Here we use a high resolution double focusing two sector mass spectrometer to separate these isobaric ions. It is thereby possible to unravel the decomposition reactions of the different transient negative ions formed upon resonant electron attachment to neutral glycine in the energy range 0-15 eV. We find that within the isobaric ion pairs, the individual components generally arise from resonances located at substantial different energies. The corresponding unimolecular decompositions involve complex reaction sequences including multiple bond cleavages and substantial rearrangement in the precursor ion. To support the interpretation and assignments we also use (13)C labelling of glycine at the carboxylic group.     

Capturing structure-activity relationships from chemogenomic spaces

Modeling off-target effects is one major goal of chemical biology, particularly in its applications to drug discovery. Here, we describe a new approach that allows the extraction of structure-activity relationships from large chemogenomic spaces starting from a single chemical structure. Several public source databases, offering a vast amount of data on structure and activity for a large number of different targets, have been investigated for their usefulness in automated structure-activity relationships (SAR) extraction. SAR tables were constructed by assembling similar structures around each query structure that have an activity record for a particular target. Quantitative series enrichment analysis (QSEA) was applied to these SAR tables to identify trends and to transform these trends into topomer CoMFA models. Overall more than 1700 SAR tables with topomer CoMFA models have been obtained from the ChEMBL, PubChem, and ChemBank databases. These models were able to highlight the structural trends associated with various off-target effects of marketed drugs, including cases where other structural similarity metrics would not have detected an off-target effect. These results indicate the usefulness of the QSEA approach, particularly whenever applicable with public databases, in providing a new means, beyond a simple similarity between ligand structures, to capture SAR trends and thereby contribute to success in drug discovery.     

掺碲硒化镓晶体的光学性能(英文)

采用水平区熔法生长了碲(Te)掺杂浓度(质量百分比)分别为0.05%,0.1%,0.5%,1%,2%的硒化镓(GaSe)晶体,并分别对掺杂浓度为0.01%,0.07%,0.38%,0.67%,2.07%的GaSe∶Te晶体的光学性能进行了表征。首次研究了GaSe∶Te晶体中刚性层声子模式的转换。吸收光谱测试结果表明:当Te掺杂浓度小于0.38%时,振动中心位于0.59 THz附近的E'(2)刚性模式吸收峰强度可达最大值,这一过程与GaSe∶Te晶体光学性能的提高密切相关。但Te掺杂浓度的进一步提高会导致E'(2)刚性模式吸收峰强度逐渐减弱,当Te掺杂浓度为1%时,E'(2)刚性模式吸收峰基本消失。这两个过程与GaSe∶Te晶体光学质量的下降密切相关。因此,E'(2)刚性模式吸收强度达到最高时对应的掺杂浓度即是GaSe∶Te晶体中Te的最佳掺杂浓度,光整流产生太赫兹过程证实了此结论的正确性。     

GaSe：AgGaSe_2晶体的光学性能及应用（英文）

从GaSe∶AgGaSe₂熔体(质量掺杂浓度为10%)中生长的非线性光学晶体ε-GaSe∶Ag晶体(质量掺杂浓度≤0.04%)是一种非中心对称晶体,可用于相位匹配频率转换。Ag的掺入使GaSe晶体的显微硬度提高了30%,从而使其可以在任意方向上进行切割和抛光。本文研究了GaSe∶AgGaSe₂晶体在可见、中红外及太赫兹波段的光学性能。实验证明:GaSe∶AgGaSe₂晶体的吸收系数是纯GaSe晶体的2倍,其CO₂激光倍频效率是ZnGeP₂晶体的1.7倍。