An Integrated Theory of Adsorption and Partition Mechanism and Eash Contribution to Solute Retention in Reversed Phase Liquid Chromatography

With the combination of the the stoichiometric displacement model for retention (SDM-R) in reversed phase liquid chromatography (RPLC) and the stoichiometric displacement model for adsorption (SDM-A) in physical chemistry,the total number of moles of the re-solvated methanol of stationary phase side.nr,and that of solute side in the mobile phase,q,corresponding the one mole of the desorbing solute,were separately determined and referred as the characterization parameters of the contributions of the adsorption mechanism and partition mechanism to the solute retention,respectively.A chromatographic system of insulin,using mobile phase consisting of the pseudo-homologue of alcohols(methanol,ethanol and 2-propanol)-water and trifluoroacetic acid was employed.The maximum number of the methanol layers on the stationary phase surface was found to be 10.6,only 3 of which being valid in usual RPLC,traditionally referred as a volume process in partition mechanism.However,it still follows the SDM-R.Both of q and nr of insulin were found not to be zero,indicating that the retention mechanism of insulin is a mixed mode of partition mechanism and adsorption mechanism.When methanol is used as the organic modifier,the ratio of q/nr was 1.13,indicating the contribution to insulin retention due to partition mechanism being a bit greater than that due to adsorption mechanism.A linear relationship between q,or nr and the carbon number of the pseudo-homologue in the mobile phase was also found.As a methodology for investigating the retention mechanism retention and behavior of biopolymers.a homologue of organic solvents as the organic modifier in mobile phase has also been explored.     

Synthesis and Characterization of a Novel Copoly(aryl ether ketone) Containing 4,4′-Biphenyl-bis[4-phthalazin-1(2H)-one] moiety

A new monomer of 4,4′-biphenyl-bis[4-phthalazin-1(2H)-one] was synthesized from biphenly and phthalic anhydride,and a novel copoly(aryl ether ketone)(PPEK) was synthesized from 2,2-bis(4-hydroxyphenyl)-propane(BPA),4,4′-biphenyl-bis-[4-phthalazin-1(2H)pne],4,4′-difluorodiphenylketone(DFK).The monomer and copolymer were characterized by FT-IR and ^1H-NMR.DSC and TGA were used to the novel polymer.     

Novel Stereoselective Synthesis of (E)- α，β-Unsaturated Esters by the Tandem Reaction of Deprotonation-Oxidation-Wittig Reaction from Phosphonium and Arsonium Salt

Phosphonium or arsonium salt 1 can undergo the tandem reaction of deprotonation -oxidation-Wittig reaction with alcohol 2 in the presence of sodium hydroxide and manganese dioxide,which affords a general simplified method for the stereoselective synthesis of (E)- α-β-unsaturated esters 3.     

Studies on Structure and Porperties of Water Soluble Polysaccharide from Fruiting Body of Cordyceps Militarvs(L.) Link

A water soluble crude polysaccharide has been isolated from the fruiting body of cultivated Cordyceps militarvs(L.)Link.The GC analysis indicated that it contained the monosaccharides of Gal,Man,Glc and GlcA.Their molar ratio is 1.00:1.58:7.89:0.19.The crude polysaccharide was fractionated with ethanol to get three fractions,which were CM-Ⅰand CM-Ⅲ,CM-Ⅱ was further purified to get one homogeneous fraction named CMB.The molecular weight was estimated to be 6000by means of gel filtration.CMB is a greyish white powder.The GC analysis indicated that it was composed of Gal.Man,Glc and the molar ratio is 1.00:1.38:5.10.Partial hydrolysis with an acid.periodate oxidation.Smith degradation.IR,GC and methylation analyses,GC/MS analyses were used for the structure analyses of CMB.Man,(1→6)-linked-Glc,(1→4)-linked-Glc and (1→4)-linked-Gal.Some of (1→4) -linked-Glc and all(1→4)-linked-Gal residues are substituted at 3-O and 6-O respectively,(1→4)-linked-Glc and minor(1→6)-linked-Gle.The nonreduced end is composed of Gal and Glc.The main glycosidic link of CMB is α configuration.     

农药甲霜林对映体的高效液相色谱分离及手性拆分热力学研究

以正己烷/异丙醇为流动相，在纤维素-三（3，5-二甲基苯基氨基甲酸酯）（CDMPC）涂敷型手性固定相上，对农药甲霜灵外消旋体进行了拆分，考察了流动相组成、柱温等对甲霜灵对映体的保留和分离的影响；对甲霜灵R、S对映体与固定相之间的保留和分离的热力学机理进行了讨论。     

Bis（ortho—）chelated Monoanionic Bisphosphinoaryl Ruthenium（Ⅱ）Complexes：Synthesis,Characterization and Reactivity

Bisphosphinoaryl ruthenium(Ⅱ）compounds are synthesized using two distinct synthetic routes.One route,direct cycloruthenation,consists of the reaction of the parent arene compound R-PCHP with [RuCl2(PPh3)3]in chlorinated solvents.However,this route suffers from major drawbacks because HCl is formed as well as free triphenylphoshine.The other route,the transcyclometalation reaction,involves the interconversion of one cyclometalated ligand metal complex,[RuCl(NCN)(PPh3)],into another complex,[RuCl(R-PCP)(PPh3)],with concomitant consumption and formation of the corresponding arenes R-PCHP and NCHN,respectively.     

微波消解试样催化极谱法测定香茹和黑木耳中痕量锗

采用双层聚四氟乙烯密闭容器，以HNO3-HClO4为溶解试剂，CaO为外层吸附剂，微波消解香菇及黑木耳试样。在草酸介质中，当有少量高氨酸存在时，锗（Ⅳ）-苏木精-钒（Ⅳ）体系可产生一灵敏的吸附催化波，峰电位在-0.59V(vs.SCE)处。锗浓度在0ng-300ng/25mL范围内与峰电流呈良好的线性关系，检出限为4.5ng/25mL,适宜于香菇和黑木耳中痕量锗的测定。     

4种喹诺酮类药物滤纸基质室温Lin光法研究

提出了以滤纸为基质的环丙沙星、氟罗沙星、洛美沙星和氧氟沙星4种喹诺酮类药物的滤纸基质室温Lin光（PS-RTP)分析的新方法。方法取样量少（1．5μL).其线性动力学范围依次为0．11－55．2、0．35－211、2．10－526、1．03－411（ng/斑点）；灵敏度高，其检出限分别为0．082、0．070、0．080、0．123（ng/斑点）；标准回收率在97．70％－102．2％之间。相对标准偏差RSD＜1．8％。