系列冠醚化合物对卤化银乳剂的增感作用初探

微粒高感是卤化银感光材料的发展方向。一般说来卤化银颗粒越小,其感光度越低,为了制备微粒高感的卤化银感光材料,在保证微粒的前提下,寻找一些有效的增感剂能达到微粒高感的目的.冠醚化合物是一类新型的增感剂。近年来,冠醚化合物增感卤化银乳剂已有过一些报道^[1,2]。作者^[3,4]对硫杂冠醚化合物增感澳化银乳剂做过一些探讨。     

羟基四氮茚在氯化银乳剂中的增感作用

自Birr发现三氮茚和四氮茚类化合物^[1]及其用作卤化银感光剂的稳定剂以来,它们一直受到广泛的关注^[2]。     

单分散扁平卤化银微晶成核过程的研究

多年来,卤化银乳剂微晶体制备的研究重点一直放在宏观相的结构与性能的关系上,已经发现卤化银照相乳剂的感光性能与晶体的结构和大小有很重要的关系^[1,2]。随着研究工作的深入,人们逐渐认识到:晶体的成核过程决定着宏观相微晶体的结构和形状,因此成核过程的研究日益受到人们的关注。Tanaka^[3,4]应用分光光度法从反应动力学角度入手研究AgX微晶的成核过程。     

冠醚对溴化银乳剂的增感作用

近年来,已有将冠醚化合物用于卤化银感光乳剂中的一些报道^[1-4]。为了改善卤化银感光材料的性能,我们将合成的一种新冠醚——N-对甲苯磺酰基-7-氮杂-1,4,10,13-四硫杂环十六烷(NTsTTH)用于卤化银乳剂中,发现它能提高卤化银乳剂的感光度。     

硫氰酸钾在超细卤化银颗粒乳剂中的作用

近年来,超细颗粒照相乳剂逐渐受到人们的注意,这是因为全息术和微电子制版材料的广泛应用,需要高解像率和高感光度的照相材料.但是,在颗粒尺寸不变的情况下,颗粒尺寸小于0.05μm的胶态卤化银乳剂难以用化学增感的方法实现感光度的提高^[1]。硫氰酸钾在常规照相乳剂中是卤化银的溶剂.而在超细卤化银颗粒乳剂中,如果控制pAg在6.1~6.8范围内,使用硫氰酸钾,能提高超细卤化银颗粒乳剂的感光度,而颗粒尺寸不变,这一效果对全息术有重要现实意义。硫氰酸钾在超细卤化银颗粒乳剂中的作用,迄今为止,在文献上还未见报导。     

非银核/卤化银壳多相组合光敏微晶体系

自从 70 年代以来, 一直有少数人在尝试制作一种新型卤化银乳剂^[1～7], 即以某些结构与卤化银相似的无机盐、胶体、染料、水溶性卤化物等作核, 在其表面上外延或聚结上很薄的卤化银壳, 使其形成有别于传统卤化银的新型多相光敏体系, 即非银核/卤化银壳多相组合光敏微晶体系。     

照相显影化学的新进展

人们对卤化银的光化学是相当了解和熟识的。而卤化银乳剂颗粒的结构和光物理一直是许多述评和专著的内容^[1]。卤化银进行光化学分解释放出金属银和游离的卤素。照相层的曝光涉及单个颗粒的曝光。     

利用新的指示反应催化光度测定痕量银

催化动力学分析法测定痕量银的报导相对较少,至今仅二十多篇^[1-4],其中大多数是以过硫酸盐作氧化剂。用H₂O₂作氧化剂的体系文献报导很少^[5]。本文在实验基础上,发现在Na₃PO₄-Na₂PO₄介质中,银能催化H₂O₂氧化硫酸对氨基二乙基苯胺,得紫红色产物,其颜色随时间延长而加深,反应速度在一定范围内随银用量增大而加速。本文研究了一系列反应条件之后,拟定出了催化光度测定痕量银的分析方法。     

卤化银乳剂颗粒上不对称菁染料J-聚体荧光的研究

光谱增感机理的研究是感光科学中的一个重要课题Gilman^[1]和Kuhn等^[2]曾经提出光谱增感的电子转移和能量传递理论。随着现代谱学手段的出现,为人们了解光谱增感的初始过程提供了条件。近年来,电子转移的机理已被广泛接受,并用来解释与光谱增感有关的各种现象。但在ns~ps范围内的光谱增感动力学方面的研究还不多见。Dahne认为光谱增感不仅决定于染料与卤化银的能级关系,而且是由动力学控制的^[3],激发态染料向卤化银导带注人电子的电子转移过程与辐射及其他无辐射去活过程是竞争的^[4]我们通过对两种不对称的苯并咪哇唾碳著染料在AgBrI乳剂颗粒上吸附形成的J一聚体的荧光性质的研究,以求深人了解光谱增感的电子转移机理及其动力学过程,无疑是有重要意义的。     

照相明胶与化学增感剂相互作用的XPS研究

本文采用X射线光电子能谱技术研究了两种照相明胶与化学增感剂相互作用的机理.当两种照相明胶样品在HAuCl₄溶液中反应5min后,明胶中的蛋氨酸、蛋氨酸亚砜均被氧化为蛋氨酸砜.与此同时,明胶吸附的大部分Au³⁺被还原为Au⁺,并且Au⁺以络合形态存在于明胶之中.根据与AuCl₃反应之后明胶中Au³⁺与Au⁺的比例,法国明胶的还原性略高于包头明胶.添加到明胶中的Na₂S₂O₃能将明胶大分子所含的蛋氨酸亚砜全部还原为蛋氨酸.S₂O₃^2-、蛋氨酸和蛋氨酸砜可以稳定共存于明胶体系之中,外加的S₂O₃^2-的还原性高于明胶中蛋氨酸、蛋氨酸亚砜的还原性.添加Na₂S₂O₃后的两种照相明胶均可以将其溶胀吸附的Au³⁺全部还原为胶态金.此时,参与氧化还原反应的主要基团是S₂O₃^2-而非明胶中的蛋氨酸残基.由于Na₂S₂O₃的添加,照相明胶对AuCl₃的还原能力增强.     

氯化银T-颗粒乳剂制备专用的氧化明胶的研究

以往的研究表明:低蛋氨酸含量的明胶能制得晶体形态比较高的高氯T-颗粒乳剂.本文用氧化方法进一步降低明胶中的蛋氨酸含量.明胶经氧化剂(H₂O₂)氧化能得到不同的氧化明胶.用电位法测定氧化明胶的还原性;用氨基酸分析仪测定它们的蛋氨酸含量;用SDS-PAGE电泳法测定它们不同结构的组份含量.结果表明,还原性及蛋氨酸含量随氧化剂加入量的多少而变化;但氧化明胶的分子量分布与原胶相比变化甚小.     

热处理对照相明胶溶液粘度和分子量分布的影响

本文以四种照相明胶为研究对象,探讨热处理对照相明胶溶液粘度和分子量分布的影响。实验结果表明,随着加热温度上升,照相明胶溶液粘度下降,数均分子量下降。照相明胶溶液粘度和数均分子量密切相关,照相明胶溶液粘度下降发生的内在原因是数均分子量下降。在本实验条件下,惰胶、活性胶的加热温度不超过75℃,PA胶的加热温度不超过60℃。     

STUDY ON HYDROLYSIS OF MACROMOLECULAR GELATIN WITH ENZYMES IN COMBINATION MODE

INTRODUCTIONMacromolecular gelatin is principally derived from type collagen. Gelatin hydrolyzate can be prepared frommacromolecular gelatin by hydrolytic reaction with acid, alkali, heating or enzyme.The gelatin hydrolyzate maintains most of the inherent physical and chemical characteristics ofmacromolecular gelatin and also acquires some new ones by taking advantage of the lowering of the molecularweight. With the advancement of science and technology, the application of gelatin hydroly…     

THE REACTION OF SINGLET OXYGEN WITH PROTEINS, WITH SPECIAL REFERENCE TO CRYSTALLINS

Photosensitized oxidation of the eye lens proteins, the crystallins, is thought to lead to protein crosslinks and high molecular weight aggregates. Such protein modifications may be important factors in the formation of lens opacities or cataracts. We focus attention here on type 2 photo-oxidation involving the reaction of singlet oxygen (1O2) with crystallins and some "control" proteins. We find that: (1) trp residues are oxidized to N-formyl kynurenine and related products, but this in itself does not lead to the production of high molecular weight protein aggregates of the protein; (2) tyr residues react with 1O2 but we do not detect dihydroxyphenylalanine or bityrosine nor are protein crosslinks formed as a result; (3) oxidation of his residues appears necessary for high molecular weight protein covalent aggregates to form. Proteins devoid of his, e.g. melittin or bovine pancreatic trypsin inhibitor, do not form high molecular weight products upon reaction with 1O2. Prior reaction and blocking of his inhibits the crosslinking reactions. (4) The oxidized protein is seen to be more acidic than the parent and has an altered tertiary structure. (5) Among the crystallins, reactivity towards 1O2 varies in the order gamma greater than beta greater than alpha and also gamma A/E greater than gamma D greater than gamma B crystallin.     

Ag+在照相明胶不同分子量组分中的分布

利用凝胶排阻层析-火焰原子吸收光谱法研究了Ag+在照相明胶中分子量的分布情况.研究表明,利用葡聚糖凝胶G-75可有效的将明胶中的γ、β、α及小分子蛋白L组分分开.发现Ag+完全分布于分子量较小的α大分子蛋白组分.γ组分、β组分中均不存在Ag+.     

照相明胶中硫存在形态的XPS研究

本文采用X射线光电子能谱技术,研究了国内外典型的两种照相明胶的空白样品、掺杂铁(Ⅲ)的样品中硫元素的存在形态。硫在明胶中主要以三种化学形态存在:蛋氨酸砜中的 基团,蛋氨酸亚砜中的 基团,蛋氨酸中的-S-基团。三种化学形态间的相对含量基本上反应出蛋氨酸及其两种氧化产物之间的相对比例。在我们的实验条件下,外来三价铁,引发部分蛋氨酸砜被还原为蛋氨酸亚砜,与此同时,明胶中的-CH₂-基团部分氧化为 基团。     

Electron-transfer polymers. XXX. Preparation of poly(1-vinyl-3,4,6-trimethyl-2,5-benzoquinone)

1-Vinyl-3,4,6-trimethyl-2-methoxy-5-hydroxy-benzene (I) was prepared in good yield by the Wittig reaction from the corresponding chloromethyl compound. It could be polymerized cationically to low molecular weight material. The polymer could be oxidized to poly(1-vinyl-3,4,6-trimethyl-2,5-benzoquinone) (III) and could be reduced to the corresponding hydroquinone. Compound (I) was acetylated at the phenolic hydroxyl group and polymerized. The acetyl group was quantitatively reduced with lithium aluminum hydride, and the resulting polymer could be oxidized quantitatively to (III). Its molecular weight was a little higher than that prepared directly from (I).     

Nanometer-sized gelatin particles prepared by means of gamma-ray irradiation

Nanometer-sized gelatin particles have been prepared by means of gamma-ray irradiation and characterized by static and dynamic light scattering combined with circular dichroism (CD) measurements. The molecular weight of the nanoparticles was much larger than that of the original gelatin molecules, whereas the hydrodynamic radius was much smaller. Radius of gyration evaluated from the angular dependence of the static light scattering intensity decreased with increasing irradiation dose. CD spectra of the gelatin nanoparticles were independent of temperature, and it is suggested that the nanoparticles consist of highly and randomly packed gelatin and their conformation is stable against the temperature change.     

“EMULSION COPOLYMER THEORY: KINETICS AND SEQUENCE DISTRIBUTIONS”

Gelatin is well suited in the preparation of nanosize particles by precipitation of organic substances. Due to their amphiphilic structure, the gelatin molecules exhibit a pronounced surface activity. The surface activity was investigated by means of the Wilhelmy plate and the maximum bubble pressure technique within a time frame of more than five orders of magnitude. The influence of an emulsifier and the gelatin/emulsifier interaction are discussed. By means of laser Doppler electrophoresis, the electrophoretic mobility of A-type and B-type gelatin is measured. The molecular weight distribution of gelatin is measured by size exclusion chromatography. The size of dissolved and adsorbed gelatin molecules is determined by means of dynamic light scattering. It is shown that the surface activity of the gelatin/emulsifier complexes controls the size of the precipitated particles. Furthermore, we show that gelatin is adsorbed by hydrophobic interactions and provides excellent colloidal stability to nanosize particles.     

明胶酯化及酞酰化对于沉降性能的影响

酞酰化明胶作为中、低感光乳剂的沉降剂已经得到了广泛的应用。这个沉降剂的优点是沉降pH范围较窄,沉降速度较快,有增感作用,复溶容剔。它的主要缺点就是不适用于氨法高感乳剂。究其原因,主要是由于PA改性明胶的等电点比较低。