Three Keggin-based complexes modified by an asymmetric ligand: structures,electrochemical, photocatalytic and fluorescence sensing properties

By using an asymmetric ligand with triazole and imidazole groups, three Keggin-based complexes were obtained, [Cu(HMET)₄(H₂O)₂](PMo₁₂O₄₀)₂·2H₂O (1), [Cu₃(HMET)₄Cl₂(H₂O)₂(XM₁₂O₄₀)₂]·4H₂O (X?=?Si, M?=?W 2, X?=?Ge, M?=?Mo 3) (MET?=?4-(2-imidazol-1-yl-ethyl)-4H-[1,3,4]triazole). Complex 1 contains discrete Keggin anions and mono-nuclear [Cu(MET)₄(H₂O)₂]²⁺ clusters. Complexes 2 and 3 are isostructural with tri-nuclear Cu clusters linked by Keggin anions to construct a 1D chain. The 1- to 3-CPEs show electrocatalytic properties and can also act as nitrite amperometric sensors. Complexes 1–3 exhibit photocatalytic activities for degradation of MB. Complexes 1–?3 own fluorescence sensing properties for detecting Hg²⁺ ions.

Graphical abstract

By using an asymmetric ligand three POM-based complexes were constructed. The 1– to 3–CPEs exhibit good electrocatalytic activities and can be used as nitrite amperometric sensors. The title complexes show good photocatalytic activities for degradation of MB. Moreover, complexes 1–3 can act as fluorescence sensors to selectively detect Hg²⁺.

     

Cr（Ⅲ）—5—Br—PADAP—Triton X—100析相光度法测定微量铬的研究

研究Cr(Ⅲ)-5-Br-PADAP-Triton X-100析相显色体系,建立测定微量铬的析相光度法。在pH 4.5乙酸-乙酸钠介质中,Cr(Ⅲ)、5-Br-PADAP、Triton X-100加热形成的配合物,于95℃恒温浴中析相1h,即被Triton X-100相完全富集,最大吸收峰为593nm,铬含量在0～10μg/5ml服从比耳定律,以硫脲、锰-EDTA、柠檬酸钠、氟化钾为掩蔽剂,测定水样中微量铬,获得满意结果。     

Selective synthesis and characterization of single-crystal silver molybdate/tungstate nanowires by a hydrothermal process

Selective synthesis of uniform single crystalline silver molybdate/tungstate nanorods/nanowires in large scale can be easily realized by a facile hydrothermal recrystallization technique. The synthesis is strongly dependent on the pH conditions, temperature, and reaction time. The phase transformation was examined in details. Pure Ag(2)MoO(4) and Ag(6)Mo(10)O(33) can be easily obtained under neutral condition and pH 2, respectively, whereas other mixed phases of Mo(17)O(47), Ag(2)Mo(2)O(7,) Ag(6)Mo(10)O(33) were observed under different pH conditions. Ag(6)Mo(10)O(33) nanowires with uniform diameter 50-60 nm and length up to several hundred micrometers were synthesized in large scale for the first time at 140 degrees C. The melting point of Ag(6)Mo(10)O(33) nanowires were found to be about 238 degrees C. Similarly, Ag(2)WO(4), and Ag(2)W(2)O(7) nanorods/nanowires can be selectively synthesized by controlling pH value. The results demonstrated that this route could be a potential mild way to selectively synthesize various molybdate nanowires with various phases in large scale.     

水煤气变换反应的微观动力学分析──Cu基催化剂上H_2S中毒失活原因的 Monte Carlo 模拟研究

用ＢＯＣＭＰ方法及ＭｏｎｔｅＣａｒｌｏ模拟技术，对Ｈ２Ｓ导致Ｃｕ基催化剂失活的原因进行了计算分析。研究结果表明，当原料气中存在Ｈ２Ｓ时，ＷＧＳ反应的活化能明显高于无Ｈ２Ｓ时的活化能，随着表面Ｈ２Ｓ浓度的增大（θ＝０，０．１０，０．２５），反应的活化能也逐渐变大（其大小比为１∶１．３４∶３．３），究其原因可归结为Ｈ２Ｓ的存在使得反应物分子的吸附热减小，从而使Ｈ２Ｏ的解离吸附（ＷＧＳ反应的速控步骤）活化能增大。     

卡尔曼滤波析相光度法同时测定锰铁铜锌镉的研究——5-Br-PADAP—Triton X-100体系

运用卡尔曼滤波递推法,以2-(5-溴-2-吡啶偶氮)—5-二乙氨基苯酚(5-Br-PADAP)为显色剂,建立了同时测定锰、铁、铜、锌、镉析相光度法.在pH9.0硼酸-氢氧化钠介质中,胶束溶液在95℃加热1h,配合物被Triton X-100相完全富集,最大吸收峰分别为锰566nm、铁556nm、铜560nm、锌562nm、镉557nm,工作曲线范围除镉为0～8μg/5ml外,其余均为0～10μg/5ml.应用于大米中锰铁铜锌镉的同时测定,结果满意.     

Measurement of the half life of126Sn using a radiochemical method

The half-life of¹²⁶Sn has never been measured accurately. The value quoted in the literature is approximately 10⁵y, which was measured in 1958. In the present work we measured accruately the half life of¹²⁶Sn to be (2.5±0.2)×10⁵y using a radiochemical method.     

A facile synthesis of bifunctional phospholipids for biomimetic membrane engineering

We report a facile synthesis of bifunctional phospholipid conjugates by acylation of N-protected lyso-phosphatidylethanolamine with 12-acryloxy-1-dodecanoic acid and followed with deprotection and conjugation with biotin, FITC, Texas Red, or EMC groups. The lipid conjugates can be used to generate a multifunctional substrate-supported phospholipid membrane via bioconjugation reaction to biotin or covalent attachment to EMC at their hydrophilic terminus. In addition, conjugation to fluorophores, FITC or Texas Red, provides a convenient mechanism to monitor lipid membrane formation and stability. Significantly, in situ photopolymerization of the acrylate group at the end of one of two hydrophobic alkyl chains stabilizes the phospholipid membrane.     

Electronic effects steer the mechanism of asymmetric hydrogenations of unfunctionalized aryl-substituted alkenes

Density functional theory (PBE and B3LYP) was used to study asymmetric hydrogenations of alkenes catalyzed by an iridium imidazolylidine oxazoline complex. The calculation predicts that the alkene preferentially coordinates to the site trans to the carbene. The coordinated alkene then reacts first with the H2 ligand, then with the hydride to form alkane. Finally, the alkane is released by equilibrating with extrinsic H2 and alkene. Enantioface selectivities for hydrogenations of trisubstituted alkenes seem to be driven primarily by steric interactions with the adamantyl part of the ligand; only the smallest substituents can adopt a site close to it. Application of this theoretical model leads to correct predictions regarding the experimentally observed sense and magnitude of the enantioselectivities.     

Iridium-mediated asymmetric hydrogenation of 2,3-diphenylbutadiene: a revealing kinetic study

Hydrogenation of 2,3-diphenylbutadiene mediated by a chiral iridium carbene oxazoline complex was studied. The kinetics of the reaction showed that it occurred in two distinct stages. The first corresponded to slow consumption of the diene to form half-hydrogenated products, i.e., monoenes. After all the diene was consumed, however, the reaction was much faster and more stereoselective. These data were interpreted in terms of possible catalytic intermediates.     

Mechanistic evaluation of the halocyclization of 4-penten-1-ol by some Bis(2-substituted pyridine) and Bis(2,6-disubstituted pyridine)bromonium triflates

The halocyclization reaction of 4-penten-1-ol mediated by various bis(2-substituted pyridine) and (2,6- disubstituted pyridine)bromonium triflates (P(2)Br(+)OTf(-)) was investigated to determine the influence of the substituents on the mechanism of reaction. In all cases, the reaction proceeds via a two-step process where the starting P(2)Br(+) reversibly dissociates to a reactive monosubstituted PBr(+), which then is captured by 4-penten-1-ol to form halocyclized product (2-bromomethyltetrahydrofuran). The dissociation rate constant of P(2)Br(+) (k(d)) is sensitive to the steric bulk at the 2- and 6-positions, and in the case of the 2, 6-dicyclohexylpyridine or 2,6-dicyclopentylpyridine, the P(2)Br(+) species are too unstable to isolate. The partitioning ratio of the reactive intermediate (PBr(+)) between reversal and product formation (k(-)(d)/k(2)) is not particularly sensitive to the nature of the pyridine, the limiting values being 3-7 except in the case of bis(2(-)-menthylpyridine)bromonium triflate where the k(-)(d)/k(2) ratio is approximately 80. The reaction of 4-penten-1-ol and its OD isotopomer with bis(lutidine)bromonium triflate was investigated to determine the deuterium kinetic isotope effect (dkie) on the bromocyclization reaction. The (k(-)(d)/k(2))(H/D) ratio is 1.0, indicating that the rate-limiting step for the bromocyclization is probably formation of a PBr(+)-4-penten-1-ol complex which does not involve substantial changes in the bonding of the OH. The cyclization of 4-penten-1-ol and 4-pentenoic acid mediated by bis(2(-)-menthylpyridine)bromonium triflate produces an enantiomeric excess in the cyclized products of only 2.4% and 4.8% respectively.