负载型贵金属催化剂的硫中毒机理——载体的酸碱性与催化剂抗硫性能的关系

以H_2S为毒物,H_2-O_2反应为催化模型反应,制备并考察了一系列不同酸碱性的负载型钯催化剂。以NH_3和吡啶为探针分子,用程序升温脱附(TPD)或红外光谱法测定了催化剂的酸碱性。用交替脉冲微反色谱技术评价了催化剂的活性和耐硫中毒性,并对催化剂的耐硫性能和载体酸碱性进行关联和解释。在以上研究基础上,指出了提高催化剂抗硫性能的途径。     

Acetylcholinesterase complexed with bivalent ligands related to huperzine a: experimental evidence for species-dependent protein-ligand complementarity

Acetylcholinesterase (AChE) inhibitors improve the cognitive abilities of Alzheimer patients. (-)-Huperzine A [(-)-HupA], an alkaloid isolated from the club moss, Huperzia serrata, is one such inhibitor, but the search for more potent and selective drugs continues. Recently, alkylene-linked dimers of 5-amino-5,6,7,8-tetrahydroquinolinone (hupyridone, 1a), a fragment of HupA, were shown to serve as more potent inhibitors of AChE than (-)-HupA and monomeric 1a. We soaked two such dimers, (S,S)-(-)-bis(10)-hupyridone [(S,S)-(-)-2a] and (S,S)-(-)-bis(12)-hupyridone [(S,S)-(-)-2b] containing, respectively, 10 and 12 methylenes in the spacer, into trigonal TcAChE crystals, and solved the X-ray structures of the resulting complexes using the difference Fourier technique, both to 2.15 A resolution. The structures revealed one HupA-like 1a unit bound to the "anionic" subsite of the active-site, near the bottom of the active-site gorge, adjacent to Trp84, as seen for the TcAChE/(-)-HupA complex, and the second 1a unit near Trp279 in the "peripheral" anionic site at the top of the gorge, both bivalent molecules thus spanning the active-site gorge. The results confirm that the increased affinity of the dimeric HupA analogues for AChE is conferred by binding to the two "anionic" sites of the enzyme. Inhibition data show that (-)-2a binds to TcAChE approximately 6-7- and > 170-fold more tightly than (-)-2b and (-)-HupA, respectively. In contrast, previous data for rat AChE show that (-)-2b binds approximately 3- and approximately 2-fold more tightly than (-)-2a and (-)-HupA, respectively. Structural comparison of TcAChE with rat AChE, as represented by the closely related mouse AChE structure (1maa.pdb), reveals a narrower gorge for rat AChE, a perpendicular alignment of the Tyr337 ring to the gorge axis, and its conformational rigidity, as a result of hydrogen bonding between its hydroxyl group and that of Tyr341, relative to TcAChE Phe330. These structural differences in the active-site gorge explain the switch in inhibitory potency of (-)-2a and 2b and the larger dimer/(-)-HupA potency ratios observed for TcAChE relative to rat AChE. The results offer new insights into factors affecting protein-ligand complementarity within the gorge and should assist the further development of improved AChE inhibitors.     

Two noncentrosymmetric complexes: [W(CO)4(bipy)] and [W(CO)4(phen)](bipy = 2,2′-bipyridine, phen = 1,10-phenanthroline) obtained through solvothermal synthesis and their optical properties

Solvothermal treatments of W(CO)₆ with 2,2′-bipyridine and 1,10-phenanthroline give [W(CO)₄(bipy)] (1) and [W(CO)₄(phen)] (2), respectively, which both crystallize in noncentrosymmetric space groups, suggesting that they meet the requirement of second harmonic generation (SHG) investigations. The preliminary experiment indicates that they are SHG active, and approximately estimated to be that of urea.     

PBA@POM Hybrids as Efficient Electrocatalysts for the Oxygen Evolution Reaction

To realize the effective conversion of renewable energy through water decomposition, efficient electrocatalysts for the oxygen evolution reaction (OER) are essential. In this article, PBA@POM was successfully prepared with a Prussian blue analogue (PBA) as the initial structure. A facile hydrothermal process is reported for obtaining PBA@POM by etching the cubic PBA with a strong Brønsted acid, H₃PMo₁₂O₄₀ (HPMo). The hollow cube structure not only exposes more active sites but also promotes electron transport, which results in excellent electrocatalytic activity for the OER. Compared with the PBA, which initially simply adhered to POM, the optimum PBA@POM hybrids display remarkably enhanced OER catalytic activity, with an almost constant overpotential of 440 mV at a current density of 10 mA cm^?2 and a small Tafel slope (23.45 mV dec^?1). The facilely prepared PBA@POM with good electrochemical activity and stability promises great potential for the OER.     

Electrocatalysis of Metalloporphyrins(Ⅷ)——Electrocatalytic Reduction of Molecular Oxygen with Water-Soluble Cobalt (Ⅱ) Tetrakis(4-Trimethyl Ammonium Phenyl) Porphyrin Catalyst

Reported here is the electrocatalytic reduction of molecular oxygen in the presence of water-soluble cobalt(Ⅱ) tetrakis(4-trimethyl ammonium phenyl) porphyrin (Co(Ⅱ)TTAPP) as catalyst in solutions of various pH values. The overpotential of molecular oxygen reduction is reduced by ca. 200-400 mV in acidic and neutral solutions compared with several decades of millivolts in alkaline solutions, indicating that Co(Ⅱ)TTAPP possesses much higher catalytic activity in acidic and neutral solutions than in alkaline. H2TTAPP in solutions of various pH exhibits no significant catalytic activity for oxygen reduction. The significant difference in the electrocatalytic activity of Co(Ⅱ)TTAPP from that of H2TTAPP for oxygen reduction indicates that the electrocatalytic activity of Co(Ⅱ)TTAPP should be attributed to the central cobalt atom (Co(Ⅱ)) coordinated by N4 internal ring in Co(Ⅱ)TTAPP. The total number of electrons involved in oxygen reduction electrocatalyzed by Co (Ⅱ)TTAPP is 2, and the product of suc     

Recovery of palladium from basic reprocessing waste of spent nuclear fuel

The methods including collection method, extraction-collection method, and special extraction-collection method have been investigated for high speed and efficient recovery of palladium from high pH reprocessing waste of spent nuclear fuel. The equilibrium of the reactions can be obtained is less than 1 minute. The maximum percent recovery of Pd is about 89%, 96% and 97% for collection, extraction-collection, and special extraction-collection methods, respectively. Nearly 100% of back extraction of Pd in the organic phase can be attained by using 7.4M ammonia solution, with a phase ratio of 1:1. The purity of the Pd product is high. The percent recovery of Pd is constant, up to 5·10³ Gy of irradiation dose.     

Synthesis of new tetrazene（N-N=N-N）-linked bi（1,2,4-triazole）

The reaction of 4-amino-1,2,4-triazole with sodium dichloroisocyanurate (SDCI) afforded new tetrazene(N-N=N-N)-linked bi(1.2,4-triazole) 2a in excellent yield.Increasing the molar ratio of SDCI to 4-amino-1,2,4-triazole,the chlorinated product 1,5,5′- trichloro-4,4′-azo-1,2,4-triazole (2b) was formed.These new compounds have been characterized by MS,~1H NMR,~(13)C NMR,and elemental analysis.     

生物,环境样品和食品中铅的痕量分析

主要根据近七年来发表的有关论文，综述了我国生物、环境样品和食品中铅和痕量分析技术进展，内容包括分子光谱、原子光谱、电化学和其他分析方法，以及联用技术和前处理等方面，收集文献３９３篇。     

Determination of in vitro permeability of drug candidates through a caco-2 cell monolayer by liquid chromatography/tandem mass spectrometry

Studying the permeability of compounds across a Caco-2 cell monolayer is an established in vitro model to screen for oral absorption and to evaluate the mechanism of transport. This assay can also be used to evaluate compounds as potential P-glycoprotein substrates and/or inhibitors. The traditional methods of sample analysis (high-performance liquid chromatography (HPLC) with a UV or fluorescence detector) limit the throughput and sensitivity of this assay. Data are presented here describing the use of liquid chromatography/tandem mass spectrometry (LC/MS/MS) for the analysis of samples derived from the Caco-2 cell studies. During the analysis an automatic switching valve was used to divert the flow from the HPLC column to waste for the first minute, preventing the early eluting salts from entering and contaminating the LC/MS interface. This approach allows the rapid and accurate determination of drug transport across the Caco-2 cell monolayer. The high sensitivity and specificity of LC/MS/MS make this technique an ideal candidate for the low concentration and high throughput routine analysis of Caco-2 cell solutions, especially if multiple compounds are administered and analyzed simultaneously. Thus, the use of LC/MS/MS will increase the value of the Caco-2 cell assay as an in vitro screening tool.     

A Novel Uranyl Complex with Dimeric Lacunary Polyoxoanion: [(A-α-SiW<Subscript>9</Subscript>O<Subscript>33</Subscript>)<Subscript>2</Subscript>K{UO<Subscript>2</Subscript>(H<Subscript>2</Subscript>O)}<Subscript>2</Subscript>]<Superscript>11−</Superscript>

A novel uranyl complex with dimeric lacunary polyoxoanion like open-mouthed clam, Na₅[(A-α-SiW₉O₃₃H₃)₂K{UO₂(H₂O)}₂], was prepared and characterized by elemental analysis, infrared and ultraviolet–visible spectroscopy and single crystal X-ray diffraction. In the anion, two A-α-SiW₉O₃₄¹⁰⁻ groups share two terminal oxygen atoms O_d′ derived from removal of three corner-shared W atoms from saturated α-Keggin anion, forming a dimeric anion with an open mouth in which potassium ion and uranyl ions are coordinated. Uranium atom adopts a pentagonal bipyramidal geometry. The coordinating anions are linked by sodium ions via coordination of terminal or bridging oxygen atoms, forming two-dimensional layer arrangement. Between the layers are the hydrogen bonds from which a supramolecular architecture is created. UV–VIS spectrum gives W–O and U–O charge transfer transitions at 230–265 and 432 nm, showing the change of geometry of the polyanion and weakening of the U–O bonds of the uranyl cation. Electronic supplementary material The online version of this article () contains supplementary material, which is available to authorized users.