几种天然黑色素分子结构的红外光谱表征研究

本文对黑头发、香蕉皮、葵花籽皮、乌贼墨及黑芝麻黑色素进行红外光谱表征研究，考察它们的官能团类型，初步判定黑芝麻黑色素是吲哚 型和邻苯二酚型的混合型黑色素。     

酪氨酸衍生物调控酶催化路径可控合成功能黑色素

利用酶催化自组装将生物小分子构筑成具有独特功能的生物大分子聚合物是制备功能生物材料极具前景的新策略,然而其挑战在于如何在底物层面调控生物大分子的结构和功能.以从酪氨酸构筑黑色素为例,通过底物结构的简单衍生化,实现了对酶催化自组装过程中关键聚合位点的控制,得到一系列尺寸、形貌各异的黑色素产物.进一步表征了各黑色素产物的光热转换性能,在细胞层次验证了结构修饰的黑色素用于光热材料的潜力.揭示了通过改变底物核心基团周边化学结构调控酶催化路径,进一步调控黑色素产物性质及功能的可行性,为构筑新型功能黑色素材料提供了新思路,同时对揭示生物大分子结构与生物功能的关系提供了有益启示.     

乌骨鸡黑色素的高效液相色谱法测定

建立了乌骨鸡黑色素氧化产物2,3-二羧酸吡咯（PDCA）和2,3,5-三羧酸吡咯（PTCA）的HPLC测定方法,对乌骨鸡中黑色素进行定量研究。采用Kromasil C18柱（250 mm×4.6 mm,5μm）分离,二极管阵列检测器检测,流动相为甲醇-0.1%甲酸,梯度洗脱,检测波长分别为282.8 nm和269.8 nm,并采用LC-MS对色谱峰进行定性。结果表明：PDCA和PTCA能得到很好的分离,经过初步分离纯化的乌骨鸡黑色素粗品中黑色素的含量为76.3279μg/mg。     

固体酸催化烯烃改性生物油酚类化合物研究

选取生物油中含量较高的愈创木酚、儿茶酚和苯酚为酚类模型化合物,以蒙脱土K-10负载的Cs2.5H0.5PW12O40为固体超强酸催化剂,苯酚/1-辛烯烷基化反应为探针,考察了催化剂负载量,反应温度及物料摩尔比等因素对酚类烷基化反应的影响.结果表明,在60～100℃范围内,30%Cs2.5H0.5PW12O40/K-10对苯酚烷基化反应具有很好的催化活性和选择性,原料摩尔比为1时苯酚氧烷基化产物的选择性最好.愈创木酚中甲氧基的位阻效应使其转化率在相同条件下比苯酚低很多,相应氧烷基化产物的选择性也很低.儿茶酚与1-辛烯反应主要生成单羟基氧烷基化产物,100℃时选择性仍高达96%.升高温度有利于烷基化改性反应的进行,但产物中氧烷基化产物的选择性随着温度升高而降低.     

壳聚糖钙/锌配位降解产物的GFC及清除O-·2研究

分别将Ca(Ⅱ)和Zn(Ⅱ)加入到壳聚糖溶液中,调节pH值使壳聚糖与金属配位.加入H2O2并升高温度对处于配位缔合状态的壳聚糖进行氧化降解,测定了降解产物寡糖的数均相对分子质量和相对分子质量分布.结果表明壳聚糖在与Ca和Zn配位的情况下,可被H2O2迅速降解;降解从大相对分子质量范围开始,降解产物寡糖相对分子质量分布较窄,且聚合度(DP数)越小,寡糖相对分子质量分布指数越小.同时对两者的降解产物进行了清除超氧阴离子自由基(O2-.)的研究,研究发现两者的降解产物均对O2-.有一定的清除作用,清除率随降解产物数均相对分子质量的减小而增大.但用完全降解产物氨基葡糖形成配合物时,清除作用几乎完全消失.     

新型仿生光催化剂HMS-FePcS催化孔雀绿在可见光下的降解历程

在可见光照射下,采用合成的新型仿生光催化剂HMS-FePcS催化降解孔雀绿模拟染料废水.由不同反应时间段反应液的HPLC谱和MS谱中产物峰的变化可知,孔雀绿的催化降解过程为先脱色后矿化.采用固体萃取法对孔雀绿降解的中间产物进行了富集和分离,并使用GC-MS对所得的中间产物进行了鉴定,确定出10余种中间产物.在此基础上对孔雀绿的降解历程进行了推测,指出孔雀绿的光催化降解主要从中心碳原子与二甲氨基苯基之间的C-C键处断裂,4-二甲氨基苯甲酮是此反应最常见的中间产物.当4-二甲氨基苯甲酮被羟基自由基进攻时,生成苯甲酸、对二甲氨基苯甲酸及对二甲氨基苯酚等化合物.这些小分子芳香类中间产物进一步发生羟基化反应,开环生成小分子脂肪酸类化合物.     

甲基叔丁基醚光催化降解的反应历程

以自制的TiO2为催化剂,在间歇式光催化反应装置中考察了水中甲基叔丁基醚的光催化降解反应.结果表明,水中MTBE在TiO2催化剂、氧气和紫外光照射的条件下能被光催化转化成无毒产物并最终被矿化.MTBE光催化降解过程中产生的主要中间产物有甲酸叔丁酯、叔丁醇和丙酮,尽管降解速率不同,它们也都能被光催化降解.通过对反应物、中间物及产物的追踪分析,认为MTBE的光催化降解首先是通过羟基化过程来进行,进而提出MTBE光催化降解的可能反应历程.     

三乙醇胺的电化学降解研究

采用电化学的方法对三乙醇胺进行降解,并研究了三乙醇胺的降解产物以及可能的降解过程.利用电化学工作站获得三乙醇胺的电化学窗口信息,电解降解后再利用气相色谱-质谱法(GC-MS)对三乙醇胺的降解产物进行分离分析.结果表明,降解三乙醇胺的最佳支持电解质为Na2SO4溶液,且三乙醇胺主要在阳极上发生氧化反应.在反应时间为150...     

Lys调节PLGA纳米纤维的体外降解产物酸度的研究

采用向PLGA纳米纤维中添加碱性氨基酸——赖氨酸(Lys)的方法来降低降解产物的集酸程度.用电纺丝技术制备载Lys的PLGA/Lys复合纳米纤维,并用SEM、DSC、及力学测试等表征手段对该复合纳米纤维的形貌、热学性质以及力学性质等方面进行表征;研究PLGA/Lys复合纳米纤维中Lys的释放特性;对PLGA与PLGA/Lys纳米纤维进行体外降解实验,评价纤维降解过程中的形貌和降解液pH值;用已降解8周的纳米纤维降解液对血管平滑肌细胞进行培养,MTT检测细胞毒性.结果表明,在电压为12 kV,注射速率1.0mL/h,温度23℃,湿度20%,接收距离14 cm时可以纺出形貌较好的PLGA/Lys复合纳米纤维,Lys含量越多,复合纳米纤维的直径越细.纳米纤维中Lys的含量影响Lys的释放特性.Lys促进PLGA的降解并对改善其降解产物的酸度有一定的缓解作用,含2%Lys的纳米纤维降解8周后可以使降解液pH维持在7.4~6.7之间.降解的酸性产物不利于平滑肌细胞生长,但含Lys降解液的培养基中细胞生长状态良好,这可能是由于Lys能减轻酸性降解产物对细胞功能的影响,同时也能为细胞增殖提供营养物质.     

含磷毒剂及其降解产物的气相色谱-质谱测定方法研究

研究了用台式气相色谱-质谱仪分析测定含磷毒剂及其降解产物,并对降解产物的衍生化方法及它们的色谱行为进行了研究,总结分析了它们的质谱裂解特点及规律,测定了水样中的含磷毒剂及降解产物。     

Melanin from epidermal human melanocytes: Study by pyrolytic GC/MS

Pigmentation of human skin is determined by the presence of melanin, the polymeric pigment that is produced in melanocytes and transferred to adjacent keratinocytes. Epidermal melanocytes produce two distinct types of melanin pigments: eumelanin, composed mainly of indole-type monomers, and pheomelanin that contains benzothiazine-type backbone. Eumelanin protects skin against UV-induced damages, whereas pheomelanin is believed to act as a potent UV photosensitizer and promote carcinogenesis. In this study, pyrolysis in combination with gas chromatography and mass spectrometry (Py-GC/MS) was applied for structural studies of the epidermal pigment isolated from the cultured human melanocytes. The analysis was preceded by investigations of DOPA-originated synthetic eumelanin and pheomelanin standards. This allowed determination of pyrolytic markers for both types of melanin pigments. To obtain additional information on the natural pigment structure, the samples were thermally degraded in the presence of tetramethylammonium hydroxide as the derivatizing agent. It was shown that the analyzed pigment from normal human epidermal melanocytes derived from moderately pigmented skin is of eumelanin type with little incorporation of a pheomelanin component. The results indicate that Py-GC/MS is a rapid and efficient technique for the differentiation of epidermal melanin types and may be an alternative to commonly used methods based on chemical degradation.     

Detection and quantitation of a pheomelanin component in melanin pigments using pyrolysis–gas chromatography/tandem mass spectrometry system with multiple reaction monitoring mode

Here, we describe the reliable method for the detection and quantitation of a pheomelanin component in melanin pigments. Synthetic melanins with various contents of pheomelanin‐type structural units were thermally degraded, and the multiple reaction monitoring mode was applied to detect the pheomelanin markers in the pyrolysates by GC/MS/MS. The method allowed the specific detection and quantitation of a pheomelanin component in melanin with the incorporation of pheomelanin‐type units as low as 0.05%. Considering highly universal character of the pheomelanin markers, the method could be applied for structural studies of natural melanin pigments being mixtures of eumelanin and pheomelanin. Copyright © 2012 John Wiley & Sons, Ltd.     

PHOTOCHIMIE DES ACIDES AMINES AROMATIQUES EN SOLUTION - I. dl-PHENYLALANINE, dl-TYROSINE ET l-DOPA

Abstract— The action of ultraviolet radiation on dl -phenyldanine, dl -tyrosine and l -dopa has been studied in dilute aqueous solutions (10^-2M–5 × 10^-3M). Irradiation was performed in nitrogen or in air, at a wavelength of 254nm. The photoproducts of low molecular weight (amino acids, carboxylic acids, amines) were isolated either by chromatography on an ion exchange column or by thin-layer chromatography and identified mainly by ultraviolet absorption and staining with ninhydrin. The isolation of photopolymers was carried out by chromatography on a Biogel column; identification of these photoproducts was mainly achieved by ultraviolet and infrared spectroscopy. With phenylalanine, which is the most photosensitive amino acid, the principal reaction results in splitting of the side chain, giving alanine, glycine, and four other amine compounds whose structure has not been determined. In air, additional minor products resulting from photooxydation are obtained: ortho, meta and paratyrosine. Traces of phenylethylamine were isolated after irradiation in an inert atmosphere. The polymers produced under air and nitrogen are similar. They probably result from rearrangement of aromatic radicals formed by splitting of the side chain. Tyrosine and dopa, irradiated in air, yield mainly melanin; before polymerization, tyrosine is first converted into dopa. In a inert atmosphere, these aromatic aminoacids also polymerize, giving monophenolic and biphenolic compounds with structure close to that of melanin. The biphenolic polymer (thus obtained from dopa) shows the properties of a leuco derivative of melanin. The monophenolic polymer can be converted into melanin by the combined action of oxygen and ultraviolet radiation. Other reactions give only minor products: parahydroxy-phenyllactic acid and 3,4-dihydroxyphenyllactic acid by deamination-hydroxylation of tyrosine and dopa (in air): meta and paratyrosine by dehydroxylation of dopa, either in air or in nitrogen.     

溶剂对脂肪酶降解高分子量PBS及改性共聚物的影响

采用固定化脂肪酶分别在四氢呋喃(THF)、甲苯及THF和甲苯的混合溶剂体系中, 对高分子量的PBS及PBS/CHDM共聚物进行了催化降解, 用GPC测定了降解产物的分子量, 用质谱(MS)对降解产物进行了分析, 用FTIR表征了产物化学结构. 研究结果表明, 在脂肪酶的作用下, 对M_n在10⁵以上的PBS, 在THF体系中可降解到1.4×10⁴, 而在甲苯体系中可降解到4×10⁴; 但在THF和甲苯的混合体系中, 可将M_n 10⁵以上的PBS和PBS/CHDM共聚物都可降解为0.1×10⁴以下的原料单体、一至四环状低聚物及少量线型低聚物. 分析了水含量对酶解反应的影响.     

The role of melanin as protector against free radicals in skin and its role as free radical indicator in hair

Throughout the body, melanin is a homogenous biological polymer containing a population of intrinsic, semiquinone-like radicals. Additional extrinsic free radicals are reversibly photo-generated by UV and visible light. Melanin photochemistry, particularly the formation and decay of extrinsic radicals, has been the subject of numerous electron spin resonance (ESR) spectroscopy studies. Several melanin monomers exist, and the predominant monomer in a melanin polymer depends on its location within an organism. In skin and hair, melanin differs in content of eumelanin or pheomelanin. Its bioradical character and its susceptibility to UV irradiation makes melanin an excellent indicator for UV-related processes in both skin and hair. The existence of melanin in skin is strongly correlated with the prevention against free radicals/ROS generated by UV radiation. Especially in the skin melanin (mainly eumelanin) ensures the only natural UV protection by eliminating the generated free radicals/ROS. Melanin in hair can be used as a free radical detector for evaluating the efficacy of hair care products. The aim of this study was to investigate the suitability of melanin as protector of skin against UV generated free radicals and as free radical indicator in hair.     

Structures of cytotoxic products from Fe-catalyzed oxidation of sesamol in ethanol

The iron-ion catalyzed oxidation of ethanol solution of sesamol, a potent antioxidant of sesame, afforded two significant cytotoxic products to normal mammalian cells. The structures were determined using extensive NMR spectroscopy as a new sesamol trimer and tetramer.     

顶空气相色谱-质谱联用结合同位素峰形校正检索技术鉴别芝麻油风味成分

采用顶空气相色谱-质谱联用(GC-MS)仪结合同位素峰形校正检索技术鉴别了市售芝麻油风味成分中的71种化合物,占总检出化合物的90.2%。检出化合物可分为吡嗪、吡咯、吡啶、噻唑、噻吩、吲哚、唑、呋喃、醛类和酚类等,其中醛、酚、吡嗪和呋喃类化合物的含量较高,分别占风味成分含量的37.4%,20.1%,10.0%和6.7%。同位素峰形校正检索技术在低分辨率质谱上可对化合物的相对分子质量实现精确测量,从而为低分辨率四极杆质谱确定化合物的元素组成和解析化合物结构提供了重要依据,同时也为芝麻油的成分分析提供了新的技术手段。     

Studies on structure characterization of tryptophan melanin: Comparison between filament and curie-point pyrolysis gas chromatography/mass spectrometry

Structural studies of a synthetic melanin, obtained by means of performic acid oxidation of tryptophan, were carried out by pyrolysis gas chromatography/mass Spectrometry (Py-GC/MS). To identify the best pyrolysis conditions, both Curie-point pyrolysis and filament pyrolysis were employed and the effects of pyrolysis temperatures and times were studied. Using the first approach, various compounds were identified: toluene, ethylbenzene, styrene, indole, methylindole, ethylindole, phenol, cresol and ethylphenol. Using filament pyrolysis some interesting differences could be observed. Whereas toluene, ethylbenzene, phenol, cresol and methylindole were found, neither indole nor ethylindole was detected. Instead, new pyrolysis products were evident, such as methylpyrrole and indolin-2-one. Hence filament pyrolysis seems to activate different thermal decomposition pathways of the melanin under study. It is suggested that tryptophan melanin is a polymer containing indole and hydroxyindole derivatives as subunits.     

Enhanced thermal stability of poly(vinyl alcohol) in presence of melanin

A novel method was developed to enhance the thermal stability of PVA by using natural and synthetic melanins from oxidation of dopamine. Thermogravimetric (TG) curves indicated that the synthetic melanin changed the thermal degradation behaviors of PVA and largely improved the decomposed temperature by 80–110 °C in nitrogen when incorporation of synthetic melanin with low content (0.5–2 mass%). The thermal degradation kinetics suggested the activation energies of PVA/synthetic melanin blends were much higher than these of pure PVA. Isothermal TG curves conformed that the PVA/synthetic melanin blends exhibited more thermal stability than pure PVA. Moreover, the chemical structure changes of macromolecular after degradation were characterized by using fourier transform infrared and the results suggested that elimination reaction on the first degradation step did not took place for the PVA/synthetic melanin blends at 270 °C.