间接原子吸收光谱法测定胱氨酸

根据胱氨酸和碘酸银中的银生成的配合物,在谷氨酸和甘氨酸存在时用间接原子吸收光谱法测定了胱氨酸。研究了pH值、反应时间、试剂用量及加入试剂顺序的影响。对合成样品的分析表明,相对误差小于3％。     

抗坏血酸及L-半胱氨酸的流动注射动力学同时测定法

pH2～9时,抗坏血酸与L-半胱氨酸均可与Fe3+-邻菲咯啉混合液反应,生成Fe2+-邻菲咯咻有色配合物,但两者反应速度相差极大。根据这个原理,采用流动注射分析停流技术,建立了抗坏血酸与L-半胱氨酸的动力学吸光光度同时测定法。两者测定的线性范围分别为0～24mg·L-1和0～280mg·L-1,相应的检出限为1mg·L-1和16mg·L-1,抗坏血酸与L-半胱氨酸浓度分别为12.0mg·L-1和160.0mg·L-1时,测定的相对标准偏差分别为0.9％和0.6％,采样频率为30样·h-1。该法灵敏、快速、准确,选择性较高,且流路及设备简单,实用性强,用于实际样品测定,抗坏血酸及L-半胱氨酸的加标回收率分别可达95.2％和92.8％。     

胱氨酸改性TiO_2可见光下催化活性及催化机理

以胱氨酸为掺杂剂,采用溶胶-凝胶法制备了胱氨酸改性的TiO2可见光催化剂,并对其进行了TG-DTA、XRD、表面光电压光谱(SPS)及XPS表征。XRD结果表明,胱氨酸有效抑制了TiO2晶粒的生长,提高了锐钛矿向金红石相的转变温度。SPS分析结果显示,改性TiO2光催化剂可见光吸收增强,吸收带边明显红移,且胱氨酸用量为4.2%的样品光伏响应强度最大。XPS分析结果表明,胱氨酸改性TiO2样品表面的羟基含量明显增加,且O2p价带的VMB(价带最大值)值为2.3 eV,小于非改性TiO2。以罗丹明B为模型污染物,考察了胱氨酸掺杂量与焙烧温度对改性TiO2在可见光下催化性能。结果表明,胱氨酸掺杂量(相对TiO2)为4.2%、350℃焙烧的催化剂催化活性最好。波长为380～630 nm、470～800 nm的光辐射120 min后,罗丹明B的降解率分别达到91.02%、78.44%。     

微量元素配合胱氨酸治疗脱发的临床研究

为评价口服氨基酸螯合钙胶囊配合胱氨酸片对脱发患者的临床疗效 ,将 1 2 0例脱发患者随机分为治疗组与对照组。治疗组 60例用氨基酸螯合钙胶囊 ( 1g/d ,1粒 ,qd ,PO)和胱氨酸片( 3 0 0mg/d ,3次 /d ,PO)治疗 ,对照组 60例用胱氨酸片 ( 3 0 0mg/d ,3次 /d ,PO)治疗 ,两组用药均为 1 2周。结果表明 ,治疗组与对照组相比 ,治疗组较对照组的临床症状有明显改善 ,头发中微量元素锌、铁、钙的含量有显著性差异 (P <0 0 5 )。脱发患者经补充有效的所需微量元素配合胱氨酸治疗收到良好效果。     

化学发光法分析胱氨酸

基于胱氨酸在酸性条件下对高锰酸钾-甲醛化学发光体系的增强作用,建立了化学发光法对胱氨酸的分析。考察了高锰酸钾、甲醛及酸性条件对发光强度的影响。在优化实验条件下胱氨酸在2.5×10~(-5)~2.5×10~(-3)mol/L浓度范围内呈良好的线性关系,线性回归方程为I=134.76+547.17c(R=0.9976);检出限2.49×10~(-6)mol/L;平行测定11次浓度为2.5×10~(-5)mol/L胱氨酸标准溶液的发光强度值,相对标准偏差为2.7%。     

水溶性发光金量子点灵敏检测L-半胱氨酸

室温下一步合成了一种蓝色发光金量子点。 该金量子点具有良好的水溶性和生物相容性,金量子点平均粒径为3.0 nm,在波长305 nm光激发下,发射430 nm蓝色荧光。 实验发现,一定量L-半胱氨酸对金量子点430 nm处荧光发射有显著的增强作用,由此可建立一种简单、迅速、灵敏检测L-半胱氨酸的新方法。在最佳条件下,金量子点荧光强度与L-半胱氨酸在0~4.0 μmol/L浓度范围内呈线性关系,线性相关系数R2=0.9976,对2.0 μmol/L L-半胱氨酸的11次测定结果的相对标准偏差（RSD）为2.8%,以3倍标准偏差计算本法对L-半胱氨酸测定的检出限为5 nmol/L。     

用自动滴定微库仑计分别测定混合物中半胱氨酸及胱氨酸的含量

半胱氨酸和胱氨酸在医药上有多种用途,能治疗多种疾病,又可供生物化学和营养学的研究之用。我们已用库仑滴定法分别测定了半胱氨酸和胱氨酸。国外已有用库仑滴定法分别测定混合物中半胱氨酸和胱氨酸含量的报导;也有用选择电流库仑法分别测出半胱氨酸、胱氨酸和蛋氨酸的报导。用自动滴定微库仑计在混合物中分别测定半胱氨酸和胱氨酸的研究是一种探索。本文利用在水溶液中溴能氧化半胱氨酸和胱氨酸,而碘只能氧化半胱氨     

粮食中胱氨酸含量的测定

本文介绍的胱氨酸分析法,采用过甲酸氧化胱氨酸为标准,10分钟分析程序,分析快速准确。经对几类样品的测定,回收率(>97%)和变异系数(<4%)均符合要求。     

Cu（Ⅱ）—胱氨酸络合物吸附波的研究及蛋白质中胱氨酸的测定

研究了Cu(Ⅱ)-胱氨酸络合物极谱波的性质;提出了一种用示波极谱法测定蛋白质中胱氨酸的新方法,可在8.0×10~(-4)mol/L Cu~(2+)+8.0×10~(-3)mol/L三乙醇胺的溶液中测定0.05～20mg/L的胱氨酸。     

离子色谱安培法测定尿液中的胱氨酸

建立离子色谱安培法检测尿液中胱氨酸的分析方法。将尿液稀释处理后,过OnGuardⅡRP前处理柱,去除尿液中的有机物,选用低容量阳离子交换柱IonPac CS17进行分离,以甲烷磺酸梯度淋洗,柱后用300 mmol/L NaOH溶液衍生,离子色谱脉冲安培法检测,外标法定量。胱氨酸的质量浓度在0.1~5.0 mg/L范围内与其色谱峰面积呈良好的线性,线性相关系数r^2=0.999 9,检出限为0.05 mg/L。测定结果的相对标准偏差为0.71%(n=6),样品加标回收率为94%~108%。该方法具有操作简单,专属性强,灵敏度高等优点,可用于临床快速检测尿液中的胱氨酸。     

A carbanion induced synthesis of highly congested pyrazole and imidazole containing heterocycles

An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Selective synthesis of 4,5-dihydroimidazo- and imidazo[1,5-a]quinoxalines via modified Pictet–Spengler reaction

An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction.     

Understanding the Diels-Alder reactivity of 1,2-azaborine analogues

The Diels-Alder reactivity of 1,2-heteroborines (H₄C₄B(H)X, X?=?NH, PH, AsH; O, S, Se) has been computationally explored by means of Density Functional Theory (DFT) calculations. The influence of the HB?=?X fragment on the reactivity of the system has been quantitatively analyzed in detail by means of the so-called Activation Strain Model (ASM) of reactivity. It is found that the interaction between these species and the dienophile is significantly stronger than that computed for their all-carbon isoelectronic counterpart, benzene. In addition, the strain energy plays a key role in the observed reactivity trends. The role of the aromaticity strength of these heteroarenes on the reactivity is also assessed.     

Synthesis of N-substituted carbazolones from α-iodo enaminones via Pd(0)-catalyzed intramolecular coupling under microwave irradiation

A variety of N-aryl and N-alkyl carbazolones were conveniently achieved in good to high yields via Pd₂(dba)₃-mediated intramolecular coupling of N-substituted α-iodo enaminones under microwave irradiation. The Pd(0)-catalyzed cyclization was found to proceed favorably with the more electron-deficient phenyl ring during the reactions involving unsymmetrical N,N-diaryl α-iodo enaminones. This unique property enables the construction of carbazolone skeleton containing nitro substituted benzenoid ring.     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles by intramolecular nitrilimine cycloaddition

Both substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles have been synthesized by the 3+2 intramolecular dipolar cycloaddition of nitrilimines to alkynes. This cyclization has been extended to more versatile 3-bromo derivatives by the use of alkynylbromides as dipolarophiles.