三元重叠色谱峰面积的定量方法

本从色谱峰的ＥＭＧ模型出发，通过对重叠色谱峰的模拟和回归分析，提出了一种三元重叠色谱峰的面积的定量方法，三元重叠色谱峰的每一个峰面积可以由峰面积比和总面积求得，此法所需的数据都由实验色谱图上测得，峰面积计算结果的相对误差小于±５％，适用于相对峰谷为５０％－９５％的三元重叠色谱峰面积的定量。     

粉末衍射峰形拟合程序包CPOWDER

开发了一个Ｘ射线和中子粉末衍射峰形拟合程序包ＣＰＯＷＤＥＲ，它是由多个最小二乘峰形拟合程序与蒙特卡罗分峰程序组成的。最小二乘峰形拟合程序可用于约束条件下的峰形拟合分析，蒙特卡罗分峰程序可用于寻找全局最优解，为最小二乘拟合程序提供优质的峰形参数初始值，两者结合使用特别适合于多个严重重叠峰的分离。     

尿毒症患者血清及正常人尿液内中分子物质的分离分析

采用凝胶色谱法，以２０６ｎｍ处的紫外吸收为检测手段，分别从尿毒症患者血 清及正常人尿液内分离出Ａ，Ｂ两个中分子峰，而从正常人血清中分离出来的Ａ峰远低 于尿毒症患者血清的Ａ峰；在Ｂ峰的位置正常人血清未出现明显的吸收．运用该方法 不仅提高了凝胶色谱的分离效果，且能方便地得到中分子级分的纯品．对清除了淋洗 液组分的中分子级分进行紫外和红外扫描，结果发现来源于尿毒症患者血清及正常人 尿液的Ａ峰物质具有相同的紫外吸收且红外吸收光谱极其相似，而不同来源的Ｂ峰物 质虽然紫外吸收相同，但它们的红外吸收却存在一定的差异．采用离子交换色谱法对Ｂ 峰物质进行进一步的分离，以２３０ｎｍ处的紫外吸收为检测手段，正常人尿液的Ｂ峰物 质被分离成１７个亚峰，尿毒症血清的Ｂ峰物质被分离成１３个亚峰．其中绝大部分亚峰 的出峰位置（洗脱体积）相同．     

γ—Mo2N合成过程中的热变化及中间产物的研究

采用ＤＴＡ技术，通过改变升温速率研究了γ－Ｍｏ２Ｎ合成过程中的热变化，并经ＸＲＤ，ＢＥＴ及ＩＲ测试，对ＤＴＡ曲线中的谱峰进行归属，考察了中间产物，ＤＴＡ结果表明，在ＭｏＯ３和ＮＨ３程序升温反应过程中有放热峰及吸热峰出现，且随升温速率的长高，放热峰面积与吸热峰面积之比逐渐减小，结合ＸＲＤ及ＩＲ结果可知，ＤＴＡ曲线听放热峰可归属为由ＭｏＯ３变化为ＭｏＯ２的还原峰，吸热峰则归属为由ＭｏＯ２变化为Ｍｏ２Ｎ     

二次微分与样条小波自卷积联用分辨重叠伏安峰

本文采用二次微分法寻找重叠峰的各个峰位置，再利用样条小波自卷积（SWSC）方法直接对重叠的伏安峰进行处理，取得了较好的结果。被处理的重叠峰可达到基线分离，且峰位置的相对误差小于3．0％（完全掩盖峰为5．39％），峰面积的相对误差小于2．0％。方法不用于铅（Ⅱ）－铊（Ⅰ）体系的微分脉冲伏安信号处理，取得满意的结果。     

基于遗传算法的色谱指纹峰配对识别方法

指纹峰配对识别是色谱指纹图谱分析中的关键环节之一，本文提出一种基于遗传算法的色谱指纹峰配对识别方法。该法根据对照色谱指纹图谱的峰分布特性初选出若干标定蜂，将其存入一个候选标定蜂库；同时根据这些候选标定峰从待测指纹图谱中选出相应的候选标定峰，也存入候选标定峰库；再用遗传算法从库中选取一组标定峰用于校正待测指纹图谱中各峰的峰位，并自动识别出与对照色谱指纹图谱相对应的各指纹峰。仿真实验及实际分析实验结果均表明，该法识别指纹峰准确可靠，可用于色谱指纹图谱相似度的快速自动计算。     

苏氨酸示波极谱分析机理的研究

在ｐＨ＝９２的硼砂－铟离子体系中，苏氨酸在示波极谱仪上，峰电位为－１０５Ｖ处出现一个极谱峰，该峰稳定，重现性好，灵敏度高，其浓度在４～１２０ｍｇ／Ｌ之间与峰电流呈线性关系。     

重叠伏安峰的样条卷积法分辨

建立了分辨重叠峰的样条卷积法；利用三阶样条函数构成的峰分辨函数与原信号进行卷积，直接对重叠的伏安峰进行处理，取得了较好的结果；被处理的重叠峰可达到其线分离，且峰位置的相对误差小于3．0％（完全重叠峰为5．4％），峰面积的相对误差小于2．0％；应用于镉（Ⅱ）－铟（Ⅲ）实验体系的微分脉冲伏安信号处理，取得满意的结果。     

一阶和二阶导数相综合的色谱峰检测法

本文提出了一种介于一阶和二阶导数之间的色谱峰检测新方法，它能排除基线漂移的影响，具有抗噪声干扰能力，能判别重叠峰，还能够得色谱峰上各拐点，的位置并发现肩峰型重叠峰。该方法只需要设置一个起动参数即可自动进行峰检测，具有很强的自适应性和健壮性，极大地方便了用户。     

氧化锶催化性质研究

本文运用吸附二氧化碳、氧气、一氧化碳和正丁胺的ＴＰＤ技术，对ＳｒＯ表面活性中心的种类和分布进行了研究。发现在９２１Ｋ和１１７３Ｋ有二个二氧化碳的脱附峰，且高温脱附峰极大；在４３６Ｋ和６７３Ｋ附近有二个氧的脱附峰，高温脱附峰也很大；在６７３－８７３Ｋ之间有一分布不很明显的一氧化碳脱附峰，但在９７３Ｋ附的家很大的一氧化碳脱附峰，在实验条件下，没有与正丁胺有关的附峰出现。这些结果表明ＳｒＯ表面不但有强和     

Preparation of stannyl complexes of ruthenium and osmium stabilised by polypyridine and phosphite ligands

Trichlorostannyl complexes [M(SnCl3)(bpy)2P]BPh4 [M = Ru, P = P(OEt)(3), 1a PPh(OEt)2 1b; M = Os, P = P(OEt)3 2; bpy = 2,2'-bipyridine] were prepared by allowing chloro complexes [MCl(bpy)2P]BPh4 to react with SnCl2 in 1,2-dichloroethane. Bis(trichlorostannyl) compounds Ru(SnCl3)2(N-N)P2 [N-N = bpy, P = P(OEt)3 3a, PPh(OEt)2 3b; N-N = 1,10-phenanthroline (phen), P = P(OEt)3 4] were also prepared by reacting [RuCl(N-N)P3]BPh4 precursors with SnCl2.2H2O in ethanol. Treatment of both mono- 1a, 2 and bis 3a trichlorostannyl complexes with NaBH4 afforded mono- and bis(trihydridestannyl) derivatives [M(SnH3)(bpy)2P]BPh4 5, 6 and Ru(SnH3)2(bpy)P2 7[P = P(OEt)3], respectively. Treatment of 1a, 2 with MgBrMe gave the trimethylstannyl complexes [M(SnMe3)(bpy)2P]BPh4 8, 9 and treatment of 3a afforded the bis(stannyl) Ru(SnClMe2)2(bpy)P2 10 derivative. Alkynylstannyl complexes [M{Sn(C triple bond CR)3}(bpy)2P]BPh4 11-13 and Ru[Sn(C triple bond CR)3]2(N-N)P2 14-17(R = p-tolyl, Bu t; N-N = bpy, phen) were also prepared by allowing trichlorostannyl compounds 1-4 to react with Li+[RC triple bond C]* in thf. The complexes were characterised spectroscopically and by the X-ray crystal structure determination of [Ru(SnMe3)(bpy)2{P(OEt)3}]BPh4 derivative.     

Phosphine-mediated dehalogenation reactions of trichloro(N-silyl)phosphoranimines

The reaction of N-(trimethylsilyl)phosphoranimine Cl3P=NSiMe3 (1) with nBu3P or Ph3P yields the N-(dichlorophosphino)phosphoranimines nBu3P=NPCl2 (4a) or Ph3P=NPCl2 (4b), respectively. Detailed studies of this reaction indicate a mechanism that involves the reductive dechlorination of 1 by the tertiary phosphine to yield nBu3PCl2 (5a) or Ph3PCl2 (5b) with the apparent formation of the transient chlorophosphinimine ClP=NSiMe3 (6), followed by condensation of 5a or 5b with 1 to form 4a or 4b and Me3SiCl. Convincing evidence for the proposed mechanism was revealed by studies of the analogous reaction between the N-(triphenylsilyl)phosphoranimine Cl3P=NSiPh3 (8) with nBu3P and Ph3P. These reactions quantitatively generated 5a and 5b and also allowed the correspondingly more stable chlorophosphinimine ClP=NSiPh3 (10) to be identified.     

Effects of aggregation of poly(3-hexylthiophene) in solution on uniaxial alignment of nanofibers during zone casting

We report on the effects of aggregation of P3HT with ordered conformation in solution on improving the uniaxial alignment of the P3HT nanofibers by zone casting.Two approaches were employed to change the aggregation of P3HT:P3HT blending with coil insulating polymer and ultrasonic oscillating.The insulator polymer(i.e.PS) which has good solubility in the solution would disturb the aggregation of P3HT to prevent the chains entanglement.The ultrasonic oscillation can further improve the P3HT aggregation with ordered conformation in the solution.As a result,the P3HT nanofibers in the film grew much orientedly by zone casting the ultrasonic oscillating P3HT/PS polymer blends solution than the same solvent P3HT solution without ultrasonic oscillating and blending.The P3HT tt-tt stacking direction is parallel to the alignment direction of the nanofibers.Meanwhile,the P3HT/PS blend ratio and PS molecular weight have influence on the uniaxial alignment of P3HT nanofibers.Only P3HT/PS is 1:1, the P3HT nanofibers oriented well.The low molecular weight PS can make the P3HT nanofibers orient better than that of the high molecular weight.     

Effects of substituents on aryl groups during the reaction of triarylphosphine radical cation and oxygen

In a previous report (S. Yasui, S. Tojo and T. Majima, J. Org. Chem., 2005, 70, 1276), we presented the results from the laser flash photolysis (LFP) and product analysis of the 9,10-dicyanoanthracene (DCA)-photosensitized oxidation of triarylphosphine (Ar(3)P) in acetonitrile under air, which showed that the photoreaction results in the oxidation of Ar(3)P to give the corresponding phosphine oxide (Ar(3)P=O) in a nearly quantitative yield, and that the reaction is initiated by the electron transfer (ET) from Ar(3)P to DCA in the singlet excited state ((1)DCA*), producing the triarylphosphine radical cation Ar(3)P (+). This radical cation decays through radical coupling with O(2) to afford the peroxy radical cation Ar(3)P(+)-O-O*, which we proposed to be the intermediate leading to the product Ar(3)P=O. We now examined this photoreaction in more detail using ten kinds of Ar(3)P with various electronic and steric characteristics. The decay rate of Ar(3)P*(+) measured by the LFP was only slightly affected by the substituents on the aryl groups of Ar(3)P. During the photolysis of trimesitylphosphine (Mes(3)P), the peroxy radical cation intermediate (Mes(3)P(+)-O-O*) had a lifetime long enough to be spectrophotometrically detected. The quantum yields of Ar(3)P=O increased with either electron-withdrawing or -releasing substituents on the aryl groups, suggesting that a radical center is developed on the phosphorus atom during the step when the quantum yield is determined. In addition, the o-methyl substituents in Ar(3)P decreased the quantum yield. These results clearly indicated that Ar(3)P(+)-O-O* undergoes radical attack upon the parent phosphine Ar(3)P that eventually produces the final product, Ar(3)P=O.     

Reduction reactions of a 1,3,5-triphosphabenzene

The reactions of the triphosphabenzene, 1,3,5-P3C3But3, with LiMH4, M = Al or Ga, lead to the triphosphabicyclo[3.1.0]hexanediyl metallate complexes, [[[Li(OEt2)][MH2(P3C3But3H2)]]2], which give exo- and endo-isomers of a triphosphabicyclo[3.1.0]hexane, P3C3But3H4 upon quenching. The related reaction of [AlH3(NMe3)] with 1,3,5-P3C3But3 affords three identifiable products, viz. a triphosphabicyclo[3.1.0]hexenyl complex, [AlH2(P3C3But3H)(NMe3)], and two triphosphabicyclo[3.1.0]hexanediyl complexes, [AlH(P3C3But3H2)(NMe3)] and [Al2H4(P3C3But3H2)(NMe3)]. In contrast, the reactions of 1,3,5-P3C3But3 with either [GaH3(quin)], quin = quinuclidine, or Me3SnH lead only to the triphosphabicyclo[3.1.0]hexenyl complexes, [GaH2(P3C3But3H)(quin)] and [Me3Sn(P3C3But3H)]. Quenching of the former affords a triphosphabicyclo[3.1.0]hexene, P3C3But3H2, while quenching the latter gives its triphosphacyclohexa-1,4-diene valence isomer. Treatment of 1,3,5-P3C3But3 with "GaI" yields a GaI3 complex of the triphosphahexa-1,4-diene, [GaI3(P3C3But3H2)], whilst treatment with the anionic Ga(I) heterocycle, [:Ga[N(Ar)C(H)]2]-, Ar = C6H3Pri2-2,6, affords the known diphospholyl anion, [1,3-P2C3But3]- via a P-abstraction from the triphosphabenzene. Finally, reaction of the 1,3,5-triphosphacyclohexane, [P(OEt)C(H)(But)]3, with thionyl chloride yields the unusual lambda5, lambda5, lambda5-1,3,5-triphosphacyclohexane, [P(O)(Cl)C(H)(But)]2[P(OEt)(S)C(H)(But)]. Suggestions as to the mechanisms of a number of these reduction reactions are made and the crystal structures of seven compounds are reported.     

Reactivity of triarylphosphine peroxyl radical cations generated through the reaction of triarylphosphine radical cations with oxygen

One-electron oxidation of triarylphosphines (Ar3P, Ar = phenyl and substituted phenyl) in benzonitrile (PhCN) has been studied using pulse radiolysis technique. One-electron oxidation of Ar3P occurred to yield the radical cation (Ar3P*+) which showed an intense absorption with a peak at 360-370 nm together with a broad band at 500-600 nm. The addition of molecular oxygen (O2) to the phosphorus atom of Ar3P*+ took place at the second-order rate constant of 10(7)-10(9) dm(3) mol(-1) s(-1) to yield the peroxyl triarylphosphinyl radical cation (Ar3P+OO*). It is found that the electron-releasing substituents on the para position of the phenyl ring of Ar3P influence the rate constants of the reaction of Ar3P*+ with O2 and that o-methyl substituents on the phenyl ring influence the reactivity of Ar3P+OO*.     

Synthesis of all-conjugated diblock copolymers by quasi-living polymerization and observation of their microphase separation

We designed and synthesized the all-conjugated diblock copolymers poly(3-hexylthiophene-block-3-(2-ethylhexyl)thiophene)s (P(3HT-b-3EHT)s) via a modified Grignard metathesis (GRIM), a type of quasi-living polymerization, and studied their microphase-separated structures. The P(3HT-b-3EHT)s synthesized had well-controlled molecular weights and very narrow polydispersity indices (PDIs), which demonstrates the usefulness of GRIM polymerization for the synthesis of semiconducting block copolymers. P(3HT-b-3EHT)s self-organized to form clear microphase-separated patterns upon thermal treatment, as observed by AFM. Interestingly, the enhancement of the interchain interaction of the P3HT segments compared with the P3HT homopolymer was clearly observed from the UV-vis spectra, despite the fact that the amount of crystalline P3HT fraction was reduced to 83% of the total polymer amount in P(3HT-b-3EHT). It is suggested that the relatively unconstrained, amorphous segments of P3EHT can enhance the crystallization of P3HT segments to form an ordered self-organized nanostructure.     

Phosphorylation of 5'-deoxy-5-fluorouridine with inorganic phosphorylating agents

The phosphorylation of 5'-deoxy-5-fluorouridine (doxifluridine, 5'-DFUR) has been achieved using inorganic cyclo-triphosphate (P(3m), Na(3)P(3)O(9)) and monoimido-cyclo-triphosphate (MCTP, Na(3)P(3)O(8)NH) in aqueous solution. In the reaction of 5'-DFUR with P(3m), 2'-monophospho-5'-DFUR and 3'-monophospho-5'-DFUR were synthesized with a total yield of more than 95%. In the reaction of 5'-DFUR with MCTP, 2'-diphosphoramidophosphono-5'-DFUR and 3'-diphosphoramidophosphono-5'-DFUR were synthesized with a total yield of more than 40%. The phosphorylated products with P(3m) and MCTP were stable in neutral and alkaline solutions.     

Effect of side‐chain end groups on the optical,electrochemical, and photovoltaic properties of side‐chain conjugated polythiophenes

Three new side‐chain conjugated polythiophene derivatives, poly{3‐[2‐(3‐methoxy‐4‐octyloxy‐phenyl)‐vinyl]‐thiophene} (P3MOPVT), poly{3‐[2‐(3,5‐dimethoxy‐4‐octyloxy‐phenyl)‐vinyl]‐thiophene} (P3DMOPVT), and poly{3‐[2‐(3,4‐dioctyloxy‐phenyl)‐vinyl]‐thiophene} (P3DOPVT), were synthesized by Wittig‐Hornor reaction and GRIM method and compared with poly{3‐[2‐(4‐octyloxy‐phenyl)‐vinyl]‐thiophene} (P3OPVT) for investigating the effect of the end groups of the conjugated side‐chain on the properties of the polymers. Owing to the electron‐donating ability of methoxy groups, the visible absorption peaks of P3MOPVT and P3DMOPVT solutions and films become stronger and red‐shifted compared with P3OPVT. The electrochemical bandgaps of the four polymers are 2.15 eV for P3OPVT, 1.99 eV for P3MOPVT, 1.85 eV for P3DMOPVT, and 2.36 eV for P3DOPVT, respectively, which indicate that the electron‐donating ability of the methoxy end group on the conjugated side chain of P3MOPVT and P3DMOPVT and the large steric hindrance of the two octyloxy end groups on the conjugated side chain of P3DOPVT have obvious influence on the electrochemical properties of the side‐chain conjugated polythiophenes. Polymer solar cells were fabricated with a structure of ITO/PEDOT:PSS/Polymer:PCBM/LiF/Al. The best device, based on P3DMOPVT, shows a power conversion efficiency of 1.63% under the illumination of AM1.5, 80 mW/cm². © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4916–4922, 2006     

A comparative study on p-doping behavior of polythiophenes with CH_3SO_3H

Four kinds of polythiophenes have been doped with CH3SO3H in CHCl3 under air,oxygen,and nitrogen. In the doping of two types of poly(3-hexylthiophene)s,P3HexTh(Zn/Ni)and P3HexTh(Fe)with different contents of a head-to-tail unit,the p-doping occurs at a similar rate.The reaction between poly(3-dodecylthiophene),P3DodTh,and the acid takes place more rapidly.P3OBuTh with a butoxy substituent undergoes more facile p-doping and receives photochemical reaction with CHCl3,and this reaction obeys a pseudo-first-order rate law with a rate constant kobs of 1.42×10-5s-1at room tempera- ture.