Polyurethanes made from bile acids

New polyurethanes based on bile acids were synthesized from alcohol derivatives of cholic and lithocholic acids and hexamethylene diisocyanate, in an effort to improve the biocompatibility and biodegradability of polyurethanes through the use of natural compounds. The hydrogen bonding in the polymers is confirmed by IR spectral analysis. The glass transition temperatures of the polymers are in the range of 82-138 ℃ and degradation temperatures in the range of 267-298 ℃ as studied by thermal analyses. Thermogravimetric studies indicate that the comonomers are of equimolar amounts in the polyurethanes derived from both bile acids.     

1,2-Dibromoethane and KI mediated α-acyloxylation of ketones with carboxylic acids

The 1,2-dibromoethane-and Kl-mediatedα-acyloxylation of ketones is reported in moderate to good yield without the use of transition metals and strong oxidants.Various acids are well tolerated with wide functional group compatibility.An 1,2-dibromoethane-and Kl-catalysed reaction mechanism is proposed based on the results of control experiments.     

Asymmetric syntheses of α-amino acids via double chiral induction in alkylation of the ketimine derived from 2-hydroxypinan-3-one and menthyl glycinate

Asymmetric syntheses of (S)-α-amino acids in 28--98% optical yields via doublechiral induction in alkylations of ketimine 1 derived from (+)-2-hydroxypinan-3-one and (-)-men-thyl glycinate which is a chiral match pair have been studied. The factors controlling the diastereoselec-tivities in alkylation reactions of the ketimine, the properties of alkylating agents and various alkylationconditions are examined.     

Oxidative Rearrangement via Oxycerication with Ce(IV) Salt

α-Arylpropanoic acids are pharmaceutically interesting compounds, some of them exhibit anti-flammatory and analgestic activities1. Even the enormous progress made in the synthesis of α-arylpropanoic acids by 1,2-aryl rearrangement of arylpropanone using thalium (III) nitrate1,2, silver (I) compounds,3,4 lead (IV) acetate5,6 and iodinate7 during the last decades. The route is, however, unsuitable for the preparation of pharmaceutical products (Naproxen, Ibuprofen and so on) because of the …     

α-氨基酸在水-乙醇中羧基质子化热力学

Enthalpy changes for the protonation of carboxyl group of four α-amino acids(glycine,L-α-alanine,L-valine and L-serine) were measured in water-ethanol mixtures (10－ 70wt％) at 298.15K using LKB-2277 Bioactivity Monitor.The corresponding entropy and Gibbs energy changes were also calculated.The results show that both enthalpy changes and entropy changes are favorable to the protonation of carboxyl groups of the investigated amino acids in water-ethanol mixtures.However,the influence of the composition of ethanol in the mixed solvents on the enthalpy change and entropy changes is complicated.Both sδ and sδ ,the differences of enthalpy changes and entropy changes in mixed solvents and in pure water respectively,show a minimum approximately at xEtOH=0.1.The effects of side chains on the enthalpy change and entropy changes were also investigated using the proton transfer process between glycine and the other three amino acids.The results demonstrate that the proton transfer processes for alanine and valine are spontaneous but not for serine,which could be interpreted in terms of the electrostatic interaction between amino group and carboxyl group within the molecule and the interaction between carboxyl group and the solvent.     

THE SYNTHESIS OF PROTECTIVE FRAGMENTS OF α-HUMAN ATRIAL NATRIURETIC POLYPEPTIDE (α-hANP)

In this paper the synthesis of α-human atrial natriuretic polypeptide fragments (positions, 1-4, 5-10, 11-16, 17-22, 23-28) by solution method is reported. In the synthesis of some peptides, the re-sults from mixed anhydride procedure and active ester procedure are compared. In the synthesis of otherpeptides, the effects of reaction temperature, basicity of catalyst, and reaction time on the specific rota-tions and yields of these compounds are observed. The sequence of amino acids of all the protective poly-peptides is confirmed by FAB-MS.     

Ab initio studies on the pyrolysis mechanism of 2-haloacetic acids in the gas phase

The dehydrohalogenation mechanism of 2-haloacetic acids (XCH2CO2H, X=F, Cl and Br) has been studied theoretically by HF/3-21G and AM1 methods. The results indicate that these reactions are most probably proceeded in terms of a polar five-membered cyclic transition state in the gas phase. Their microscopic processes are beleived to be a stepwise reaction and the rate-determining step is the first one. By comparing the energy barriers of different 2-haloacetic acids, it can be realized that 2-fluoroacetic acid is easier to react than 2-chloroacetic and 2-bromoacetic acids.     

SIMULTANEOUS DETERMINATION OF MULTICOMPONENT IN MIXED ACIDS BY MATHEMATICAL METHOD

A new method for the determination of components in mixed acids has beendeveloped.The mathematical model is obtained from samples of known composition and isthen used to predict the concentrations of components in unknown sample.The practicalutility of this method is demonstrated for simultaneous determination of two systems ofternary mixed acids and the results are satisfactory.     

Determination of D- and L-amino acids in biological samples by two-dimensional column liquid chromatography

Summary A two-dimensional, column liquid chromatographic system is used for the determination of the D- and L-enantiomers of amino acids in biological samples. Separation of the amino acids is first on ion-exchange column by gradient elution with a sodium citrate-sodium chloride buffer. Enantioseparation is by subsequent injection of 3 μl heart-cuts of the individual amino acids onto a second column with a chiral crown ether stationary phase. Finally, fluorescence detection is after post-column labelling of the amino acids using ano-phthalaldehyde-2-mercaptoethanol reagent solution. The high separation power and selectivity of the system allow processing of complex samples with hardly any additional treatment and the determination of small quantities of D-amino acids in the presence of excess L-form. Applicability of the system is illustrated by the determination of D- and L-aspartate, serine, glutamate and alanine in various complex biological samples, such as protein hydrolysates, urine and biotechnological and food samples. Data are given on detectability, repeatability and linearity.     

FAST ATOM BOMBARDMENT MASS SPECTROMETRY OF BILE ACIDS AND THEIR SUCCINYL DERIVATIVES

The new technique of fast atom bombardment mass spectrometry has.been applied to the investigation of some free bile acids and their succinyl derivatives using glycerol or thioglycbl as "matrix compatible solvent".The pseudomoiecular species are observed giving molecular weight information.In negative ion mass spectra the(M-1)-ion is the most intense ion which is the base peak for each of the samples.Additionally,dimer ions and adduct ions with species which are from the matrix are obtained with low intensity.The technique allows the determination of the mixture of bile acids and the pseudomoiecular species observed to give molecular weight information for the component.     

A Convenient Synthetic Method of Metal Dendritic Porphyrins

Metal porphyrins are natural antioxidant reagent1-3. However, due to the characteristics of structures, they are only soluble in inorganic acids and part of polar organic solvents. Thus, it is limited to be used as effective pharmaceutical preparations. T…     

DIMENSIONS OF ATACTIC POLY(α-METHYLSTYRENE) CHAINS WITH SIDE GROUPS

An improved configurational-confomational statistical method is developed and the mean-square radius of gyration for atactic poly(α-methylstyrene)(PαMS) chains is studied, in which the effect of large side groups is considered. The deduced formulas, based on the rotational isomer state theory, are used to investigate the configuration-dependent properties of the atactic polymer chain, and the statistical correlation of the unperturbed polymer chain dimension and structure parameters are calculated. For the fraction of meso dyads wm= 0.4, the dependence of the radius of gyration Rg and the intrinsic viscosity [η] on the molecule mass M are Rg = 2.63 × 10-2M0.50 nm and [η] = 7.36 × 10-2M0.497, respectively, which are in agreement with the previous experimental data for the PαMS samples. A small hump is detected in the curve of the characteristic ratio of the unperturbed mean-square radius of gyration versus the chain length for short PαMS chains. The Rg increases linearly with the temperature T, and the effects of the chain length and the tacticity on the temperature coefficient are remarkable. These are quite different from the results for PαMS chains not considering side groups or for the monosubstituted polystyrene chain.     

STUDY ON ADSORPTION OF HUMIC AND PHYIC ACIDS USING RESINS

1. INTRODUCTION
Humic acid （HA） and Phytic acid （PA） are present in environment as a result of the decomposition of plant biomass, they are the major components of natural dissolved organic matter （DOM） in natural systems. It is now generally believed that these potentially carcinogenic chlorinated hydrocarbons such as THMs can be formed in the presence of these acids during the disinfection, which can cause liver, kidney or central nervous system problems . In order to reduce the formation of THMs, it is necessary to remove these substances as much as possible prior to chlorination. The aim of the present paper is tO Study the adsorption of HA and PA using different resins. Furthermore, the effect of HA molecular weight （MW） on adsorption are performed, and the adsorption of HA on different non-polar resins are investigated to elucidate the relationship between resin pore diameter and critical molecular size of HA adsorbed. Finally, the capacity of the bi-function resin WJN-10 to adsorb these acids in the presence of Pb（ II ） is investigated.     

Nucleic acids analysis

Nucleic acids are natural biopolymers of nucleotides that store, encode, transmit and express genetic information, which play central roles in diverse cellular events and diseases in living things. The analysis of nucleic acids and nucleic acids-based analysis have been widely applied in biological studies, clinical diagnosis, environmental analysis, food safety and forensic analysis.During the past decades, the field of nucleic acids analysis has been rapidly advancing with many technological breakthroughs.In this review, we focus on the methods developed for analyzing nucleic acids, nucleic acids-based analysis, device for nucleic acids analysis, and applications of nucleic acids analysis. The representative strategies for the development of new nucleic acids analysis in this field are summarized, and key advantages and possible limitations are discussed. Finally, a brief perspective on existing challenges and further research development is provided.     

Rapid Determination of Amino Acids in Ginseng by High Performance Liquid Chromatography and Chemometric Resolution

Ginseng is one of the most important traditional Chinese medicines and functional foods.A method for the fast determination of amino acids in ginseng samples using high performance liquid chromatography（HPLC） was developed,in which strong isocratic elution was employed for simplifying the separation and speeding up the analysis.All amino acids were eluted within 3 min with the chromatogram composed of overlapped peaks from the interferences.Then,non-negative immune algorithm（NNIA） was adopted to resolve the chromatographic signals of the components from the chromatogram measured.The results show that the signals of the amino acids can be correctly extracted by NNIA and the signal extracted can be used for the quantitative analysis.The method was validated via determining six amino acids of four different samples of ginseng.The recoveries of the spiked samples are in a range of 96.6％-106.3％.     

ASYMMETRIC SYNTHESIS——ENANTIOSELECTIVE SYNTHESIS OF (R)-α-AMINO ACIDS USING L-ISOLEUCINE AS CHIRAL AUXILIARY REAGENT

Enantioselective synthesis of (R)-α-amino acids via heterocyclic intermediate-(3S)-2,5-dimethoxy-3-see-butyl-3, 6-dihydropyrazine (5), using L-isoleucine as chiral auxiliaryreagent and glycine as raw meterial, has been studied. The alkylation of compound 5 withbutyllithium affords its lithium derivative (6) according to the cardanion mechanism. Then 6reacts with alkyl halide RX (7) to give the alkylated products (8) with very high diastereo-selectivity. In this reaction, the group R of 7 enters trans to the see-butyl group at C-3, i. e.the (R)-configuration is induced at C-6 of 8. After hydrolysis the (R)-α-amino acid methylesters (9) are obtained.     

DIMENSIONS OF ATACTIC POLY（α-METHYLSTYRENE） CHAINS WITH SIDE GROUPS

An improved configurational-confomational statistical method is developed and the mean-square radius of gyration for atactic poly(α-methylstyrene)(PαMS)chains is studied,in which the effect of large side groups is considered. The deduced formulas,based on the rotational isomer state theory,are used to investigate the configuration-dependent properties of the atactic polymer chain,and the statistical correlation of the unperturbed polymer chain dimension and structure parameters are calculated.For the fraction of meso dyads w_m=0.4,the dependence of the radius of gyration R_g and the intrinsic viscosity[η]on the molecule mass M are R_g=2.63×10~(-2) M~(0.50) nm and[η]=7.36×10~(-2) M~(0.497),respectively, which are in agreement with the previous experimental data for the PαMS samples.A small hump is detected in the curve of the characteristic ratio of the unperturbed mean-square radius of gyration versus the chain length for short PαMS chains.The R_g increases linearly with the temperature T,and the effects of the chain length and the tacticity on the temperature coefficient are remarkable.These are quite different from the results for PαMS chains not considering side groups or for the monosubstituted polystyrene chain.     

Organic Reactions in Ionic Liquids： An Efficient Method for the Synthesis of Phenacyl Esters by Reaction of Carboxylic Acids with α-Bromoacetophenone Promoted by Potassium Fluoride

An efficient method is reported for the synthesis of phenacyl esters by reaction of carboxylic acids with a-bromoacetophenone promoted by potassium fluoride in ionic liquid [Bmim]PF6, the yield of the reaction is almost quantitative and the products are essentially pure.     

Resonance Rayleigh scattering spectral characteristics of interaction of nucleic acids with some cationic surfactants and their analytical applications

In near neutral medium, the resonance Rayleigh scattering (RRS) intensities of an alone cationic surfactant and nucleic acid are very weak. However, when they combine with each other to form a complex, the RRS intensity of the solution is enhanced greatly. In this paper the reactions of five cationic surfactants with nucleic acids have been studied. The results show that the reaction conditions and RRS spectral characteristics of these reactions are similar, but their sensitivities are obviously different. Among them, the sensitivity of cetyldimethyl benzylammonium chloride (CDBAC) with an aryl and large molecular weight is the highest, while that of cetyl-trimethylammonium bromide (CTAB) without aryl and with small molecular weight is the lowest. The detection limits for ctDNA and yRNA of the former are 6.6 and 29.4 ng · mL-1, while that of the latter are 13.3 and 53.6 ng · mL-1. The method has better selectivity and can be applied to the determination of trace amounts of nucleic acids. Furthermore, i     

Investigation of side chain liquid crystal polymers bearing cholesterol and bile acid derivatives

Cholic acid (or 3α,7α,12α-trihydoxyl-5β-cholan-24-oic acid) and lithocholic acid (or 3α-hydroxyl-5β-cholanic-24-oic acid) are commonly occurring bile acids synthesized from cholesterol in the liver in mammals. They all possess a steroid skeleton containing four rings, three with six carbons and one with five carbons. The transformation of cholesterol to cholic acid results in two major structural changes that affect the steroid skeleton. The first is the hydrogenation of the double bond …