DUAL ROLE OF MELANINS AND MELANIN PRECURSORS AS PHOTOPROTECTIVE AND PHOTOTOXIC AGENTS: INHIBITION OF ULTRAVIOLET RADIATION-INDUCED LIPID PEROXIDATION

Ultraviolet radiation (UVR) is one of the risk factors for skin cancer and the main inducer of melanin pigmentation, the major protective mechanism of mammalian skin against radiation damage. The melanin pigments, eumelanin and pheomelanin, are likely to be important in protection against UVR, but their precursors are generally considered as phototoxic. The available data suggest DNA damage as the mechanism of phototoxicity. However, the effect of melanin precursors on membrane damage through lipid peroxidation, another important and probably more relevant (from the point-of-view of the melanosomal confinement of these molecules) mechanism of phototoxicity, is not known. As a model system for UVR–melanin–membrane interactions, we irradiated liposomes in the presence of eumelanin, pheomelanin and two of their major precursors, 5,6-dihydroxyindole (DHI) and 5-S-cysteinyldopa (SCD). The presence of the two melanin precursors substantially reduced the formation of lipid peroxidation products resulting from UVR exposure. The antioxidant activity of the melanin precursors was diminished under strong prooxidant conditions (presence of Fe³⁺). These results suggest that melanin precursors may have an important role in the protection of skin against the harmful effects of UVR including photocarcinogenesis.     

HYDROCOLLOIDS AS EMULSIFYING AGENTS FOR OIL-IN-WATER EMULSIONS

Hydrocolloids are water-soluble biopolymers consisting of high molecular weight polysaccharides. For generations, these biopolymers were also termed gums or stabilizers imparting viscosity, gelification and long-term stability to food systems.

Some hydrocolloids were also considered as emulsifying agents, since they help to form and stabilize oil-in-water emulsions. Only in the last two decades questions have been raised as to the mode of their action in low viscosity and low concentrations dispersed systems consisting of oil and water.

Gum Arabic is the only gum in use in dilute emulsion systems which was proved to be a good emulsifier - adsorbing onto oil-water interfaces and imparting steric stabilization.

However, other gums have been known to reduce surface and interfacial tensions, to adsorb onto solid surfaces and to improve stability of oil-in-water emulsions. Only recently attention has been paid to the structure-surface activity relationship between the gums and their emulsification abilities. Galactomannans, xanthans, pectins, etc. are being considered as emulsifying agents, and correlation between their internal composition and activity are being studied.

This review will discuss the drawbacks and prospects of hydrocolloids as food emulsifying agents, as native hydrocolloids and as modified (chemically, enzymatically) macrobiopolymeric amphiphiles.     

含牛磺酸交联聚乙烯醇的合成及其对甘油三脂吸附性能*

以牛磺酸修饰交联聚乙烯醇凝胶合成了吸附剂。吸附实验结果表明：该类吸附剂对血清中甘油三脂具有良好的吸附效果,而对血清中总蛋白的吸附性能相对较弱。它们对甘油三脂的吸附性能着吸附剂上功能基含量的增加而加强,但随着载体的交联度的提高而降低。血清中致病因子的浓度影响吸附性能。     

蒙脱石-石墨-聚氯乙烯复合电极的研制

化学修饰电极自1975年正式问世以来^[1],经过多年的不断发展,现已出现了许多修饰方法^[2];如表面吸附法,聚合物薄膜法,共价键合法等。这些方法虽在一定程度上改善了修饰电极的表面结构,提高了电极的灵敏度和选择性,但由于此类修饰都是在电极表面附上一层修饰剂,容易因修饰层不牢而脱落,或修饰厚度不均匀而影响电极的性能,近年来出现了组合法制作碳糊电极^[3]及蒙脱石修饰碳糊电极^[4]的研究,但由于碳糊及其修饰电极存在电极表面柔软的缺点而使其生理性,稳定性欠佳,本文用聚氯乙烯作粘合剂,在其融状态下,将石墨和蒙脱石混合,加压,冷却制成复合电极,该复合电极用于苯酚测定时,表现出良好的稳定性,重现性和催化效果,并克服了蒙脱石修饰碳糊电极稳定性,重现性差的缺点。     

改性明胶沉降剂的研制

沉降法在浓缩乳剂的制备中起着很重要的作用,改性明胶沉降剂的应用越来越被人们重视。本文研究了多种改性明胶的合成、取代度的测定、物理性能、沉降条件、沉降过程中明胶及卤化银的回收率和改性明胶卤化银乳剂的感光性能等。研究结果表明:改性明胶沉降剂具有以下的优点:取代度高、沉降诱发期短,沉降的pH范围较窄(一般0.6pH单位),卤化银的回收率高,而改性明胶沉降乳剂的性能比传统的水洗乳剂的性能优异:表现在灰雾小,最大密度高,分辨率好,感光度高和自然保存性能好。文章对造成上述现象的原因也进行了初步的分析和讨论。     

改性羧甲基羟丙基纤维素在聚醋酸乙烯乳液中的增稠效应

用旋转粘度计研究了改性羧甲基羟丙基纤维素在聚醋酸乙烯乳液中的增稠效应。通过与非离子型羟乙基纤维素及离子型羧甲基纤维素的比较试验表明,改性羧甲基羟丙基纤维素用作聚醋酸乙烯乳液增稠剂有良好的增稠性、稳定性和配伍性。     

BIS-(SULFONYLFORMYL)-DIAMINES AS POTENTIAL CYTOSTATIC AGENTS

Abstract

Four bis-(sulfonylformyl)-diamines 11a-c,e have been prepared by oxidation of the corresponding bis-thiolcarbamates 1 with 3-chloroperbenzoic acid. Bis-thiolcarbamate Id could not be oxidized because of insufficient solubility. Bis-thiolcarbamates IXa,b decomposed upon attempted oxidation.     

ANTIFOULING PROPERTIES OF POLYVINYL CHLORIDE) MEMBRANES MODIFIED BY AMPHIPHILIC COPOLYMERS P(MMA-A-MAA)

Three well-defined diblock copolymers of poly(methyl methacrylate-b-methacrylic acid)(P(MMA-b-MAA))were synthesized using atom transfer radical polymerization method and varying poly(methacrylic acid)(PMAA)chain lengths. These copolymers were blended with PVC to fabricate porous membranes via phase inversion process.Membrane morphologies were observed by scanning electron microscopy(SEM),and chemical composition changes of the membrane surfaces were measured by X-ray photoelectron spectroscopy(XPS).Static and dynamic protein adsorption experiments were used to evaluate antifouling properties of the blend membranes.It was found that,the blend membranes containing longer PMAA arm length showed lower static protein adsorption,higher water permeation flux and better protein solution flux recovery.     

吡唑啉衍生物作为空穴传输层在电致发光材料中的应用

我们曾报道过有关1,3二苯基吡唑啉衍生物的光谱和光物理行为^[1,2],并详细地研究了它们在受激发后的辐射和非辐射衰变过程.该类化合物作为一种良好的光致发光材料,由于存在着分子内共轭的电荷转移结构,因此表现出较强的光诱导分子极化能力,可用作为有机非线性光学材料^[3]、光折变材料等.此外,还发现该类化合物在组合型光导器件中可用作空穴传输层材料.既然这类化合物兼具光致发光和空穴传输功能,很自然的会考虑到,它是否也能用作为一种有机的电致发光(EL)材料.有机电致发光材料的重要性自不待言,特别近年来许多科学家致力于此,因此进展很快.但寻找新的高效材料,不论是用作主要的发光层或其它的辅助性化合物,仍在继续.本简报即是对上述化合物用作EL材料的初步研究.     

化学修饰电极的研究ⅩⅢ. 聚乙烯二茂铁(PVFc)薄膜电极和电催化效应

本文研究了影响PVFc薄膜电极伏安性质的各种因素, 讨论了聚合物薄膜电极的电荷传递过程。溶液平衡离子的水合半径大小、离子强度、溶剂对薄膜的溶胀性质以及聚合物薄膜的厚度是影响聚合物薄膜电极伏安性质的主要因素。研究了PVFc薄膜电极对亚铁氰化钾、左旋多巴和儿茶酚的电催化作用, 用旋转园盘电极研究了催化过程动力学。抗坏血酸和儿茶酚的混合物在PVFc薄膜电极上呈现分开的氧化还原峰, 有应用于生物化学分析的意义。     

活性基质在降烯烃渣油裂化催化剂中的应用

研究了渣油裂化催化剂的基质改性对催化剂性能的影响。结果表明，经高温及酸处理后，高岭土的孔容、比表面及其表面酸性明显增加；对拟薄水铝石进行磷改性，可增加氧化铝的表面酸性中心数目，降低酸强度。用改性的高岭土和氧化铝作为降烯烃渣油裂化催化剂的活性基质，可提高催化剂的渣油裂化及氢转移、异构化活性，并减少催化剂上的积碳。     

FLAVIN COMPOUNDS AS AGENTS FOR THE OXIDATION OF PLASTOCYANIN IN BLUE LIGHT

Abstract—Flavins, flavin nucleotides and selected flavoproteins have been compared in a reaction using blue light. in which plastocyanin is oxidized as the flavin is photoreduced. Per unit of light absorbed. flavin mononucleotide is more effective than flavin adenine dinucleotide, ribotlavin or lumiflavin. Of the flavoproteins tested, diaphorase from Clostridium kluyveri was most effective, but was less active than free flavin mononucleotide. The oxidation of plastocyanin requires aerobic conditions. and appears to be mediated by the production of singlet oxygen when the flavin is irradiated.     

苯并噻唑衍生物用作EL器件中发光材料的研究

在多层结构的有机电致发光器件(EL)研制中,一个最富吸引力的提高器件发光效率的方法是通过选择具有高荧光量子产率的发光染料为掺杂剂,加入到作为主体的电子或空穴传输层内,经电子与空穴在主体化合物层内的复合形成激子,经能量转移,激发染料分子,发射染料荧光.     

新型电致发光材料1,5-萘二胺衍生物的合成和性质研究

合成了一种新型的有机电致发光材料:N,N'-二苯基-N,N'-二(1-萘基)-1,5-萘二胺(NPN),测定了其吸收光谱和荧光发射光谱.该材料具有很好的热稳定性,DSC测定其玻璃化温度(T_g)高达127℃,循环伏安法(CV)测定其电离势(I_p)为5.30eV,可望用作有机电致发光空穴传输或蓝色发光材料.     

普鲁士兰修饰碳黑微电极同时微分伏安法测定多巴胺和坑坏血酸

将含有1.0%普鲁士蓝的碳黑与固体石蜡按2.5∶1(质量比)混合后装入φ0.2mm的石英毛细管中,在其上端插入一铂丝并抛光后即制成普鲁士蓝修饰碳黑微电极.对多巴胺(DA)及抗坏血酸(VC)在此电极上的电化学行为及应用此电极测定两组分的最佳条件进行了研究,在定量测定中采用二次微分线性扫描伏安法.在最佳条件下,DA与VC的峰电流(i″p)分别与各自的浓度保持如下线性关系:DA为4.0×10-6～8.0×10-4mol·L-1,VC为6.0×10-5～1.0×10-3mol·L-1;检出限(3σ)依次为2.0×10-6mol·L-1及1.0×10-5mol·L-1.应用此方法分析了3种含DA及VC的混合溶液,测得结果的相对标准偏差(n=8)依次小于2.0%及3.0%,回收率范围依次为96.5%～101.0%及95.0%～102.5%.     

普鲁士兰修饰碳黑微电极同时微分伏安法测定多巴胺和抗坏血酸

将含有1.0%普鲁士蓝的碳黑与固体石蜡按2.5∶1(质量比)混合后装入φ0.2mm的石英毛细管中,在其上端插入一铂丝并抛光后即制成普鲁士蓝修饰碳黑微电极.对多巴胺(DA)及抗坏血酸(VC)在此电极上的电化学行为及应用此电极测定两组分的最佳条件进行了研究,在定量测定中采用二次微分线性扫描伏安法.在最佳条件下,DA与VC的峰电流(i″p)分别与各自的浓度保持如下线性关系DA为4.0×10-6～8.0×10-4mol·L-1,VC为6.0×10-5～1.0×10-3mol·L-1;检出限(3σ)依次为2.0×10-6mol·L-1及1.0×10-5mol·L-1.应用此方法分析了3种含DA及VC的混合溶液,测得结果的相对标准偏差(n=8)依次小于2.0%及3.0%,回收率范围依次为96.5%～101.0%及95.0%～102.5%.     

聚(甲基丙烯酸-2-羟乙酯)改性金表面用于构建生物检测基材

采用电子活化再生原子转移自由基聚合(AGET ATRP)的方法将聚(甲基丙烯酸-2-羟乙酯)(PHEMA)接枝在金表面,对经修饰的金表面的生物惰性做了系统的研究,并利用PHEMA的羟基末端固定生物素(biotin)分子,以biotin对抗生物素蛋白(avidin)的识别为模型,研究了不同厚度的PHEMA对结合avidin的影响,以及该表面作为生物检测基材的可行性.生物惰性研究表明,PHEMA修饰的金表面不但能够有效的排斥纤维蛋白原(Fg)、人血清白蛋白(HSA)和溶菌酶(Lys)的非特异性吸附,还能够抑制3种细胞(L02、L929和EC)的黏附,是一种良好的抗污表面.通过控制聚合时间制备了不同厚度的PHEMA-biotin修饰的表面,同位素125I标记HSA吸附结果表明这几种表面均能够有效排斥非特异性蛋白质吸附,特异性FITC-avidin吸附结果表明,厚度较小时(16 nm)由于荧光淬灭而难以检测到荧光信号,厚度在16 nm和49 nm之间,荧光信号随厚度增加而增强,通过比较信噪比,认为厚度在49 nm以上时比较理想.该表面在应用于QCM与荧光检测中均表现出良好的检测性能.     

CATIONIC VESICLE PRECURSORS AS RETARDING AND LEVELLING AGENTS FOR THE DYEING OF ACRYLIC FIBRES

The use of a double-tailed cationic surfactant as additive in the dyeing of polyacrylonitrile with cationic dyes is proposed. Single-tailed colorless cations usually compete with the dyes for the anionic sites within the fibre and at the fibre surface, thus retarding and giving levelness to the dyeings. A set of comparative tests has shown that di-methyl-di-dodecylammonium chloride (DDDAC) behaves better by far, as retarding and levelling agent, than commercially well known single-tailed cations.     

FURTHER STUDY OF ALLYL ETHERS AND RELATED COMPOUNDS AS TRANSFER AGENTS IN RADICAL POLYMERIZATIONS

Allyl glycidyl ether (AGE), allyl 1,1,2,3,3,3-hexafluoropropyl ether (AFE), allyl 2-naphthyl ether (ANE), 2-vinyl-1,3-dioxolane (2VD) and allyl alcohol (AA) have been examined as transfer agents in the radical polymerization of methyl methacrylate (MMA) at 60°C; the transfer constants are 1.1 × 10^?3, 0.1 × 10^?3, 0.2 × 10^?3, 1.1 × 10^?3 and 0.6 × 10^?3, respectively. AFE and AA barely affect the rate of polymerization: AGE, ANE, and 2VD act as weak retarders. There is no direct correlation between effectiveness as a transfer agent and the extent of retardation for these additives. For copolymerization with MMA (monomer-1), the monomer reactivity ratios r₁ are 42 ± 5 and 32 ± 5 for AGE and ANE, respectively; for both cases, r₂ is very close to zero; 2VD engages in copolymerization with MMA to a negligible extent. Experiments involving styrene or acrylonitrile gave results consistent with those obtained using MMA.     

DIKETONES AS PHOTOSENSITIZING AGENTS: APPLICATION TO αLAMINO ACIDS and ENZYMES

Abstract— 2,3-Butanedione (biacetyl), phenylglyoxal, 1,2-cyclohexanedione and similar carbonyl compounds have been used as specific arginyl probes in enzyme chemistry. Depending on irradiation conditions, these and other related carbonyl compounds may, however, cause extensive changes in the structure of an enzyme regardless of the essentiality or unessentiality of arginyl residue for enzyme activity. Particularly biacetyl and 2,3-pentanedione are powerful and general photoinactivators of enzymes in the visible region. A striking result of this process is the virtually total, time-dependent loss of tryptophan fluorescence of the enzyme, which is accompanied by other irreversible structural changes. Several ketones and ketone aldehydes photoinactivate enzymes in UV light as well; phenylglyoxal and 1,2-cyclohexanedione effectively inactivated enzymes at 254 nm and in the far UV region. In most cases, these photosensitized inactivations of an enzyme can be prevented by keeping the reaction mixture in anoxic conditions or adding singlet oxygen quenchers to the reaction mixture. 2-Thiol-L-histidine, 3-methyl-L-histidine and other imidazole derivatives are more effective protectors of enzymes against photodestruction than N_3-.