水溶性凝胶色谱测定碱木素和硫酸盐木素的相对分子质量分布

用凝胶色谱测定碱木素和硫酸盐木素相对分子质量分布,多在聚苯乙烯凝胶柱上,以四氢呋喃淋洗.因这两种木素在四氢呋喃中溶解度很小,故需经乙酰化处理.该过程会使木素相对分子质量发生变化,且较为繁琐.本文在Ultrahydrogel柱上用水溶性流动相淋洗,测定了桉木碱木素和桦木硫酸盐木素及其改性产物的相对分子质量及其分布.鉴于水溶性凝胶色谱中存在明显的非体积排除效应,本文探讨了影响测定结果的因素,并将测定结果与传统方法进行了比较.     

测定木素磺酸盐和磺化碱木素相对分子质量分布的凝胶色谱法

用水溶性流动相在Ultrahydrogel柱上测定了木素磺酸盐和磺化碱木素的相对分子质量及其分布。流动相的离子强度和 pH值对样品和标样的保留时间和峰面积都有显著的影响。根据色谱峰的位置、峰面积和样品的分离程度 ,确定以 pH=7.0的0.1mol/LNaNO3 溶液为适宜的流动相。     

麦草碱木素及其热化学降解产物相对分子质量分布的测定

以pH=10的0．1mol/L NaNO3溶液为流动相，在Ultrahydrogel柱上测定麦草碱木素及其热化学降解产物的相对分子质量分布，测定碱木素降解产物所用洗脱液宜用pH10的0．1mol/LNaNO3水溶液，比较了由于样品结构特性和物理性质差异而造成的流动行为的差异，并确定两种样品各自的色谱条件。     

高效液相色谱法测定辣椒中的辣椒碱和二氢辣椒碱

建立了高效液相色谱法(HPLC)测定辣椒中辣椒碱、二氢辣椒碱的检测方法.实验考察了仪器条件、不同流动相体系、流动相配比、柱温、流速等因素对分离的影响.确定了最佳色谱条件为ZORBAX SB-C18色谱柱(250mm×4.6 mm,5μm);二极管阵列检测器,辣椒碱、二氢辣椒碱的最佳检测波长为280 nm;色谱柱温度为2...     

高效液相色谱法测定五味子和含五味子的制剂中五味子乙素及多种活性成分时流动相体系的选择

建立了用高效液相色谱法测定五味子和含五味子的制剂中五味子乙素的流动相体系。用Shim-pack VP-ODS (250 mm×4.6 mm,5 μm)色谱柱,在柱温30 ℃、检测波长285 nm、流速1.0 mL/min的条件下,用不同的流动相组成及其不同比例研究了五味子提取液中3种木脂素(五味子乙素、安五脂素和五味子甲素)的保留时间及其分离情况,从中选择测定五味子乙素的最佳流动相体系。结果表明,在甲醇-水、甲醇-冰醋酸-水的流动相体系中,安五脂素和五味子乙素很难完全分离;而在乙腈-甲醇-水和乙腈-冰醋酸-水流动相体系中,3种木脂素可很好地分离。以乙腈-甲醇-水(体积比为17:58:25)为流动相测定五味子和护肝片中3种木脂素的含量,相对标准偏差(n4)为0.95%～5.8%,平均加标回收率为94.50%～105.6%。将该流动相体系用于供试品中3种木脂素含量的测定,分离效果好,结果令人满意。     

凝胶渗透色谱对二次催化溶胶-凝胶法制备硅胶微球过程的监控

采用凝胶渗透色谱法(GPC),通过对二次催化溶胶-凝胶法制备硅胶微球原料硅酸乙酯 40(TES40)、中间产物聚硅酸乙酯(PES)分子量的在线测定,实现了对反应过程的监控.采用Shodex KF-802凝胶色谱柱,以四氢呋喃为流动相,流速0.5 mL/min,柱温40 ℃,采用示差折光检测器检测.校正曲线为1gMw= ...     

4，4'-（-3，3'二甲基）联苯二胺（o-Tolidine）作紫外探针试剂的间接光度色谱法研究(I)—o-Tolidine在反相色谱柱上的吸附性能

]用甲醇-水缓冲溶液作流动相,测定紫外探针试剂o-Tolidine在反相（ODS）柱上的吸附等温线。Freundlich吸附等温方程能解释探针试剂在ODS上的吸附。分别得到了在不同流动相条件下o-Tolidine的吸附等温方程。流动相的组成如流动相的PH值、甲醇含量以及有机添加剂的性质和浓度均影响o-Tolidine在柱上的吸附。o-Tolidine在反相色谱柱上的吸附量与间接光度色谱中的溶质保留和检测响应有一定的关系。     

4,4′-(-3,3′-二甲基)联苯二胺(o-Tolidine)作紫外探针试剂的间接光度色谱法研究(Ⅰ)——o-Tolidine在反相色谱柱上的吸附性能

用甲醇-水缓冲溶液作流动相,测定紫外探针试剂o-Tolidine在反相(ODS)柱上的吸附等温线。Freundlich吸附等温方程能解释探针试剂在ODS上的吸附。分别得到了在不同流动相条件下o-Tolidine的吸附等温方程。流动相的组成如流动相的pH值、甲醇含量以及有机添加剂的性质和浓度均影响o-Tolidine在柱上的吸附。o-Tolidine在反相色谱柱上的吸附量与间接光度色谱中的溶质保留和检测响应有一定的关系。     

4，4''-（-3，3''二甲基）联苯二胺（o-Tolidine）作紫外探针试剂的间接光度色谱法研究(I)—o-Tolidine在反相色谱柱上的吸附性能

]用甲醇-水缓冲溶液作流动相，测定紫外探针试剂o-Tolidine在反相（ODS）柱上的吸附等温线。Freundlich吸附等温方程能解释探针试剂在ODS上的吸附。分别得到了在不同流动相条件下o-Tolidine的吸附等温方程。流动相的组成如流动相的PH值、甲醇含量以及有机添加剂的性质和浓度均影响o-Tolidine在柱上的吸附。o-Tolidine在反相色谱柱上的吸附量与间接光度色谱中的溶质保留和检测响应有一定的关系。     

色氨酸在TOYOPEARL HW-40S 凝胶填料上非理想排阻行为的研究

在发现１８种氨基酸特别是色氨酸在ＴＯＹＯＰＥＡＲＬＨＷ－４０Ｓ树脂所填色谱柱上表现出非理想排阻行为的基础上,以色氨酸在ＨＷ柱上的保留时间为指标,探讨不同的流动相改良剂对ＨＷ凝胶与色氨酸之间相互作用的影响,从而阐明这种反常行为是疏水、离子交换以及氢键三者综合作用的结果,而疏水作用是最主要的影响因素。实验结果说明流动相组成对ＨＷ凝胶色谱行为有明显的影响作用,这不但有助于确立ＨＷ凝胶理想的排阻色谱条件,而且为利用其所具有的吸附性能分离分析肽类和氨基酸等小分子物质奠定了基础。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

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.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.     

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%).     

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.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.