两亲性D-п-A型有机染料在染料敏化太阳能电池中的应用

设计合成了6个带有烷基链的D-п-A型有机光敏染料应用于染料敏化太阳能电池.发现长链烷基有利于电池开路光电压的提高.利用脂肪酸共敏化可进一步提高染料分子的敏化效果,且提高的程度与脂肪酸的链长有重要关系.     

长链双烷基次膦酸作为共吸附剂修饰TiO_2光阳极

对TiO2/染料/电解质界面进行修饰是提高染料敏化太阳电池(DSC)性能的有效手段,其中引入共吸附剂有机小分子和染料共同吸附在TiO2表面是一种简单有效提高DSC性能的方法.本文合成了长链的双正十二烷基次膦酸(DDdPA)作为染料的共吸附剂应用于染料敏化太阳电池.通过红外光谱(FT-IR)表征DDdPA在TiO2表面的吸附;借助电化学阻抗谱(EIS)及强度调制光电流谱(IMPS)/强度调制光电压谱(IMVS)等技术表征了电子的传输与复合动力学过程.研究发现,DDdPA可以很好地与染料共同吸附在TiO2表面;与二(3,3-二甲基丁基)次膦酸(DINHOP)相比,DDdPA的引入可以更好地抑制TiO2/染料/电解质界面处的电子复合;在优化浓度配比下,DDdPA的引入有效提高了器件的电子寿命,使TiO2导带边负移约30 mV,最终使器件的开路电压提高了47 mV,光电转换效率提升约10%.     

共吸附剂在染料敏化太阳电池中的应用

简述了染料敏化太阳电池中引入共吸附剂对光阳极界面进行修饰的作用机制。按照共吸附剂的分子结构特性和应用状况,初步将共吸附剂划分为胆酸衍生物共吸附剂、链状脂肪酸共吸附剂和多羟基化合物共吸附剂。综述了这几类共吸附剂在染料敏化太阳电池中的应用状况并进行了展望。     

羟基取代对称恶碳菁染料的合成

菁染料作为在近紫外至近红外区域内的光谱增感剂,其主敏化区受到分子结构中的次乙基链长度和不同杂环结构的影响。     

含苯并噻二唑的二维有机染料的合成与光伏性能研究

通过引入烷基二噻吩苯并噻二唑窄带隙基元到D-π-A有机染料体系中,设计并合成了两种二维结构的有机染料DD2和DH2,系统地研究了以烷基二噻吩苯并噻二唑基元作为侧基或桥联基元对染料敏化剂的光物理性能、电化学性能和光伏性能的影响.含有烷基二噻吩苯并噻二唑基元的这两种染料都具有较宽的吸收光谱.在氙灯光源(100mW?cm-2,AM 1.5 G)下,基于有机染料DH2和DD2的染料敏化太阳能电池的能量转换效率分别为1.67%和3.26%.采用鹅去氧胆酸(CDCA)共吸附剂优化后,染料DH2表现出较好的抗聚集能力,能量转换效率几乎没有变化;而DD2的能量转换效率提高到了5.53%.     

一种高效染料敏化太阳电池电解质添加剂

报道了一种新型染料敏化太阳电池电解质添加剂——N-十六烷基吡啶碘(N-CPI).往电解质中添加0.02MN-CPI,能同时提高染料敏化太阳电池(DSSC)的短路电流和开路电压,光电转换效率也由4.429%提高到6.535%,增幅高达47.55%,由此可见,N-CPI是一种高效电解质添加剂.N-CPI这种功能来源于其双极性基团的特殊分子结构,这种结构使N-CPI在电解质中如表面活性剂那样形成有序分布,影响I-/I3-的扩散和氧化还原性能,进而影响DSSC的光电性能.     

二氢吲哚类染料用于染料敏化太阳能电池光敏剂的比较

采用密度泛函理论(DFT)和含时密度泛函理论(TD-DFT)对四种二氢吲哚染料进行研究, 从中筛选出相对优秀的染料敏化太阳能电池光敏剂. 对前线分子轨道的计算表明, 二氢吲哚染料的前线分子轨道结构非常有利于染料激发态向TiO2电极的电子注入. 对真空中的紫外和可见光吸收光谱的计算表明, 二氢吲哚染料的吸收光谱与太阳辐射光谱匹配较好. 对染料分子的能级计算表明, 二氢吲哚染料的能级结构比较适合于I-/I-3作电解液的TiO2纳米晶太阳能电池的光敏剂. 二氢吲哚染料最低未占据分子轨道(LUMO) 能级均比TiO2晶体导带边能级高, 能够保证激发态染料分子高效地向TiO2电极转移电子. 二氢吲哚染料最高占据分子轨道(HOMO)的能级比I-/I-3能级低, 保证了失去电子的染料分子能够顺利地从电解液中得到电子. 与实验数据比较, 得出在提高染料敏化太阳能电池转换效率方面, 对染料的关键要求是LUMO能级的位置. 染料分子的稳定性是染料敏化太阳能电池使用寿命的关键因素. 通过对化学键键长的比较表明, 二氢吲哚染料的分子稳定性基本相同. 对计算结果的分析表明, 二氢吲哚染料1(ID1)的LUMO能级最高, 分子稳定性最好, 在酒精溶液中的吸收光谱与太阳辐射光谱匹配很好, 在同类染料中是较好的染料敏化太阳能电池光敏剂.     

含苯并噻二唑的吩噻嗪染料分子的设计合成及其在染料敏化太阳能电池中的应用

设计合成了三种含苯并噻二唑的吩噻嗪类有机染料光敏剂JY50~JY52,在对其光物理和电化学性质进行研究的基础上,使用三种染料对纳米TiO₂电极进行敏化制备太阳能电池器件,并系统研究了其光电转化效率及电荷传输阻抗等光伏特性.研究结果表明,在染料分子中引入共轭基团有助于其摩尔吸光系数的提升,从而提升光电流.两个长烷基链的引入能够有效地抑制染料分子激发态电子在TiO₂光阳极表面的电子复合,从而提升其电子注入效率.其中,在AM 1.5（100 mW·cm^-2）的模拟光强下,基于碘电解质的染料JY51电池器件获得了7.61%的光电转化效率.     

基于不同取代基的噻吩-三苯胺染料敏化剂的合成与光伏性能

本文合成了含3种不同取代基的噻吩-三苯胺染料敏化剂(H1,H2和H3),并将其应用于二氧化钛纳米晶染料敏化太阳能电池.系统地研究了3种染料的光物理、电化学和光伏性能.基于H1的染料敏化太阳能电池获得了9.10%的光电转换效率(Voc=0.72V,Jsc=18.03mAcm-2,FF=0.70).     

有序宏孔-介孔TiO_2薄膜的制备及其在染料敏化太阳能电池中的应用

我们使用表面活性剂P123和聚苯乙烯球双模板技术,合成了多级有序的宏孔/介孔TiO2薄膜,并将其与P25多孔薄膜复合形成双层结构的染料敏化太阳能电池光阳极.实验结果表明,宏孔/介孔TiO2薄膜层的引入,有效地提高了光阳极对太阳光的散射以及捕获能力,从而提高了染料敏化太阳能电池的光电转化效率.与使用单一P25光阳极的染料敏化太阳能电池相比,双层TiO2结构的染料敏化太阳能电池所产生的短路光电流密度从7.49上升到了10.65mA/cm2,开路电压也从0.65提高到了0.70V.在太阳光强度为AM1.5时所测得的光电转化效率表明,双层TiO2结构的染料敏化太阳能电池的光电转化效率为5.55%,比单层P25结构的染料敏化太阳能电池的光电转化效率提升了83%.     

Photoinduced Palladium-Catalyzed Dicarbofunctionalization of Terminal Alkynes

Herein, a conceptually distinct approach was developed that allowed for the dicarbofunctionalization of alkynes at room temperature using simple, bench-stable alkyl iodides and a second molecule of alkyne as coupling partner. Specifically, the photochemical activation of palladium complexes enabled this strategic dicarbofunctionalization via addition of alkyl radicals from secondary and tertiary alkyl iodides and formation of an intermediate palladium vinyl complex that could undergo subsequent Sonogashira reaction with a second alkyne molecule. This alkylation–alkynylation sequence allowed the one-step synthesis of 1,3-enynes including heteroarenes and biologically active compounds with high efficiency without exogenous photosensitizers or oxidants and now opens up pathways towards cascade reactions via photochemical palladium catalysis.     

Chiral N-alkyl-2,4,6-triphenylpyridiniums as enantioselective triplet photosensitizers. laser flash photolysis and preparative studies

Three N-alkylpyridinium photosensitizers having chiral alkyl groups have been prepared by reacting 2,4,6-triphenylpyrylium tetrafluoroborate ion with (1R,2S)-(-)-norephedrine, (S)-(+)-2-(aminomethyl)pyrrolidine, and (R)-(-)-1-cyclohexylethylamine. Laser flash photolysis allows detection of the corresponding triplet excited states that are quenched by hydrogen atom donors and electron donors. Asymmetric quenching of the chiral triplet excited state was observed using enantiomerically pure 1,2-diamino cyclohexane as quencher. Low enantiomeric excess values (up to 7%) were measured for the photochemical cyclization of 5-methyl-4-hexenoic acid to its corresponding gamma-lactone using these chiral N-alkylpyridinium as photosensitizers.     

A BIOCHEMICAL SCREENING TEST FOR THE PHOTOSENSITIZING POTENTIAL OF DRUGS AND DISINFECTANTS

Abstract— A series of photosensitizers known to cause photodermatitis were tested with respect to photosensitizing properties. Irradiation of these sensitizers together with unsaturated fatty acids or amino acids showed that few of them can be transformed by most of the photosensitizers. SH groups can. however, be destroyed by most of the photosensitizers known in dermatological practice. At low photosensitizer-to-SH group ratios, GSSG is formed; at higher ratios, other transformations of GSH predominates. The reactivity of GSH with ninhydrin is decreased after irradiation with a photo-sensitizer. Glutathione seems to be a biomolecule that is suitably sensitive to photosensitized modification and thus suitable for evaluation of any photosensitizing activity that new drugs may have as an unwanted side effect.     

Melting of saturated fatty acid zinc soaps

The melting of alkyl chains in the saturated fatty acid zinc soaps of different chain lengths, Zn(C(n)H(2n+1)COO)(2); n = 11, 13, 15, and 17, have been investigated by powder X-ray diffraction, differential scanning calorimetry, and vibrational spectroscopy. These compounds have a layer structure with the alkyl chains arranged as tilted bilayers and with all methylene chains adopting a planar, all-trans conformation at room temperature. The saturated fatty acid zinc soaps exhibit a single reversible melting transition with the associated enthalpy change varying linearly with alkyl chain length, but surprisingly, the melting temperature remaining constant. Melting is associated with changes in the conformation of the alkyl chains and in the nature of coordination of the fatty acid to zinc. By monitoring features in the infrared spectra that are characteristic of the global conformation of the alkyl chains, a quantitative relation between conformational disorder and melting is established. It is found that, irrespective of the alkyl chain length, melting occurs when 30% of the chains in the soap are disordered. These results highlight the universal nature of the melting of saturated fatty acid zinc soaps and provide a simple explanation for the observed phenomena.     

Trace analysis of surfactants derived from fatty alcohols II. Hydrolysis and enrichment techniques

Summary Acid catalyzed hydrolysis of fatty alcohol sulfates under reflux condition or by microwave heating is compared. Microwave hydrolysis turned out to be faster and more convenient to use. The combination of reflux hydrolysis of fatty alcohol sulfates or alkyl polyglycosides and the simultaneous steam distillation of the generated fatty alcohols gives a very powerful sample preparation and enrichment method for fatty alcohol sulfates and alkyl polyglycosides. The preconcentrated fatty alcohols are derivatized and detected via fluorescence detection. The applicability of the method is demonstrated by the analysis of fatty alcohol sulfates in cosmetics and in river water as matrices spiked with approximately 4 ppb fatty alcohol sulfates.     

Photoinitiated free radical carbonylation enhanced by photosensitizers

[reaction: see text] The enhancing effect of several photosensitizers in photoinitiated radical carbonylation is demonstrated and applied to accelerate the synthesis of compounds labeled with short-lived 11C. With the sensitizers, the synthesis of [carbonyl-11C]esters and acids from alkyl iodides, [11C]carbon monoxide, alcohols, and water provided up to 75-85% decay-corrected radiochemical yields in 6-min reactions under mild conditions. Acetone was used as a sensitizer in preparing 13C-substituted 1,10-decanedicarboxylic acid from (13C)carbon monoxide.     

Mechanism and efficiency of cell death of type II photosensitizers: effect of zinc chelation

A series of meso-substituted tetra-cationic porphyrins, which have methyl and octyl substituents, was studied in order to understand the effect of zinc chelation and photosensitizer subcellular localization in the mechanism of cell death. Zinc chelation does not change the photophysical properties of the photosensitizers (all molecules studied are type II photosensitizers) but affects considerably the interaction of the porphyrins with membranes, reducing mitochondrial accumulation. The total amount of intracellular reactive species induced by treating cells with photosensitizer and light is similar for zinc-chelated and free-base porphyrins that have the same alkyl substituent. Zinc-chelated porphyrins, which are poorly accumulated in mitochondria, show higher efficiency of cell death with features of apoptosis (higher MTT response compared with trypan blue staining, specific acridine orange/ethidium bromide staining, loss of mitochondrial transmembrane potential, stronger cytochrome c release and larger sub-G1 cell population), whereas nonchelated porphyrins, which are considerably more concentrated in mitochondria, triggered mainly necrotic cell death. We hypothesized that zinc-chelation protects the photoinduced properties of the porphyrins in the mitochondrial environment.     

Biodiesel fuel from vegetable oil by various supercritical alcohols

Biodiesel was prepared in various supercritical alcohol treatments with methanol, ethanol, 1-propanol, 1-butanol, or 1-octanol to study transesterification of rapeseed oil and alkyl esterification of fatty acid at temperatures of 300 and 350°C. The results showed that in transes terification, the reactivity was greatly correlated to the alcohol: the longer the alkyl chain of alcohol, the longer the reaction treatment. In alkyl esterification of fatty acids, the conversion did not depend on the alcohol type because they had a similar reactivity. Therefore, the selection of alcohol in biodiesel production should be based on consideration of its performance of properties and economics.     

Novel enzymatic assay for determination of alkyl polyglycosides with short chain fatty alcohols

An enzymatic assay has been developed for the quantitative detection of alkyl polyglycosides after enzymatic hydrolysis with different carbohydrolases. A three-step enzymatic method was used for the quantification of alkyl polyglycosides. In the first step the enzymatic hydrolysis of alkyl polyglycosides was performed with different carbohydrolases, or an acid hydrolysis was used. The second step was quantification of free glucose with an enzyme electrode, which was covered with an immobilized glucose oxidase membrane; glucose was used as standard. The last step was the enzymatic quantification of fatty alcohols, which are the second substrate after enzymatic hydrolysis of alkyl polyglycosides. Surprisingly, the enzyme alcohol dehydrogenase ADH (E.C. 1.1.1.1) from bakers' yeast could efficiently oxidize a wide variety of aliphatic alcohols and had the highest catalytic specificity with short and medium fatty alcohol substrates, including octanol and decanol.     

Iron-catalyzed alkyl-alkyl suzuki-miyaura coupling

Chemoselective Suzuki-Miyaura coupling of primary and secondary alkyl halides is realized by using an iron/Xantphos catalyst. Primary and secondary alkyl bromides undergo the reaction to give the coupling products in good yields. Application to the synthesis of long-chain fatty acid derivatives is also described.