Phenothiazine–BODIPY–Fullerene Triads as Photosynthetic Reaction Center Models: Substitution and Solvent Polarity Effects on Photoinduced Charge Separation and Recombination

Novel photosynthetic reaction center model compounds of the type donor₂–donor₁–acceptor, composed of phenothiazine, BF₂‐chelated dipyrromethene (BODIPY), and fullerene, respectively, have been newly synthesized using multistep synthetic methods. X‐ray structures of three of the phenothiazine‐BODIPY intermediate compounds have been solved to visualize the substitution effect caused by the phenothiazine on the BODIPY macrocycle. Optical absorption and emission, computational, and differential pulse voltammetry studies were systematically performed to establish the molecular integrity of the triads. The N‐substituted phenothiazine was found to be easier to oxidize by 60 mV compared to the C‐substituted analogue. The geometry and electronic structures were obtained by B3LYP/6‐31G(dp) calculations (for H, B, N, and O) and B3LYP/6‐31G(df) calculations (for S) in vacuum, followed by a single‐point calculation in benzonitrile utilizing the polarizable continuum model (PCM). The HOMO?1, HOMO, and LUMO were, respectively, on the BODIPY, phenothiazine and fullerene entities, which agreed well with the site of electron transfer determined from electrochemical studies. The energy‐level diagram deduced from these data helped in elucidating the mechanistic details of the photochemical events. Excitation of BODIPY resulted in ultrafast electron transfer to produce PTZ–BODIPY^.+–C₆₀^.?; subsequent hole shift resulted in PTZ^.+–BODIPY–C₆₀^.? charge‐separated species. The return of the charge‐separated species was found to be solvent dependent. In nonpolar solvents the PTZ^.+–BODIPY–C₆₀^.? species populated the ³C₆₀* prior to returning to the ground state, while in polar solvent no such process was observed due to relative positioning of the energy levels. The ¹BODIPY* generated radical ion‐pair in these triads persisted for few nanoseconds due to electron transfer/hole‐shift mechanism.     

Aromatic Nitrogen Mustard‐Based Prodrugs: Activity,Selectivity, and the Mechanism of DNA Cross‐Linking

Three novel H₂O₂‐activated aromatic nitrogen mustard prodrugs ( 6 – 8 ) are reported. These compounds contain a DNA alkylating agent connected to a H₂O₂‐responsive trigger by different electron‐withdrawing linkers so that they are inactive towards DNA but can be triggered by H₂O₂ to release active species. The activity and selectivity of these compounds towards DNA were investigated by measuring DNA interstrand cross‐link (ICL) formation in the presence or absence of H₂O₂. An electron‐withdrawing linker unit, such as a quaternary ammonia salt ( 6 ), a carboxyamide ( 7 ), and a carbonate group ( 8 ), is sufficient to deactivate the aromatic nitrogen mustard resulting in less than 1.5 % cross‐linking formation. However, H₂O₂ can restore the activity of the effectors by converting a withdrawing group to a donating group, therefore increasing the cross‐linking efficiency (>20 %). The stability and reaction sites of the ICL products were determined, which revealed that alkylation induced by 7 and 8 not only occurred at the purine sites but also at the pyrimidine site. For the first time, we isolated and characterized the monomer adducts formed between the canonical nucleosides and the aromatic nitrogen mustard ( 15 ) which supported that nitrogen mustards reacted with dG, dA, and dC. The activation mechanism was studied by NMR spectroscopic analysis. An in vitro cytotoxicity assay demonstrated that compound 7 with a carboxyamide linker dramatically inhibited the growth of various cancer cells with a GI₅₀ of less than 1 μM , whereas compound 6 with a charged linker did not show any obvious toxicity in all cell lines tested. These data indicated that a neutral carboxyamide linker is preferable for developing nitrogen mustard prodrugs. Our results showed that 7 is a potent anticancer prodrug that can serve as a model compound for further development. We believe these novel aromatic nitrogen mustards will inspire further and effective applications.     

聚合物负载的钯-咪唑催化烯烃加氢

A polymer-supported palladium-imidazole catalyst was used to catalyze the hydrogenation of various olefins under mild conditions. The rate of hydrogenation was studied. The effects of factors such as substrate concentration,catalyst concentration,partial pressure of hydrogen and temperature on initial rate of reaction of selected olefins were investigated. A mechanism for the reaction was proposed from the rate equation. The effects of the solvent and structure of the olefin on the rate of hydrogenation were investigated. The catalyst showed good reusability without any leaching of metal from the support. The homologous analog of the polymer-supported catalyst could not be used as catalyst for the hydrogenation of olefins in methanol because there was precipitation of the metal during reaction.     

顺序注射催化光度分析法测定环境水样中痕量钼

基于钼（VI）对碘化钾/过氧化氢反应体系催化作用的反应产物在350 nm处的吸光度与钼在一定浓度范围内呈线性关系的原理,建立了灵敏的顺序注射催化动力学光度分析新方法。方法的线性范围是2~300 μg/L,方法的检出限（3s）为1.1μg/L,相对标准偏差（RSD）为 0.6%（n=11）。 每次测定仅消耗100μL试样,75μL KI和125μL H2O2 , 对4个不同水样的钼测定回收率在95.2%~105.2%之间。顺序注射催化动力学光度分析测定环境水样中痕量钼的方法是一种快速、准确的新方法。     

关于陀螺信号处理中小波基选取的研究

在建立陀螺漂移的数学模型的基础上，使用不同的小波基对陀螺输出信号进行多尺度小波分解，去除由噪声产生的小波系数，从而达到消除噪声的目的。从不同小波基的滤波效果来看，双正交样条小波Biorl.5具有较好的去噪效果，从而也验证了小波对称性在陀螺信号去噪中的重要性。     

跨音涡轮叶栅底压的无粘模型

本文提出一个无粘的底部压力模型。证明了在给定反压的情况下,超音出口的涡轮叶栅的叶片尾缘的底压以及叶型损失可由该模型确定。与无粘的流场计算相结合,可用该模型计算二维叶栅的底压。对模型的参数研究表明:具有正曲率的喉道下游叶背型面将有利于减少损失;而出口为音速时流动则最为不利。     

An inviscid model for the base pressure of transonic turbine cascade

An inviscid base pressure model for transonic turbine blade has been presented. It has been shown that for a given back pressure the base pressure at the trailing edge, and the profile loss of a turbine blade are fixed according to the model and the base pressure can be calculated with the help of an inviscid numerical scheme. A parameteric study on the model shows that a blade profile with positive curvature downstream of the throat is advantageous for generating less loss, whilst the worst situation is when the exit flow reaches the sonic condition.     

Cloud point extraction for the determination of cadmium and lead employing sequential multi-element flame atomic absorption spectrometry

A cloud point extraction procedure for pre-concentration and determination of cadmium and lead in drinking water using sequential multi-element flame atomic absorption spectrometry is described. 4-(2-thiazolylazo)-orcinol (TAO) has been used as complexing agent and the micellar phase was obtained using the non-ionic surfactant octylphenoxypolyethoxyethanol (Triton X-114) and centrifugation. The conditions for reaction and extraction (surfactant concentration, reagent concentration, effect of incubation time, etc) were studied and the analytical characteristics of the method were determined. The method allows the determination of cadmium and lead with quantification limits of 0.30?µg?L^?1 and 2.6?µg?L^?1, respectively. A precision expressed as relative standard deviation (RSD, n?=?10) of 2.3% and 2.6% has been obtained for cadmium concentrations of 10?µg?L^?1 and 30?µg?L^?1, respectively, and RSD of 1.3% and 1.7% for lead concentrations of 10?µg?L^?1 and 30?µg?L^?1, respectively. The accuracy was confirmed by analysis of a natural water certified reference material. The method has been applied for the determination of cadmium and lead in drinking water samples collected in the cities of Ilhéus and Itabuna, Brazil. Recovery tests have also been performed for some samples, and results varied from 96 to 105% for cadmium and 97 to 106% for lead. The cadmium and lead concentrations found in these samples were always lower than the permissible maximum levels stipulated by World Health Organization and the Brazilian Government.     

Anodic stripping voltammetry of antimony at unmodified carbon electrodes

Antimony is an element of significant environmental concern, yet has been neglected relative to other heavy metals in electroanalysis. As such very little research has been reported on the electroanalytical determination of antimony at unmodified carbon electrodes. In this paper we report the electrochemical determination of Sb(III) in HCl solutions using unmodified carbon substrates, with focus on non-classical carbon materials namely edge plane pyrolytic graphite (EPPG), boron doped diamond (BDD) and screen-printed electrodes (SPE). Using differential pulse anodic stripping voltammetry, EPPG was found to give a considerably greater response towards antimony than other unmodified carbon electrodes, allowing highly linear ranges in nanomolar concentrations and a detection limit of 3.9?nM in 0.25?M HCl. Furthermore, the sensitivity of the response from EPPG was 100 times greater than for glassy carbon (GC). Unmodified GC gave a comparable response to previous results using the bare substrate, and BDD gave an improved, yet still very high limit of detection of 320?nM compared to previous analysis using an iridium oxide modified BDD electrode. SPEs gave a very poor response to antimony, even at high concentrations, observing no linearity from standard additions, as well as a major interference from the ink intrinsic to the working electrode carbon material. Owing to its superior performance relative to other carbon electrodes, the EPPG electrode was subjected to further analytical testing with antimony. The response of the electrode for a 40?nM concentration of Sb(III) was reproducible with a mean peak current of 1.07?µA and variation of 8.4% (n?=?8). The effect of metals copper, bismuth and arsenic were investigated at the electrode, as they are common interferences for stripping analysis of antimony.     

负载型复合半导体V2O5-TiO2/SiO2表面V2O5和TiO2的相互修饰作用

 采用表面改性法制备了负载型复合半导体材料V2O5-TiO2/SiO2,并用X射线衍射、比表面积测定、拉曼光谱、程序升温还原和紫外-可见漫反射光谱等技术对固体材料的结构和光响应性能进行了表征. 结果表明,V2O5和TiO2在负载型复合半导体V2O5-TiO2/SiO2表面有相互修饰的作用. 一方面,V2O5能扩展TiO2的光响应范围,使TiO2的吸光区域由紫外光区拓宽至可见光区,从而提高了复合半导体对光能的利用率; 另一方面,TiO2则有助于提高V2O5在载体表面的分散程度,抑制VOx的聚合,减小V2O5的微晶尺寸,提高固体材料的能隙值和氧化还原能力.