酸敏变色记录材料的光谱特性及其光量子产率

本文研究了由偏二氯乙烯-丙烯酸甲酯共聚合物(VdCl₂-MA)和五甲氧基红指示剂组成的酸敏变色记录材料的光谱特性,测定了其光分解量子产率.通过添加光敏剂使原来只有在254nm紫外光下曝光才能发生光分解反应的酸敏变色材料在35nm紫外光下曝光也可发生光分解而变色.酸敏变色材料在254nm处紫外光曝光量子产率为0.032-0.020;在35nm处紫外光曝光量子产率为0.110-0.034.光敏剂的加入使酸敏变色材料量子产率提高了2-4倍.     

复阻抗法分析聚吡咯材料的湿敏特性

通过延长聚合时间到96 h合成了一种对湿度敏感的聚吡咯材料. 采用红外(IR)光谱, X射线衍射(XRD)和扫描电子显微镜(SEM)的方法对合成的材料进行了表征. 测量了基于该材料的湿敏元件的湿度特性, 并且得到了在20 Hz-100 kHz频率范围内的复阻抗谱图. 基于测量结果讨论了该材料制备的湿敏元件的湿度敏感机制. 通过对复阻抗谱的分析研究了该湿敏元件的工作机理并且分析了参与导电的粒子.     

3-取代-5(3-乙基-4,5-二苯基噻唑叉)洛丹宁的增感性能

简单份菁(或称零甲川份菁)是一种可以用作卤化银感光乳剂层感蓝增感的染料。彩色正性材料的发展,要求感蓝乳剂层使用氯溴化银乳剂,并配合使用感蓝增感染料以符合感蓝区域的光谱要求。以氩离子激光为光源的电子分色片乳剂要求对波长488nm附近有较高的敏感,此种乳剂本身感色范围偏离氩离子激光发射峰。寻找增感效率高、光谱增感峰适合的感蓝染料很有必要。本文用2-甲硫基-3-乙基-4,5二苯基噻唑对甲苯磺酸盐(1)分别与3-取代洛丹宁(2)在无水乙醇存在下反应,制得六个未见文献报导的3-取代-5-(3-乙基-     

纳米SnO2增敏鲁米诺化学发光的研究与应用

采用溶胶-凝胶法制得平均粒径约10 nm的SnO2粒子.将该纳米SnO2粒子加入碱性鲁米诺-O2化学发光体系,体系的化学发光强度明显增强,这种增敏作用与纳米SnO2的加入量以及体系中溶解氧的质量浓度有关,基于此得出了纳米SnO2存在下溶解氧质量浓度与鲁米诺化学发光强度之间的线性关系,可用于溶解氧测定,检出限达0.3 mg/L,该纳米增敏化学发光体系有望用于进一步提高基于鲁米诺化学发光测定方法的灵敏度.文中还应用紫外-可见光谱和荧光光谱研究了这种增敏作用的机理,并应用该体系考察了水果的抗氧化能力.     

光敏元的化学增感对以甲基苯并三氮唑银为银源的光敏热成像材料感光性能的影响

研究了把经传统化学增感即硫增感、金增感、S+Au增感、二甲氨基硼烷(DMAB)还原增感的AgBr乳剂引入光敏热成像(PTG)体系后对PTG材料感光性能的影响。结果表明,AgBr乳剂经传统化学增感后感光度均大幅增加,其中经S+Au增感后感光度可较未增感的提高6倍,将增感后的AgBr乳剂作为PTG体系的光敏元,PTG材料在感光度增加的同时灰雾并没有明显地增加。以S+Au增感和还原增感的效果为最佳,感光度可增加4倍。     

Zn(Ⅱ)-EDTA和Cd(Ⅱ)-EDTA在草酸根掺杂溴化银颗粒乳剂中的增感效应

使用反馈式微机控制双注乳化仪,在晶体生长过程特定时间内,加入一定量的草酸盐,制得了草酸根离子处于晶体次表面的立方体溴化银微晶乳剂,并对其进行传统的硫加金化学增感、Zn(Ⅱ)-EDTA或Cd(Ⅱ)-EDTA增感以及光谱增感.对实验过程的考察和感光性能的测试结果表明,Zn(Ⅱ)-EDTA或Cd(Ⅱ)-EDTA对细微粒溴化银颗粒乳剂均有显著的增感效应;Zn(Ⅱ)-EDTA或Cd(Ⅱ)-EDTA增感可在传统硫加金增感基础上与光谱增感协同作用,三者具有兼容和可加和性;Zn(Ⅱ)-EDTA或Cd(Ⅱ)-EDTA增感可在传统硫加金增感与光谱增感协同作用的基础上,与草酸根内部掺杂增感兼容,实现四者的协同作用,而不引起乳剂灰雾增加.     

铽-氟罗沙星配合物光化学荧光增强研究

铽 氟罗沙星 (FLRX)配合物在 36 5nm紫外光照射一定时间后 ,Tb3 的特征荧光强度大大提高。通过对该体系的荧光光谱、磷光光谱、荧光量子效率和荧光寿命等的测定 ,证实Tb3 FLRX配合物光照后发生了光化学反应 ,形成了更有利于分子内能量传递的Tb3 配合物。探讨了其荧光增敏机制。     

胶束增敏分光光度法水相测定乳制品中三聚氰胺

建立了一种基于胶束增敏缔合反应水相测定乳制品中三聚氰胺的分光光度法,研究了在阴离子表面活性剂十二烷基硫酸钠(SDS)形成的胶束体系中,茜素红(AR)阴离子与三聚氰胺阳离子反应产物的紫外-可见光谱特性。实验发现,加入三聚氰胺后,体系λmax由426nm红移到516nm,加入SDS对缔合物有显著的增稳、增敏效应。三聚氰胺质量浓度在1.9～25mg/L范围内符合比尔定律,缔合物的表观摩尔吸光系数为6.9×103L.mol-1.cm-1。本方法用于液态奶及奶粉中三聚氰胺的测定,回收率分别为94.5%～104.8%和95.5%～100.4%,相对标准偏差分别为1.6%～2.2%和1.7%～2.6%。考察了酸效应、胶束对体系的作用机理,发现三聚氰胺与AR缔合物之间主要是通过静电引力和疏水作用力相结合。     

酸敏变色记录显示片再生方法的研究

我们进行了酸敏变色记录显示片(简称酸敏片)重复使用的试验,并对其实用性在实验中给予证实。实验结果表明:酸敏片经曝光后,由于释放 HCI 酸源使酸性指示剂变色形成图像,通过还原酸性指示剂,使曝     

金纳米催化鲁米诺-铁氰化钾化学发光体系测定克拉维酸钾

碱性条件下,金纳米对鲁米诺-铁氰化钾化学发光体系有增敏作用,克拉维酸钾可以显著增强该化学发光体系的发光信号。基于此,在优化化学发光反应条件的基础上,结合流动注射技术,提出了测定克拉维酸钾的新方法,并对其可能的化学发光机理进行了探讨。测定克拉维酸钾的线性范围为0.01~1.0μg/m L,相关系数(r)为0.9964,检出限为6.9 ng/m L,相对标准偏差(RSD)为1.1%(0.6μg/m L克拉维酸钾溶液,n=11)。方法可用于牛奶中克拉维酸钾的测定,回收率为96.0%~99.7%。     

高分子化8-羟基喹啉锂的合成与静电自组装研究

设计合成了甲基丙烯酸二甲氨基乙酯(DM)含量为9.69%的丙烯酸甲酯共聚物(CPA),将制得的5-氯甲基-8-羟基喹啉(CHQ)挂接到CPA上,得到季铵型高分子化8-羟基喹啉(CPA-HQ)后,与金属离子Li+配位得到CPA-HQ-Li.化合物结构通过红外、紫外和荧光光谱等表征.多层超薄膜用CPA-HQ-Li和聚阴离子电解质(全氟磺酸)通过静电自组装制得.自组装膜的紫外和荧光相对于溶液(溶剂为四氢呋喃)发生了红移,膜的紫外吸收强度随组装膜层数增加线性增大,荧光强度随膜层数增加线性递减.高分子化8-羟基喹啉锂溶液和自组装膜的紫外和荧光光谱与文献报道一致.实验结果表明这种材料可用于有机电致发光器件(OLEDs)的制备.     

烷基和烷氧基取代聚噻吩的合成、表征与光电性能

Fe(Ⅲ )氧化催化法合成了 4种聚噻吩衍生物 ,3 十二烷基聚噻吩 (Pat12 ) ,3 辛氧基聚噻吩 (Paot8) ,3,4 二 (十二烷基 )聚噻吩 (Pat12 12 )和 3 (十二烷基 )噻吩 3 (辛氧基 )噻吩共聚物 (CoPt12 o8) .发现这些衍生物易溶于多种常用有机溶剂 .用GPC法测定了各聚合物分子量 ,用1 H NMR法表征了各聚合物化学结构 .对比研究了这些聚合物紫外 可见吸收性能 ,光致发光性能和能隙 .对其电致发光性能进行测定的结果 ,得到了Pat12 ,Pat12 12和Paot8的电致发光光谱 .发射峰分别为 6 70nm ,5 6 0nm和 6 4 0nm .发光颜色分别为红色 ,黄色和红橙色 .聚合物的光电性能与主链电子结构有密切关系 .探讨了取代基种类和数量对聚合物能带结构 ,光电性能的影响 .     

ELECTROCHROMETIC STUDIES ON POLAR MULTILAYERS OF LIQUID CRYSTALLINE POLYMERS

Electrochrometic measurements were carried on the Z-type Langmuir-Blodgett films oftwo liquid crystalline polymers: mono-{6-[4-(phenylazo) naphthyloxy] hexyl} (1a) andmono-{6-[4-(anthraquinone-1-azo) naphthyloxy] hexyl} (2a) ester of polymaleic acid. Itwas found that for both polymers, poling fields parallel and antiparalle1 to dipole momentsof the polymer side chains induce red and blue shift in absorption bands, respectively. Forpolymer la blue shift is accompanied by absorbance increase, while red shift by absorbancedecrease;but for polymer 2a only decrease in absorbance is observed. A simple model wasproposed to analyze the results.     

Investigating the Red Shift between in vitro and in vivo Urocanic Acid Photoisomerization Action Spectra

Abstract— Trans-urocanic acid (UCA) is found in the upper layer of the skin and UV irradiation induces its photoisomerization to cis -UCA. Cis -UCA mimics some of the immunosuppressive properties of UV exposure. The wavelength dependence for in vitro photoisomerization of trans-UCA (15 μM) over the spectral range 250 nm-340 nm (10 nm intervals) was determined. The action spectrum revealed that maximal cis-UCA production occurred at 280 nm, which is red-shifted by 10-12 nm from its absorption peak at 268 nm and differs markedly from the reported action spectra for cis-UCA production in mouse skin in vivo , which peaks at 300-310 nm. The reasons for the red shift between the in vitro and in vivo action spectra are not clear. There is limited evidence suggesting that the UV absorption maximum of trans- UCA red shifts from 268 nm in vitro to 310 nm on interaction with stratum corneum proteins in vivo. This phenomenon was investigated by applying trans-UCA (2.5 mg/cm²) in an oil emulsion to isolated human stratum corneum. After incubation at 37°C for 1 h, the absorption spectra of stratum corneum with UCA and with oil only were compared using a Xe arc source and a spectrora-diometer. A moderate red shift in trans-UCA absorption from ∼268 nm to 280 nm was observed. In summary, we suggest that the 10-12 nm red shift between the UCA absorption spectrum peak and the action spectrum peak in vitro may be accounted for by the wavelength dependence of quantum yields reported over the 254-313 nm range. The red shift between the in vitro and in vivo photoisomerization action spectra may result from the 10 to 12 nm red shift in the absorption of UCA in association with stratum corneum proteins, combined with increasing quantum yields over the 254-313 nm range.     

Novel mesogen‐jacketed poly(p‐phenylenevinylene) derivatives bearing oxadiazole pendants: Design,synthesis, and optoelectronic properties

1,3,4‐oxadiazole moieties were laterally linked to the phenyl rings via a short ? OCH₂ spacer and a series of novel poly(p‐phenylenevinylene) derivatives have been successfully synthesized through Horner–Witting–Emmons coupling reaction. The structures and properties of the monomers and the resulting conjugated polymers were characterized by nuclear magnetic resonance spectroscope, Fourier transform infrared, elemental analysis, gel permeation chromatography, thermogravimetric analysis, UV–vis absorption (UV) spectroscopy, photoluminescence spectroscopy and cyclic voltammetry. The UV spectra at solution state was similar to what's observed at film state while the PL spectra at film state had a red shift from 19 to 28 nm compared with the results at solution state, which implied that the unique bulky jacketed structure containing oxadiazole unit of these copolymers could effectively suppress π‐stacking/aggregation. LUMO levels of these polymers varied from ?3.44 to ?3.63 eV with increasing content of oxadiazole units, which facilitated electron injection. PLEDs with the configuration of ITO/PEDOT/Polymer/TPBI (15 nm)/LiF (1 nm)/Al (100 nm) were fabricated, which emit a yellowish green light around 540 and 570 nm with a maximum brightness of 1074.7 cd/m² and luminous efficiency of 0.108 cd/A. The introduction of the unique bulky OXD unit into PPVs at a low molar content largely improved the electroluminescence properties of PPV. © Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7173–7186, 2008     

Effect of film thickness controlled by ink‐jet printing method on the optical properties of an electroluminescent polymer

Ink‐jet printing (IJP) represents a highly promising liquid processed polymer deposition method for the film preparation of functional polymers in photo‐electronic devices. In this report, the results on the IJP of a fluorene‐based electroluminescent polymer, poly(9,9‐dihexylfluorene‐alt‐2,5‐dioctyloxybenzene) (PF6OC8), from a piezoelectric droplet generator are presented. The polymer film thickness has been found to show an approximate linear relation with the number of droplets per unit area; it is thus convenient to control the film thickness by the space of printed dots in IJP process. In comparison, spin coating approach is also used to prepare polymer films with different thicknesses by varying solution concentration and spinning speed. However, it is found that spin coating is difficult to control the film thickness quantitatively. The influence of film thickness on the photoluminescence (PL) properties of PF6OC8 films prepared by IJP and spin coating is comparatively investigated. For both ink‐jet printed and spin coated films, the intensity of PL spectra first increases and then decreases with increase in the film thickness, probably due to the exciton quenching in thicker films. When the polymer film thickness is at nanoscale, the major peak in the PL spectrum is the 0–0 vibronic emission at about 420 nm, and with increase in the film thickness, the 0–1 vibronic peak at about 440 nm becomes dominant. The red‐shifted PL spectra with increase in film thickness show the change from the 2D exciton state to the 3D one. Copyright © 2009 John Wiley & Sons, Ltd.     

THE ''Q-BAND'' ABSORPTION spECTRA OF HEMATOPORPHYRIN MONOMER AND AGGREGATE IN AQUEOUS SOLUTION

Abstract The resolution of the absorption spectra in the Q band (480 nm-620 nm) spectral region of monomeric and dimeric hematoporphyrin species present in aqueous solutions has been achieved using absorption, fluorescence and computer analysis methods. The absorption maxima of the dimer in this spectral region are red shifted about 12 nm with respect to those of the monomer. The significance of this finding in relationship to the well documented blue shift of hematoporphyrin aggregate observed in the Soret band region (λ_malx∼400 nm) of the absorption spectrum is discussed.     

Preparation and chemical properties of soluble π‐conjugated poly(aryleneethynylene) consisting of azabenzothiadiazole as the electron‐accepting unit

A soluble charge‐transfer type poly(aryleneethynylene), PAE‐AzaBzTdz , consisting of a highly electron‐accepting azabenzothiadiazole unit was prepared in 99% yield by palladium‐catalyzed polycondensation between 4,7‐dibromo‐2,1,3‐azabenzothiadiazole ( Br₂‐AzaBzTdz ) and 1,4‐diethynyl‐2,5‐didodecyloxybenzene. PAE‐AzaBzTdz showed a number‐average molecular weight, M_n, of 6000 in gel‐permeation chromatography analysis and had good thermal stability as measured by TGA. UV–vis spectrum of PAE‐AzaBzTdz exhibited an absorption peak at 529 nm in chloroform, and the absorption peak shifted to a longer wavelength (601 nm) in film. Addition of MeOH to a CHCl₃ solution of PAE‐AzaBzTdz led to aggregation of the polymer to form stable colloidal particles. Results of filtration experiments using 0.2 and 0.02 μm membranes supported aggregation of the polymer. Addition of trifluoroacetic acid (TFA) to a chloroform solution of PAE‐AzaBzTdz led to a red‐shift of the UV–vis peak from 529 to 640 nm. An X‐ray diffraction pattern of powdery PAE‐AzaBzTdz indicated that the polymer assumed a layer‐to‐layer stacked structure with an interlayer distance of 3.4 Å in the solid state. An X‐ray diffraction pattern of cast film of PAE‐AzaBzTdz revealed that the polymer molecules in the cast film were ordered on the surface of Pt plate with the dodecyl side chain oriented toward the surface of the Pt plate. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2975–2982, 2008     

ACTION SPECTRUM FOR PHOTOREVERSION OF THE ACTIVE Pfr-FRACTION OF Mougeotia in vivo

Abstract— The dichroic oriented fraction of the far-red light absorbing form of phytochrome (Pfr) in the green alga Mougeotia was characterized by action spectroscopy. Microbeam irradiations had to be used for the induction of chloroplast movement in Pfr-containing cells, because of the special dichroic absorption characteristics of the red light absorbing form of phytochrome (Pr) and Pfr in the alga. Fluence-response curves were elaborated especially in the far-red spectral region by reverting Pfr to Pr at the flanks of the cells and thus generating Pfr-gradients. Linearly polarized light vibrating perpendicularly to the cell axis was used, thus corresponding to the S,-transition moments of Pfr at the flanks of the cells. The action spectrum is characterized by a peak at approximately 715 nm and a very pronounced decrease towards 728 and 734 nm. The data indicate that the spectral absorption of the active Pfr-fraction in green Mougeotia is shifted towards shorter wavelengths as compared to extracted phytochrome from etiolated or even green higher plants. This "blue shift" seems to be typical for Pfr from green lower plants.     

Hydrogen bonding in polymer mixtures

The enthalpy–infrared frequency shift correlation for simple acids and bases is extended to study hydrogen bonding in polymer systems. The acidity of a polymer is calibrated by comparing the shifts in hydroxyl absorption frequency of the acidic polymer when mixed with a series of bases with the corresponding spectral shifts of known acids with the same bases. The basicity of a polymer is calibrated by measuring the hydroxyl frequency shifts of known acids when mixed with the basic polymer. For polymers containing carbonyl groups, the shift in carbonyl absorption is also a measure of basicity. The acidity and basicity constants obtained for polymers are in good agreement with the values for small-molecule analogs. The enthalpies of hydrogen bond formation in polymer mixtures are calculated from the acidity or basicity constants.