Synthesis of Amino Acid Derived β-Cyclodextrins Used in Chiral Separation by Capillary Electrophoresis

Six new kinds of amino acid derived β-cyclodextrins were synthesized to improve their water solubility and chiral separation properties. They are heptakis {2,6-di-O-[3-L-(1-isopropyl carboxyl methyl amino)-2-hydroxy propyl]}-β-cyclodextrin (i.e. L-Val-β-CD), heptakis {2,6-di-O-[3-L-(1-benzyl carboxyl methyl amino)-2-hydroxy propyl]}-β-cyclodextrin (i.e. L-Phe-β-CD), heptakis{2,6-di-O-[3-(D, L-1-benzyl carboxyl methyl amino)-2-hydroxy propyl]}-β-cyclodextrin (i.e. D,L-Phe-β-CD), heptakis {2,6-di-O-[3-(L-1-hydrox-ymethyl carboxyl methyl amino)-2-hydroxy propyl]}-β-cyclodextrin (i.e. L-Ser-β-CD), heptakis{2,6-di-O-[3-(L-1-carboxylmethyl carboxyl methyl amino)-2-hydroxy propyl]}-β-cyclodextrin (i.e. L-Asp-β-CD), heptakis{2,6-di-O-[3-(L-2-carboxyl tetramethylene amino)-2-hydroxy propyl]}-β-cyclodextrin (i.e. L-Pro-β-CD).Their chemical structures were certified using FTIR and ^1H NMR. Except for L-Phe-β-CD and D,L-Phe-β-CD,that are in soluble in water, the other amino acid derived β-CDs all have good water solubility. D,L-tyrosine and promethazine were baselinely separated by L-Val-β-CD in capillary electrophoresis.     

Synthesis of ino Acid Derived β-Cyclodextrins Used in Chiral Separation by Capillary Electrophoresis

Six new kinds of ino acid derived β-cyclodextrins were synthesized to improve their water solubility and chiral separation properties. They are heptakis{2,6-di-O-[3-L-(1-isopropyl carboxyl methyl ino)-2-hydroxy propyl]}-β-cyclodextrin (i.e. L-Val-β-CD), heptakis{2,6-di-O-[3-L-(1-benzyl carboxyl methyl ino)-2-hydroxy propyl]}-β-cyclodextrin (i.e. L-Phe-β-CD), heptakis{2,6-di-O-[3-(D, L-1-benzyl carboxyl methyl ino)-2-hydroxy propyl]}-β-cyclodextrin (i.e. D,L-Phe-β-CD), heptakis{2,6-di-O-[3-(L-1-hydroxymethyl carboxyl methyl ino)-2-hydroxy propyl]}-β-cyclodextrin (i.e. L-Ser-β-CD), heptakis{2,6-di-O-[3-(L-1-carboxylmethyl carboxyl methyl ino)- 2-hydroxy propyl]}-β-cyclodextrin (i.e. L-Asp-β-CD), heptakis{2,6-di-O-[3-(L-2-carboxyl tetrethylene ino)-2-hydroxy propyl]}-β-cyclodextrin (i.e. L-Pro-β-CD). Their chemical structures were certified using FTIR and 1H NMR. Except for L-Phe-β-CD and D,L-Phe-β-CD, that are in soluble in water, the other ino acid derived β-CDs all have good water solubility. D,L-tyrosine and promethazine were baselinely separated by L-Val-β-CD in capillary electrophoresis.     

Template synthesis and adsorption properties of chitosan salicylal Schiff bases

To improve the adsorption properties of chemically modified chitosan, the chelating resin of salicylal chitosan Schiff bases was prepared by the template cross-linking method using Cu(Ⅱ) as template ion and ethylene glycol bisglycidyl ether as cross-linking agent in microwave, and was characterized by IR. The adsorption capacity and selectivity coefficient of the chemically modified chitosan for Cu(Ⅱ), Fe(Ⅲ) and Zn(Ⅱ) were investigated, respectively. The results show that the adsorption capacity of the resin 2.73 mmol/g for Cu(Ⅱ) is bigger than that for other two metal ions, 0.22 mmol/g for Fe(Ⅲ), and 0.42 mmol/g for Zn(Ⅱ), and the selectivity coefficients are as follows: KCu(Ⅱ)/Fe(Ⅲ)=12.4, KCu(Ⅱ)/Zn(Ⅱ)=6.5.     

Enantioselective extraction of clorprenaline enantiomers with hydrophilic selector of sulfobutylether-β-cyclodextrin by experimentand modeling简

Enantioselective extraction of hydrophobic clorprenaline （CPE） enantiomers from organic phase to aqueous phases with sulfobutylether-β-cyclodextrin （SBE-β-CD） as the selector was investigated with insight into a number of important process variables, such as the type of organic solvent, concentration of selector, pH, and temperature. Equilibrium of the extraction system was modeled using a reactive extraction modcl with a homogeneous aqueous phase reaction. The important parameters of this model were determined experimentally. The physical distribution coefficients for molecular and ionic CPE were determined as 0.3 and 8.93, respectively. The equilibrium constants of the complexation reaction with SBE-β-CD were determined as 152 and 110 L/mol for R- and S-CPE, respectively. Results show that the experimental data agree with the model predictions perfectly. Comprehensively considering the experiment and model, the extraction conditions are optimized and the best extraction conditions are： pH of 6.0, SBE-β-CD concentration of 0.04 tool/L, and temperature of 5 ℃, providing the enantioselectivity （a） of 1.25, the fraction of R-CPE （φR） in aqueous phase of 0.71 and performance factor （pf） of 0.025.     

Systematically structural identification of nitriccompounds in crude oil with chemometric resolution

Aimed at the problem of classification of non-hydrocarbons of crude oil, the theoretical standpoint that the polarity of a compound depends on the whole structure and composition of molecule instead of a kind of heteroatom or its functional group was presented. A method was established for the systematically structural identification of nitric compounds in crude oil. The pre-fractionation of a crude oil sample into 7 fractions was performed by diadsorption column chromatography with neutral aluminum oxide and silica gel. Subsequently, the individual components were obtained by using capillary column gas chromatography, and the types of compounds were detected by a mass spectrometer. In combination with a chemometric resolution, the compounds of fraction were further identified. This method can relieve the difficulty of classical analysis in identifying those species with very low contents or without being completely separated. The structures of 168 nitric compounds in a crude oil sample were determined by this method.     

Phase and Rietveld Refinement of Pyrochlore Gd_2Zr_2O_7 Used for Immobilization of Pu(Ⅳ)

The phase of pyrochlore Gd2Zr2O7 used for immobilization of Pu(Ⅳ) was investigated, tetravalent cerium was used as the simulacrum for plutonium with tetravalence, and the compounds in the system Gd2Zr2-x Ce x O7(0.0 x 2.0) were synthesized via a high temperature solid reaction method with Gd2O3 and ZrO2 powders being used as the starting materials. Based on the collected XRD data of the gained samples, the phase and microstructural change of compounds were calculated by means of rietveld structural refinement method. The experimental results indicated that the phases of compounds were changed from pyrochlore to fluorite-type phase with the increasing x. The linear relation between a and x was discovered in the range of fluorite-type phase, which accorded with a = 0.52748 + 0.00825 x(0.2 x 2.0), while V = 0.14668 + 0.00711 x(0.2 x 2.0) was also achieved.     

Rapid and simultaneous determination of ten off-flavor compounds in water by headspace solid phase microextraction and gas chromatography-mass spectrometry

A simple and sensitive analytical procedure for the determination of multi-component compounds in water samples was developed and optimized using the headspace solid-phase microextraction(HSSPME) coupled with gas chromatography-mass spectrometry(GC-MS). Ten off-flavor compounds, including geosmin(GSM), 2-methylisoborneol(2-MIB), 2-isopropyl-3-methoxypyrazine(IPMP), 2-isobutyl-3-methoxypyrazine(IBMP), β-ionone, trans-2,cis-6-nonadienal(NDE), 2,3,4-trichloroanisole(2,3,4-TCA), 2,3,6-trichroloanisole(2,3,6-TCA), 2,4,6-trichloroanisole(2,4,6-TCA), and 2,4,6-tribromoanisole(2,4,6-TBA) were used as the target analytes. The optimization of extraction parameters including fibers types, extraction time, extraction temperature, stirring rate, sample volume, and ionic strength was carried out through the univariate approach. Ten off-flavor compounds were quantified within 50 min under the optimal conditions. Calibration curves with good linearity(r~2=0.990-0.998) were obtained in the range 1.0/2.0-100 ng/L, while the limits of detection for all compounds were lower than or close to the odor threshold concentration. Furthermore, the proposed method was applied to analyzing and determining the off-flavor compounds in real water samples from water-treatment plants.     

Beckmann Rearrangement of Erythromycin A 9（E）－Oxime

9-Deoxo-6-deoxy-6, 9-epoxy-9, 9α-didehydro-9α-aza-9α-homoerythromycin A ( 1 ), 9-deoxo-11-deoxy-9, 11-epoxy-9, 9α-didehydro-9α-aza-9α-homoerythromycin A (2) and 9α-aza-9α-homoerythromycin cyclic lac-tam (3) were synthesized by the Beckmann rearrangement of erythromycin A 9(E )-oxime (4). The structures of compounds (1), (2) and (3) have been identified by their spectral data. The reaction mechanism was also dis-cussed. The yield of the Beckmann rearrangement of compounds (4) was better than that reported in literatures.     

Preparation and Evaluation of Insulin-loaded Nanoparticles based on Hydroxypropyl-β-cyclodextrin Modified Carboxymethyl Chitosan for Oral Delivery

Novel insulin-loaded nanoparticles based on hydroxypropyl-β-cyclodextrin modified carboxymethyl chitosan(CMC-HP-β-CD) were prepared to improve the oral bioavailability of insulin. The CMC-HP-β-CD was characterized by FT-IR spectroscopy and 1H-NMR spectra. The insulin-loaded nanoparticles were prepared through crosslinking with calcium ions, and the morphology and size of the prepared nanoparticles were characterized by transmission electron microscopy(TEM) and dynamic light scattering(DLS). Cumulative release in vitro study was performed respectively in simulated gastric medium fluid(SGF, p H=1.2), simulated intestinal fluid(SIF, p H=6.8) and simulated colonic fluid(SCF, p H=7.4). The encapsulation efficiency of insulin was up to 87.14 ± 4.32% through high-performance liquid chromatography(HPLC). Statistics indicated that only 15% of the encapsulated insulin was released from the CMC-HP-β-CD nanoparticles in 36 h in SGF, and about 50% of the insulin could be released from the nanoparticles in SIF, whereas more than 80% was released in SCF. In addition, the solution containing insulin nanoparticles could effectively reduce the blood glucose level of diabetic mice. The cytotoxicity test showed that the samples had no cytotoxicity. CMC-HP-β-CD nanoparticles are promising candidates as potential carriers in oral insulin delivery systems.     

Oxidation Reactivities of Organic Sulfur Compounds in Fuel Oil Using Immobilized Heteropoly Acid as Catalyst

Heteropoly acid of Keggin structure phosphotungstic(HPW)and phosphomolybdic(HPMo) were chemically anchored to the modified SBA-15 channel.The materials were used as catalyst for oxidative desulfurization of organic sulfur compounds including benzothiophene(BT),dibenzothiophene(DBT)and 4,6-dimethydibenzothiophene(4,6-DMDBT).The experimental results show that the catalysts are efficient and reusable,the catalytic activity is hardly reduced even in the 5th cycle of use.     

Study of oxidization of coal–pitch by O_3

For the purpose of obtaining small molecular and oxygen-containing aromatic compounds,taking a toluene-extracted coal pitch as the research object,the oxidation of coal–pitch by ozone(O_3) in formic acid was studied.The coal–pitch sample and the oxidized pitch residue were characterized by elementary analysis and Fourier transform infrared spectroscopy(FTIR),while the small molecular products were analyzed by a gas chromatography–mass spectrometer(GC–MS).The results show that the highest oxygen content of oxidized coal pitch had been acquired at a reaction temperature of 50 °C,an O_3 flow rate of6300 mg/h and a reaction time of 4 h.Quite a lot of hydroxyls and carbonyls were introduced into the structure of the oxidized coal–pitch,while the small molecules produced mainly involve nonpolar aromatic compounds,aromatic anhydride and quinone compounds.It is speculated that the mechanism is direct electrophilic oxidation in which the molecules of O_3 directly attack the aromatic ring at its carbon atoms with high electron density,and then generate hydroxyl or carbonyl until the aromatic ring cracks.This study shows that O_3 can make the fused aromatic ring of coal–pitch become oxidized and depolymerized,and hence the ozonization of coal–pitch can be a potential method for obtaining oxygencontaining aromatic compounds.     

Sensing characterization of Sn/In/Ti nanocomplex oxides for CO, CH_4 and NO_2

The nanocomplex oxides of Sn-In and Sn-In-Ti were prepared by controlled co-precipitation method as sensing materials of semiconductor gas sensors for detection of CO, CH4 and NO2. Through manipulating the Sn/In cation ratio, metal salt total concentration, precipitation pH value and aging time, the nanocrystalline powders were successfully derived with chemical homogeneity and superior thermal stability, compared with the single component oxides. The particle size and morphology, surface area, and thermal and phase stabilities were characterized using TEM, TG-DTA, BET and XRD. The sensing tests showed that the Sn-In com-posites exhibit high sensitivity and selectivity for CO and NO2. The introduction of TiO2 enhanced CH4 sensitivity and selectivity, particularly, additives of Pd and Al2O3 as a dopant and surface modification greatly enhanced the sensing properties. The sensitivity depended on the composition of composites, calcination temperature and operating temperature. The optimal values were (25%In2O3- 75%SnO2)-20%TiO2 for ternary composite, 600 and 300℃, respectively. Temperature-programmed de-sorption (TPD) studies were employed to explain the gas adsorption behavior dis-played by the surface of nanocomposites and X-ray photoelectron spectroscopic (XPS) analysis was used to confirm the electronic interactions existing between oxide components. The sensing mechanism of the nanocomposites was attributed to chemical and electronic synergistic effects.     

Aerobic oxidation behavior of α-ionone catalyzed by N-hydroxyphthalimide combined with acetylacetone cobalt(Ⅱ)

A practical catalytic method to oxidize α-ionone with molecular oxygen using N-hydroxyphthalimide(NHPI) combined with acetylaeetone cobatt(Ⅱ) (Co(acac)2) was developed, and the probable catalytic mechanism was proposed. The influences of the reaction conditions on conversion of α-ionone and the selectivity of the major product (5-keto-ct-ionone) were investigated, and the technical parameters for 5-keto-α-ionone were optimized. The results show that the primary product is 5-keto-α-ionone, and by-products include epoxy-α-ionone, as well as rearrangement products 4-keto-β-ionone and epoxy-β-ionone, which are characterized by infrared spectra, proton nuclear magnetic resonance spectra, mass spectra and elemental analysis. The selectivity of 5-keto-α-ionone and the conversion of α-ionone are 55.0% and 97.0%, respectively, when 30%(molar fraction) NHPI, 1.0%(molar fraction) Co(acac)2 and no solvent are employed under O2 pressure of 1.0 MPa and the reaction temperature of 65℃ for 11 h. The procedure shows good reproducibility in the parallel experiments.     

Action of Selenium Compounds on the Cellular Metabolism by Microcalorimetry

A new method is introduced to study the action between biomaterials and organism. By using an LKB- 2277 bioactivity monitor and ampoule method, the fundamental thermogenesis curves of the metabolic process of pk-15 and the toxic effect of three kinds of selenomorpholine compounds on it were studied at 37℃. From the thermogenesis curves, the heat released by pk-15 metabolism was calculated. The results show that the selenium compounds all have toxic action on the metabolism process of pk-15 at the range of experimental concentrations. The sequence of the toxic action of selenium compounds is: Na2SeO3>β- ( N- selenomorpholine) -ethyl phenyike-tone hydrochloride > selenomorpholine.     

Room temperature gas sensor based on tube-like hydroxyapatite modified with gold nanoparticles

The main goal of this work is to explore the possibility of using Au-modified hydroxyapatite(HA) as a potential sensor material. Tube-like HA structure was fabricated with the aid of a Nafion N-117 cation exchange membrane and gold(Au) nanoparticles were added by a hydrothermal method. The morphology, structure and composition were characterized by scanning electron microscopy(SEM), transmission electron microscopy(TEM), X-ray diffraction(XRD), and X-ray photoelectron spectroscopy(XPS). The gas sensing properties were also investigated. Results show that Au nanoparticles are dispersed into the HA powder, which is tube-like, with rough inner and outer surfaces. Compared with pure HA, Au-modified HA exhibits improved sensing properties for NH_3. 5%(mass fraction) Au-modified HA shows the highest response with relatively short response/recovery time. The response is up to 79.2% when the corresponding sensor is exposed to 200×10~(-6) NH_3 at room temperature, and the response time and recovery time are 20 s and 25 s, respectively. For lower concentration, like 50×10~(-6), the response is still up to 70.8%. Good selectivity and repeatability are also observed. The sensing mechanism of high response and selectivity for NH_3 gas was also discussed. These results suggest that Au-HA composite is a promising material for NH_3 sensors operating at room temperature.     

Alkylated and silylated β-cyclodextrin for gas chromatographic chiral stationary phases

Three new ehiral stationary phases, 2, 6-di-O-heptyl-3-O-trimethylsilyl-β-cyclodextrin( DHTBCD), 2,6-di-O-pentyl-3-O-trimethylsilyl-β-cyclodextrin (DPTBCD) and 2,6-di-O-butyl-3-O-trimethylsilyl-β-cyclodextrin (DBTBCD), were synthesized. Chromatographie properties sueh as eolumn efficieney, thermal stability and eolumn life span, were studied. The separations of enantiomers, sueh as ketone, esters, alcohols and olefines, were investigated on the alkylated and silylated β-eyelodextrin stationary phases. The influenee of diluent on ehiral separation was studied. The experimental results indieate that the stationary phases show good ehromatographie properties in separating enantiomers. It is observed that inelusion eomplexafion and hydrogen bonding interaction hardly play a role in separating enantiomers.     

Synthesis and adsorption properties for Au(Ⅲ) of alkoxycarbonyl thiourea resin

A novel alkoxycarbonyl thiourea resin(ATR) was synthesized by monomer polymerization of oxydiethane-2,1-diyl dicarbonisothiocyanatidate and polyethylene polyamine, and characterized by FT-IR. The adsorption properties of ATR were investigated by batch test. The adsorption capacities for Au(Ⅲ), Ag(Ⅰ), Cu(Ⅱ), Zn(Ⅱ), Fe(Ⅲ), Ca(Ⅱ) and Mg(Ⅱ) are 4.65, 4.40,0.40, 0.90, 0.86, 0.0080 and 0.016 mmol/g, respectively, when the adsorption condition is as follows: contact time 24 h, temperature 30 ℃, initial concentration of Au(Ⅲ) 5.08 mmol/L and that of other metals 0.10 mol/L, and concentration of acid 1.0 mol/L. The adsorption capacity for Au(Ⅲ) increases with the increase of contact time, temperature and initial concentration of Au(Ⅲ). The capacity after five adsorption-desorption cycles remains 90% that of the first time, and the separation factors of ATR for binary metal ion solutions are larger than 995, indicating that ATR is of good regeneration property and selectivity. XPS results show that the functional atoms of ATR supply electrons for Au and coordinate with Au during the adsorption.     

Determination of constituents of essential oil from Angelica sinensis by gas chromatography-mass spectrometry

Gas chromatography-mass spectrometry （GC-MS） coupled with chemometric resolution upon twodimensional data was employed to analyze the constituents of essential oils of Angelica sinensis. Constituents in essential oils of Angelica sinensis root were identified by GC-MS with the help of subwindow factor analysis （SFA） method resolving two-dimensional original data into mass spectra and chromatograms. 76 of 97 separated constituents in essential oil of Angelica sinensis root were identified and quantified, and they account for about 91.36% of the total content. The results show that ligustilide, butylene phthalide, 2-methoxy-4-vinylphenol, carvacrol, alloocimene, 2,6,6-trimethylbicyclo-[3,1,1] hept-2-ene are the main constituents in essential oil of Angelica sinensis root.     

Computational studies on the structure and detonation properties of nitro-substituted triazole-furazan derivatives

Some nitro-substituted triazole-furazan derivatives are considered as potential candidates for high energy density compounds through quantum chemical treatment. Their geometric and electronic structures, band gap, thermodynamic properties and detonation properties were studied using the density functional theory at the B3LYP/6-311+G^** level. The calculated energy of explosion, density, and detonation properties of model compounds were comparable to 1,3,5-trinitro-1,3,5-triazinane (RDX) and 1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX). The heats of formation and bond dissociation energy were also analysed to understand the nature of thermal stabilities and the trigger bond in the pyrolysis process.     

The Crosslinking Mechanism of Camellia Oleifera Protein Adhesive with Amine Resins by 13C-NMR and ESI-MS

A new protein wood adhesive was studied with Camellia oleifera protein. Formaldehyde and N-(2)-L-Ala-L-Gln(LAG) were used as the model compounds of amino resins and Camellia oleifera protein, aiming to provide scientific foundations for the improvement and applications of Camellia oleifera protein adhesive by the reaction of model compounds. The experimental results demonstrate that, under alkaline conditions, formaldehyde is easier to react with Camellia oleifera protein by quicker reaction and...