高效液相色谱法制备人胆汁中结合胆红素

 针对单结合胆红素（ｍｏｎｏｃｏｎｊｕｇａｔｅｄｂｉｌｉｒｕｂｉｎ，ＭＣＢ）理化性质极不稳定而造成对其分析、制备的困难性，在Ｓｐｉｖａｋ和Ｔｒｏｔｍａｎ方法的基础上建立了一个简单可行的人胆汁结合胆红素（ｃｏｎｊｕｇａｔｅｄｂｉｌｉｒｕｂｉｎ，ＣＢ）高效液相色谱（ＨＰＬＣ）二次洗脱的制备方法，并对方法的可靠性作了论证，得到了ＭＣＢ较为满意的量与纯度，为进一步探讨ＭＣＢ的理化性质及其与胆石形成的关系提供了条件。     

致孔剂对HP（MA—VAc—MMA）载体孔结构的影响

以二乙烯苯和双丙烯酸多缩乙二醇酯为交联剂、聚醋酸乙烯酯（ＰＶＡｃ）或它与醋酸丁酯（ＢＡＣ）的混合物为致孔剂、ＢＰＯ为引发剂，用悬浮聚合随后水解的方法制得了部分水解聚（丙烯酸甲酯－醋酸乙烯酯－甲基丙烯酸甲酯）［ＨＰ（ＭＡ－ＶＡｃ－ＭＭＡ）］多孔载体，研究了ＰＶＡｃ及（ＰＶＡｃ＋ＢＡＣ）用量、分子量及混合比对ＨＰ（ＭＡ－ＶＡｃ－ＭＭＡ）孔结构的影响。结果表明，当ＰＶＡｃ的Ｍ＞２．５×１０５，ＰＶＡｃ／ＢＡＣ为２．３，用量为１０～２０％时，可制得孔隙率较高，孔径分布较窄，孔表面积较大的多孔载体。这种载体适用于微生物固定化。     

CMC d－p π Bond in Solid State（Ⅱ） Band Structure and Metallic Properties in Incommensurate Misfit Layer Compounds（MS）_xTS_2（M＝Sn，Pb and La；T＝V，Nb，Ta and Cr）

ＣＭＣｄ－ｐπＢｏｎｄｉｎＳｏｌｉｄＳｔａｔｅ（Ⅱ）ＢａｎｄＳｔｒｕｃｔｕｒｅａｎｄＭｅｔａｌｌｉｃＰｒｏｐｅｒｔｉｅｓｉｎＩｎｃｏｍｍｅｎｓｕｒａｔｅＭｉｓｆｉｔＬａｙｅｒＣｏｍｐｏｕｎｄｓ（ＭＳ）_ｘＴＳ_２（Ｍ＝Ｓｎ，ＰｂａｎｄＬａ；Ｔ＝Ｖ，Ｎｂ...     

三卤代锡钨（钼）双核化合物的制备和晶体结构

ＣｐＭ（ＣＯ）３ＳｎＰｈ３和ＣｐＭ（ｃｏ）３ｓＮｐＨ２ｘ（Ｃｐ＝Ｃ５Ｈ４ＣＨ３，Ｃ５Ｈ４ＣＯＣＨ３；Ｍ＝Ｍｏ，Ｗ；Ｘ＝Ｃｌ，Ｂｒ）与ＨＣｌ或ＨＢｒ发生取代反应，得到三氯、三溴以及混合三卤代锡钨（钼）双核化合物，并经元素分析、＾１Ｈ ＮＭＲ、ＩＲ表征。化合物Ｃｌ３ＳｎＷ（ＣＯ）３Ｃ５Ｈ４ＣＯＣＨ３的晶体属单斜晶系，空间群为Ｐ２１／ｃ，ａ＝０．７６８６（３）ｎｍ，ｂ＝１．２６２２（２）ｎｍ，ｃ＝１．６     

含手性膦配体2-MBPA铂(Ⅱ)配合物的2DNMR

利用一维和二维ＮＭＲ技术,对含有手性膦配体的铂配合物ｃｉｓ－〔Ｐｔ（２－ＭＢＰＡＨ）２Ｃｌ２〕（１）,ｔｒａｎｓ－〔Ｐｔ（２－ＭＢＰＡＨ）２Ｃｌ２〕（２）,ｃｉｓ－〔Ｐｔ（２－ＭＢＰＡ）２〕（３）和ｃｉｓ－〔Ｐｔ（２－ＭＢＰＡ）（２－ＭＢＰＡＨ）Ｃｌ〕（４）进行１Ｈ和１３ＣＮＭＲ谱分析,区分了化合物（３）和（４）,归属了糖苷部分的１Ｈ和１３ＣＮＭＲ谱线,并根据磷和铂及磷与磷的偶合常数确定化合物（３）和（４）是顺式构型     

Crystal Structure and Molecular Structure of Binuclear Copper（Ⅱ）Complex，［Cu（C_5H_5NO）（C_6H_5COO）_2］_2

ＣｒｙｓｔａｌＳｔｒｕｃｔｕｒｅａｎｄＭｏｌｅｃｕｌａｒＳｔｒｕｃｔｕｒｅｏｆＢｉｎｕｃｌｅａｒＣｏｐｐｅｒ（Ⅱ）Ｃｏｍｐｌｅｘ，［Ｃｕ（Ｃ_５Ｈ_５ＮＯ）（Ｃ_６Ｈ_５ＣＯＯ）_２］_２￥ＹａｎｇＲｕｉ－Ｎａ；ＨｏｕＹｉ－Ｍｉｎ；ＸｕｅＢａｏ－Ｙｕ；Ｊｉ...     

金属基上以YSZ为过渡层的YBCO薄膜的微观结构

采用透射电子显微术（ＴＥＭ），研究了用磁控溅射技术在柔性金属基体上制备的、钇稳定的ＺｒＯ２（ＹＳＺ）为过镀层的ＹＢａ２Ｃｕ３Ｏ７－ｙ（ＹＢＣＯ）薄膜的横断面结构。所得ＹＢＣＯ膜的超导临界转变温度Ｔｃ为９１Ｋ，临界电流密度Ｊｃ＝２×１０３Ａ／ｃｍ２（７７Ｋ，０Ｔ）。基体为Ｎｉ基合金（ＨａｓｔｅｌｏｙＣ）。ＹＳＺ层为致密、均匀的细晶组织，约１２μｍ厚，具有织构取向，并与基体紧密连接。ＹＢＣＯ层的厚度不均匀，约５００ｎｍ；ＹＢＣＯ／ＹＳＺ界面有时连接较差，在该界面上有杂质出现，杂质有可能引发裂纹。     

单核铁配合物与过氧酸反应的研究

本文用波谱及高压液相色谱（ＨＰＬＣ）方法研究了二氯代三－２－吡啶甲基胺的铁（Ⅲ）配合物（ＦｅＴＰＡＣｌ＿２ＣｌＯ＿４），三─６─甲基─２─吡啶甲基胺合铁（Ⅱ）与苯甲酸的配合物（Ｆｅ（Ⅱ）ＴＬＡＯＢｚＣｌＯ＿４）同单过氧化邻苯二甲酸六水合镁盐（ｍｏｎｏｐｅｒｏｘｙｐｈｔｈａｌｉｃａｃｉｄ，ｍａｇｎｅｓｉｕｍｓａｌｔｈｅｘａｈｙｄｒａｔｅ，即ＭＰＰＡ）的反应。提出了过氧键的两种断裂（即均裂和异裂）机理，分析了中心离子价态、配体结构等因素对反应机理的影响；并通过ＦｅＴＰＡＣｌ＿２ＣｌＯ＿４与间氯代过氧代苯甲酸（ｍｃＰＢＡ）的反应，研究了过氧酸结构对反应机理的影响。实验结果表明：就过氧酸中过氧键发生均裂的程度而言：三价铁配合物与过氧酸的反应＞二价铁配合物与过氧酸的反应；ＭＰＰＡ反应体系＞ＭＣＰＢＡ反应体系。     

Crystal Structure and Spectrum Properties of a Manganese Complex with Schiff Base Ligand，Mn（bzacen）（pyrimidine）（NCS）

ＣｒｙｓｔａｌＳｔｒｕｃｔｕｒｅａｎｄＳｐｅｃｔｒｕｍＰｒｏｐｅｒｔｉｅｓｏｆａＭａｎｇａｎｅｓｅＣｏｍｐｌｅｘｗｉｔｈＳｃｈｉｆｆＢａｓｅＬｉｇａｎｄ，Ｍｎ（ｂｚａｃｅｎ）（ｐｙｒｉｍｉｄｉｎｅ）（ＮＣＳ）￥ＦｅｎｇＹｕｎ－Ｌｏｎｇ；ＬｉｕＳｈｉ－...     

乳液共聚反应过程与聚合物结构关系及~（13）C－NMR对聚合物结构的表征

用间歇法和半连续法进行了丙烯酸丁酯（ＢｕＡ）与醋酸乙烯酯（ＶＡｃ）乳液共聚合．１３Ｃ－ＮＭＲ对共聚产物分子结构测试表明，在间歇法共聚合中随着反应进行其组成及结构发生很大变化，而半连续法确能制得成份及结构均匀一致的Ｐ（ＢｕＡ－ＶＡｃ）共聚物．由于ＢｕＡ水溶性小于ＶＡｃ，而其竟聚率远大于ＶＡｃ，间歇法共聚合反应初期只有少量ＶＡｃ参加共聚合．通过对间歇法共聚合中不同反应时间聚合物的１３Ｃ－ＮＭＲ测试，表明反应初期聚合的ＶＡｃ以单链节或二元序列形式存在于主要由ＢｕＡ单元构成的分子链中，而并未形成较长ＶＡｃ链段．对上述试样玻璃化转变温度的测试结果与１３Ｃ－ＮＭＲ实验结果颇为一致．     

Progress in the study on the composition and formation mechanism of gallstone

Our serial studies from 1970s on chemical composition, structure determination and formation mechanism of gallstones were reviewed. The chemical component investigation of brown-pigment gallstone demonstrated that it consists of macromolecules such as proteins, glyco-proteins, polysaccharides, bilirubin polymers and pigment polymers, and biomolecules such as cholesterol, bile salts, calcium salts of carbonate, phosphate, fatty acids and bilirubinate as well as various metal ions. The binding of metal ions with bile salts and bilirubin plays important roles in gallstone formation, i.e., calcium bilirubinate complex is the major constitute of brown-pigment gallstones, and copper bilirubinate complex is critical in the black color appearance of black-pigment gallstone. The cross section of many gallstones exhibits a concentric ring structure composed of various small particles with a fractal character. This is nonlinear phenomenon in gallstone formation. A typical model system of metal ions-deoxycholate (or cho     

游离胆红素与固体碳酸钙的相互作用

应用红外光谱的方法研究了溶液中游离胆红素与固体碳酸钙的相互作用,探讨了色素型胆结石的形成机理.研究结果表明,溶液中游离的胆红素可以与固体碳酸钙作用,游离胆红素通过与固体碳酸钙表面的钙作用生成难溶性的胆红素钙络合物.牛磺胆酸钠、胆酸钠和脱氧胆酸钠的加入能阻止游离胆红素与碳酸钙的作用,其中加入牛磺胆酸钠后,游离胆红素几乎不与碳酸钙作用.     

Determination of Methanol Increment in Mobile Phase Consisting of Methanol and Water by On—line UV Spectrometry in Reversed Phase Liquid Chromatography

ＩｎｔｒｏｄｕｃｔｉｏｎＦｒｏｎｔａｌｃｈｒｏｍａｔｏｇｒａｐｈｙ (ＦＣ) ,ａｎｏｌｄｂｒａｎｃｈｉｎｌｉｑｕｉｄｃｈｒｏｍａｔｏｇｒａｐｈｙ (ＬＣ) ,1ｈａｓｂｅｅｎｓｕｃｃｅｓｓｆｕｌｌｙｅｍ ｐｌｏｙｅｄｉｎｔｈｅｓｏｌｕｔｉｏｎｏｆｍａｎｙｔｈｅｏｒｅｔｉｃａｌａｓｗｅｌｌａｓａｐ ｐｌｉｅｄｐｒｏｂｌｅｍｓ—ｓｕｃｈａｓｍｅａｓｕｒｉｎｇｂｉｎｄｉｎｇｃｏｎｓｔａｎｔｂｅ ｔｗｅｅｎｃｏｍｐｏｎｅｎｔｓ2 ａｎｄｋｉｎｅｔｉｃｐａｒａｍｅｔｅｒｓｏｆｃｈｅｍｉｃａｌｒｅａｃｔｉｏｎｓ ,3 ａｄｓ…     

High-performance liquid chromatographic method for the direct determination of 4-methylumbelliferone and its glucuronide and sulfate conjugates. Application to studies in the single-pass in situ perfused rat intestine-liver preparation

A direct high-performance liquid chromatographic (HPLC) assay was developed for the separation and determination of 4-methylumbelliferone (4MU) and its glucuronide (MUG) and sulfate (MUS) conjugates in the cell-free perfusate ("plasma") from in situ perfused rat intestine-liver preparation. In addition, a procedure was developed to extract and determine 4MU in the whole blood perfusate. Perfusate plasma containing an internal standard (umbelliferone) was precipitated with methanol (1:4, v/v), and injected into a reversed-phase HPLC system with gradient elution. 4MU and the same internal standard were also extracted directly from the whole blood perfusate with ethyl acetate and injected into a reversed-phase HPLC system with isocratic elution. Inter- and intra-day precision studies (n = 5 for each) for both the plasma and whole blood procedures demonstrated relative standard deviation of less than 10% at all concentrations studied. The compounds were stable in either the plasma or blood extracts at room temperature for up to 72 h. The procedures were successfully used to analyze perfusate samples obtained from the single-pass in situ perfusion of rat intestine-liver system with either trace (0.95 nM) or 32.3 microM concentrations of 4MU. The intestine was responsible for the formation of most of the MUG formed by the intestine-liver preparation during steady-state perfusion with either input concentration of 4MU.     

Excimer and Exciplex Formation in Gold(I) Complexes Preconditioned by Aurophilic Interactions

Excimers and exciplexes are defined as assemblies of atoms or molecules A / A ′ where interatomic/intermolecular bonding appears only in excited states such as [ A ₂]* (for excimers) and [ AA ′]* (for exciplexes). Their formation has become widely known because of their role in gas‐phase laser technologies, but their significance in general chemistry terms has been given little attention. Recent investigations in gold chemistry have opened up a new field of excimer and exciplex chemistry that relies largely on the preorganization of gold(I) compounds (electronic configuration Au^I(5d¹⁰)) through aurophilic contacts. In the corresponding excimers, a new type of Au???Au bonding arises, with bond energies and lengths approaching those of ground‐state Au?Au bonds between metal atoms in the Au⁰(5d¹⁰6s¹) and Au^II(5d⁹) configurations. Excimer formation gives rise to a broad range of photophysical effects, for which some of the relaxation dynamics have recently been clarified. Excimers have also been shown to play an important role in photoredox binuclear gold catalysis.     

Gallstone formation analysis using the particle appearance,the particle binding to calcium ions,and the cholesterol nucleation with time in supersaturated taurocholate–lecithin–calcium ion solutions

We conducted a time-dependent study of cholesterol (Ch) nucleation to investigate the effect of calcium ions in the moderate supersaturated bile. In taurocholate/lecithin (TC/L) bile at a TC to L ratio of 5.1, the presence of calcium ions enhanced the nucleation rate of Ch. Contrarily, we observed the delayed nucleation of Ch after ~30 days in TC/L bile at a ratio of 2.0, regardless of the calcium ions. From the physical chemistry standpoint, the cholesterol activity (ChA_T) is believed to be the driving force for Ch nucleation together with the sufficient nucleation sites. Hence, the micellar formation models along with the binding of TC monomers to calcium ions interpreted the time-dependent results. Furthermore, a quasielastic light–scattering technique detected the formation of micelles and vesicles. In conclusion, the presence of calcium ions in TC/L bile at a high ratio enhances the vesicle appearance for nucleation sites and the high ChA_T values for fast nucleation rate of Ch. However, an increase in the L concentration (i.e., low ratio bile) plays a significant role in the prevention of Ch gallstone formation, compared to the decrease in calcium ion concentration.     

Synthesis and metabolism of the first thia-bilirubin

A symmetrical C(10)-thiabilirubin analogue, 8,12-bis(2-carboxyethyl)-2,3,17,18-tetraethyl-7,13-dimethyl-10-thia-(21H,23H,24H)-bilin-1,19-dione (1), was synthesized from 8-(2-carboxyethyl)-2,3-diethyl-7-methyl-10H-dipyrrin-1-one in one step by reaction with sulfur dichloride. The thia-rubin exhibited the expected IR, UV-vis, and NMR spectroscopic properties, which are rather similar to those of mesobilirubin-XIIIalpha. Like bilirubin and mesobilirubin, 1 adopts an intramolecularly hydrogen-bonded conformation, shaped like a ridge-tile but with a steeper pitch. The longer C-S bond lengths and smaller bond angles at C-S-C, as compared to C-CH(2)-C, lead to an interplanar angle between the two dipyrrinones of only 74 degrees -or considerably less than that of bilirubin (approximately 100 degrees). On normal- and reversed-phase chromatography, 1 is substantially less polar than bilirubin. Despite this conformational distortion, 1 is metabolized in normal rats to acyl glucuronides, which are secreted into bile. In mutant (Gunn) rats lacking bilirubin glucuronosyl transferase, 1 (like bilirubin) was not excreted in bile.     

二价金属离子对磷脂聚集体的影响

通过浊度分析和激光光散射光谱研究了二价金属离子（Ca2＋、Cu2＋和Mn2＋）对蛋黄卵磷脂(EYPC)聚集态的影响.结果表明，自由的二价金属离子对EYPC囊泡有破坏作用,并使EYPC囊泡发生相转变,形成胶束;而与牛磺胆酸钠(TC)结合的二价金属离子使EYPC囊泡半径减小,但不破坏EYPC囊泡.     

High-performance liquid chromatographic separation of bilirubin conjugates: the effects of change in molarity and pH

A fast, sensitive high-performance liquid chromatographic method has been developed for the separation and quantitation of biliary bile pigments; this utilizes a C18 reversed-phase column with two solvents, a buffer and an organic solvent, which were changed in a linear gradient from a polar to a less polar combination. Nine glycosidic conjugates of bilirubin as well as unconjugated bilirubin and a suitable internal standard, unconjugated mesobilirubin IX alpha, were all separated to baseline by gradient elution; the species eluted in a polar to less polar fashion. Increasing the molarity of the solvent decreased the binding of non-glucuronide pigments to the column, with a decrease in their retention times, whereas for bilirubin monoglucuronide they increased. Decrease in pH, similarly, preferentially increased bilirubin monoglucuronide retention times.     

Protective effects of various Chinese traditional medicines against experimental cholestasis

In a previous paper, we reported that methanol extracts obtained from 13 Chinese traditional medicines showed remarkable choleretic effects in normal rats. This paper examines the protective effects against experimental cholestasis induced by carbon tetrachloride (CCl4) or alpha-naphthylisothiocyanate (ANIT) in rats. No medicines, including sodium dehydrocholate and 1-phenylpropanol which are used clinically as choleretic drugs, inhibited the decrease of bile flow induced by CCl4. On the other hand, Intinko-to, Saiko-seikan-to and Bohu-tusyo-san revealed marked improvement of the dysfunction in bile secretion induced by ANIT. These three medicines inhibited the decrease of excretion of bile acid or bilirubin in the bile. They also exerted a protective effect against the alterations of serum components induced by ANIT, i.e., of glutamic oxaloacetic transaminase, glutamic pyruvic transaminase, alkaline phosphatase and the concentration of serum bilirubin. These results indicate that methanol extracts of Intinko-to, Saiko-seikan-to and Bohu-tusyo-san demonstrate not only choleretic effects but also improvement of cholestasis and liver parenchymal injury in rats.