Investigation of Surface-Enhanced Raman Spectra of Human Gallstones on Colloidal Silver

The surface-enhanced Raman scatterihg (SERS) spectra of human gallstones is investigated. Complicated Raman bands were due to multiple components that include bilirubin, bilirubinate salts, cholesterol, fatty salts and proteins. The results suggest that besides bilirubin and cholesterol, fatty salts and proteins may play an important role in the formation of gallstone. The experimental data supply an useful information for the research of the formation mechanism of gallstones.     

人体胆结石难溶物的扫描电镜观察和红外光谱研究

用傅里叶变换红外光谱仪和扫描电镜研究了胆色素型和混合型胆结石经氯仿、乙醇、乙醚、盐酸等溶剂溶解剩余的主要组分和微观结构。结果表明，胆红素盐、蛋白质、脂肪酸盐、碳酸钙等为难溶物；棕色色素胆石中的蛋白质的二级结构似a-螺旋为主。扫描电镜观察显示，在色素型和混合型胆石难溶物中都出现了可能为蛋白质的薄膜带状物，讨论了难溶物与结石形成的关系。     

徐州地区胆结石的溶剂萃取的FTIR研究

胆石病是徐州地区的多发病之一,针对徐州地区临床术中取出的五类胆结石利用系列溶剂萃取,用傅里叶变换红外光谱(FTIR)分别表征萃取前后的成分、结构及形态变化。结果表明:所取的五类徐州地区胆结石分别为胆固醇型、难溶物分别为胆红素盐、蛋白质的胆固醇为主的混合型、棕色色素型和黑色色素型胆结石。蛋白质为胆结石的形成提供沉淀基质,对于胆结石成核具有重要意义;胆结石难溶物中胆固醇和羟基碳酸磷灰石相伴而生,羟基磷灰石与胆固醇存在相互作用,促使其结晶析出,从而加速胆结石的形成。结果可以为胆结石的临床诊断、治疗及预防提供一定的参考。     

胆结石的FT－Raman光谱研究

胆结石的ＦＴ－Ｒａｍａｎ光谱研究徐智勇，李维红，王立波，许振华，吴瑾光（北京大学化学与分子工程学院，稀土材料化学与应用国家重点实验室北京１００８７１）ＴｈｅＩｄｅｎｔｉｆｉｃａｔｉｏｎｏｆＴｈｒｅｅＤｉｆｆｅｒｅｎｔＴｙｐｅｓｏｆＧａｌｌｓｔｏｎｅｓ...     

几种饱和脂肪酸及其盐的拉曼光谱研究

饱和脂肪酸及其盐在自然界中广泛存在,它们也是重要的化工原料。但是有关此类物质拉曼光谱特征的研究尚属少见。为了进一步了解它们的拉曼光谱特征,对乙酸、硬脂酸及乙酸钙、乙酸镁、硬脂酸钙、硬脂酸镁进行了拉曼光谱研究。从指认这6种物质拉曼光谱的特征峰拉曼位移出发,对它们的相应谱峰进行比对与分析,探讨了阳离子的引入对饱和脂肪酸及其盐的拉曼光谱的影响,找出了它们拉曼光谱的差异。比较不同阳离子形成的饱和脂肪酸盐的特征峰拉曼位移的差别,从折合质量和核外电子构型角度解释了造成差异的原因。同时发现了长碳链可以减弱不同阳离子对饱和脂肪酸盐拉曼光谱造成的影响。     

人体胆结石红外光谱的比较分析

用红外光谱法测量了系列胆结石成分的红外光谱。比较标准化合物的红外光谱,分析人体胆结石的成分。按胆结石的红外光谱特征进行分类,获得胆固醇、胆红素钙、硬酯酸钙、碳酸钙、羟基碳酸磷灰石和混合物等六种类型的光谱图。提出相应地将胆结石分为六种类型：如果根据是否含钙,则分为胆固醇和钙盐型两种类型。     

胆红素络合物的表面增强拉曼光谱研究

本文通过对近红外激发傅里叶变换拉曼光谱(NIR-FT-Raman)与表面增强拉曼散射(Surface Enhanced Raman Scattering,SERS)技术的联用,测得胆红素及其络合物Na     

用MRI无损检测胆囊中的胆汁成

为了探索用磁共振成象方法无损伤检测胆囊中的胆汁成分的可能性,我们用0.5T的磁共振成象仪,对38例禁食期胆囊疾病患者(12例急性无并发症胆囊炎及胆结石,1例化浓性胆囊炎,2例急性出血性胆囊炎,14例慢性胆囊炎及胆结石,5例胆囊息肉,4例障碍性黄疸进行了轴向腹部胆囊部位T1-加权自旋-回波成象.结果表明:禁食或胆囊疾病患者胆汁中胆固醇(p=0.014),脂肪酸(p=0.001),和铁(p<0.001)的浓度对T₁-加权成象(TR/TE=620/25ms)的肝-胆信号强度比有明显的负影响,同时发现总蛋白质,总胆红素及Na⁺,K⁺,Cl^-,Mg⁺⁺离子的浓度对肝-胆MRI信号强度比无显著影响,由此可见,T₁-加权MRI中的肝-胆信号强度比反映了胆囊中的胆汁成分,其中影响肝-胆信号强度比的最重要因素是胆囊中胆汁所含胆固醇、脂肪酸和铁的浓度.     

Raman spectroscopy of lipids: a review

Raman spectra of 35 lipids are presented and analyzed in this work. Selected compounds, i.e. saturated/unsaturated fatty acids, triacylglycerols, cholesterol, cholesteryl esters and phospholipids, were chosen to review key lipids involved in cardiovascular disease development. Differences in Raman signatures both between diverse groups of lipids as well as various members of the same family are investigated in detail in order to elucidate marker features enabling detection and discrimination of lipids in complex samples, particularly of biological origin. This work complements our previous review on important biomolecules, i.e. proteins, and presents a comprehensive database of Raman spectra of naturally occurring lipids. Copyright © 2014 John Wiley & Sons, Ltd.     

Solid state C NMR analysis of human gallstones from cancer and benign gall bladder diseases

Natural abundance ¹³C cross polarized (CP) magic angle spinning (MAS) nuclear magnetic resonance (NMR) analysis of human gall bladder stones collected from patients suffering from malignant and benign gall bladder disease was carried out which revealed different polymorphs of cholesterol in these stones. All gall bladder stones in present study had cholesterol as their main constituent. ¹³C CP-MAS NMR analysis revealed three forms of cholesterol molecules in these stones, which are anhydrous form, monohydrate crystalline with amorphous form and monohydrate crystalline form. Our study revealed that stones collected from patients associated with chronic cholecystitis (CC) disease have mostly different polymorph of cholesterol than stones collected from patients associated with gall bladder cancer (GBC). Such study will be helpful in understanding the mechanism of formation of gallstones which are associated with different gall bladder diseases. This is the first study by solid state NMR revealing different crystal polymorphism of cholesterol in human gallstones, extending the applicability of ¹³C CP-MAS NMR technique for the routine study of gallstones.     

Identification of cholesterol gallstones using in vitro low-fluence laser-induced fluorescence spectroscopic analysis

Identifying the chemical composition of gallstones may be important in certain cases of calculus biliary disease when planning a dissolution therapy or a fragmentation of the calculi using pulsed lasers. The present study was conducted in vitro to evaluate the feasibility of distinguishing cholesterol gallstones from pigment stones. We propose an identification method in which the stone fluorescence spectrum, induced by a low fluence laser, is recorded using an optical multichannel analyser. Fluorescence spectra of twenty-two stones were recorded together with the fluorescence spectra of various pure compounds likely to compose the gallstones, using successively four different pump lasers (_p=308 nm, 337 nm, 423 nm, 469 nm). The fluorescence spectra of cholesterol gallstones are quite different from the pigment ones. Ratios of fluorescence intensities taken at three different wavelengths enable one to distinguish easily between cholesterol and pigment stones.     

人体胆结石成分及无机元素的分析探讨

本文运用三种仪器对胆结石中无机元素含量和成分进行测定,对照标准谱图分析.四个样品的主要成分均为胆固醇,含有较多的元素依次为Ca、Na、P、K和Mg.通过所得结果对胆固醇的成因、无机元素含量变化的作用进行了讨论.     

胆红素—氟化钡体系固相研磨反应的红外光谱研究

本文利用红外光谱法对胆红素－氟化钡体系的固相研磨反应进行了研究。结果表明，该固相研磨反应具有氧参加的自由基反应机制，并且反应产物中胆红素与钡离子的络合形式五液相反应合成的胆红素钡络合物不同。     

Surface-enhanced Raman scattering and theoretical study of the bilichromes biliverdin and bilirubin

The surface-enhanced Raman scattering spectra of biliverdin and bilirubin were obtained and analyzed; a physical silver ligand interaction was inferred. The structural conformation of biliverdin is practically the same when passing from the dry to solution relative to that observed in Raman solid. However, the surface effect induces a different molecular orientation on the surface in dry and in solution. The conformational structure of bilirubin is modified when passing from dry to solution conditions; the orientation of the analyte on the surface is different in both media. The carboxylate groups interact with the surface more closely in bilirubin than in biliverdin. The unsaturated methine bridge in biliverdin confers an additional stability by delocalizing the π-electronic cloud. Both sides of the molecule could be in the same plane. On contrary, bilirubin with a tetrahedric carbon (methylene bridge) confers the whole system a rather free rotation of each side of the whole molecule. Theoretical model calculations of the biliverdin and bilirubin onto the silver surface predict a nearly coplanar orientation of the whole molecules and non-bonded interaction.     

金属离子Zn^2＋,Cd^2＋对胆红素,胆绿素表面增强拉曼光谱的影响

为了研究胆红素（ＢＲ）在体内的新陈代谢以及生物功能与分子结构间的关系，Ｍｏｒｒｉｓ等报道了胆红素的激光拉曼光谱研究，但关于胆红素金属离子（锌、镉）络合物的拉曼光谱至今未见报道，本文研究了金属离子（锌，镉）与胆红素，胆绿素（ＢＶ）的表面增强拉曼光谱，对金属离子半径，电子结构，形成络合物的杂化方式进行了讨论，得出了Ｚｎ＾＋Ｃｄ＾２＋络合物的构型。     

New insights in the activation of human cholesterol esterase to design potent anti-cholesterol drugs

Primary hypercholesterolemia is the root cause for major health issues like coronary heart disease and atherosclerosis. Regulating plasma cholesterol level, which is the product of biosynthesis as well as dietary intake, has become one of the major therapeutic strategies to effectively control these diseases. Human cholesterol esterase (hCEase) is an interesting target involved in the regulation of plasma cholesterol level and thus inhibition of this enzyme is highly effective in the treatment of hypercholesterolemia. This study was designed to understand the activation mechanism that enables the enzyme to accommodate long chain fatty acids and to identify the structural elements for the successful catalysis. Primarily the activation efficiencies of three different bile salts were studied and compared using molecular dynamics simulations. Based on the conformations of major surface loops, hydrogen bond interactions, and distance analyses, taurocholate was concluded as the preferred activator of the enzyme. Furthermore, the importance of two bile salt binding sites (proximal and remote) and the crucial role of $7\upalpha $ -OH group of the bile salts in the activation of hCEase was examined and evidenced. The results of our study explain the structural insights of the activation mechanism and show the key features of the bile salts responsible for the enzyme activation which are very useful in hypolipidemic drug designing strategies.     

胆红素铬合物的表面增强拉曼光谱研究

本文通过对近红外激发傅里叶变换拉曼光谱（ＮＩＲ－ＦＴ－Ｒａｍａｎ）与表面增强拉曼散射（Ｓｕｒｆａｃｅ Ｅｎｈａｎｃｅｄ Ｒａｍａｎ Ｓｃａｔｔｅｒｉｎｇ,ＳＥＲＳ）技术的联用,没得胆红素及其络合物Ｎａ２ＢＲ,ＣａＢＲ与ＣｕＢＲ在银溶胶中的ＳＥＲＳ光谱。结果表明,这一类与胆结石密切相关的生物分子络合物具有不同的配位方式,且在银胶表面采取不同的吸附取向,并从配位化学角度初步解释了黑色结石的黑色成因。     

原位低温拉曼光谱技术在储层流体包裹体分析中的应用

准确获取流体包裹体中盐的类型一直是包裹体研究的重要问题。采用原位低温拉曼光谱技术对民丰洼陷深部天然气储层流体包裹体进行了分析。常温拉曼光谱综合分析表明,包裹体中流体为含甲烷的盐水溶液。在—180℃下对包裹体进行了原位低温拉曼光谱分析,结果显示包裹体中含有NaCl,CaCl_2,MgCl_2等盐类,其中以NaCl为主,CaCl_2含量很少,MgCl_2含量极少。根据沉积成岩过程分析了包裹体中流体的成因,解释了储层成岩作用的机理。研究结果表明,原位低温拉曼光谱是获取储层包裹体中流体性质的一种有效方法。在包裹体原位低温拉曼光谱分析技术基础上,结合沉积成岩过程,可以给储层的成岩作用类型和成岩反应机理给出重要证据。     

饱和一元醇类分子拉曼光谱振动峰的归属研究

选用B3LYP/6-31G(d)优化并计算了31种饱和一元醇类分子的拉曼光谱,以甲醇为例,考察了理论计算结果的准确性,分析了碳原子数小于7的直链饱和一元醇拉曼光谱振动峰的归属。研究结果显示,B3LYP/6-31G(d)用于饱和一元醇类分子拉曼光谱振动的模拟计算较为准确,通过饱和一元醇拉曼光谱振动峰归属分析,确认C—O伸缩振动引起的振动峰可作为饱和一元醇类分子拉曼光谱的特征峰;进一步研究还发现,饱和一元醇类分子拉曼光谱的特征峰与其极化率、热力学、能量等主要参数具有显著的相关性(sig.为0.015),为同系物的拉曼光谱研究提供了一定的参考价值。     

胆石病人胆汁的光谱及稳定性分析

采用红外光谱及二阶导数谱、紫外光谱、动态激光光散射粒度分析、Zeta电位等测试与分析方法,对胆石病人的原胆汁及经离心处理后的胆汁进行了分析。结果表明,胆石病人的胆汁是一个非均匀体系, 处于相对不稳定状态;离心后的胆汁聚沉物主要含有胆固醇、胆红素及其钙盐、蛋白、磷脂等物质,与该病人胆石核心的主要成分非常相似。胆汁中磷脂类囊泡的破坏以及一些难溶性钙盐的生成是影响胆汁稳定性及胆石形成的主要因素。磷脂和蛋白等有机基质在该病人结石的成核过程中可能起诱导和调控作用。