Abstract:2-Amino-5-bromo-3-morpholin-4-ylpyrazine was prepared from 2-amidopyrazine in an overall yield of 45.9% via bromination and substitution by morpholine, and its structure was confirmed by 1HNMR. The reaction conditions were optimized for temperature, reactant proportions, and reaction time. The optimized reaction conditions are as follows: n(2-Amidopyrazine):n(Bromine):n(Pyridine)=1:2.1:2.1, react at 40℃，kept in dark place; m(3,5-dibromopyrazin-2-amine):V(Morpholine)=1g:4mL, react at 80℃ for an hour. The improved process has the advantages of mild reaction conditions, simple operation, low cost and it is also suitable for large scale synthesis.

Abstract:Water plugging is an important means for the field to stabilize oil production and to control water cut. Due to the complexity of the formation, the plugging agent needs salt tolerance and washing stability. A swellable type blocking agent was synthesized by copolymerizing using acrylic acid (AA), acrylamide (AM), 2 - acrylamido - 2 - methylpropane sulfonic acid (AMPS), and acryloyloxyethyl trimethyl ammonium chloride (DAC) as monomer, N, N-methylene-bis-acrylamide (MBA) as a cross-linking agent. The effects of reaction conditions on the properties were studied and the optimal synthesis conditions were determined as follow: mass ratio of AA to AM was 4:1, the reaction temperature was 60 ℃, the amount of initiator, cross-linking agent, AMPS, DAC and MBA were 0.5% , 0.05%, 7% and 4% separately. The blocking agent had good salt tolerance and hardly expanded in kerosene. Plugging ability and resistance to scour of the plugging agent were evaluated by core flow tests and the plugging agent plugging rate reached 86.1% and injection pressure decreased slightly, after more than 25 times pore volume subsequent water scouring. The blocking agent had a strong resistance to erosion capacity.

Abstract:In this paper, process improvements of the synthesis of Tenofovir disoproxil fumarate started from (R)-propylene carbonate was optimized. The process improvements were included in simply microwave-assisted acid hydrolysis of phosphonate ester, alkylation promoted with magnesium ethoxide, and iodine methyl isopropyl carbonate as an efficiently esterification reagent. The overall yield of the process of synthesis of Tenofovir disoproxil fumarate was not only improved from 24% to 33.5%, but also the identified process were more environmentally friendly, lower cost, and more suitable for productive and robust production.

Abstract:Thiodiglycolic acid was refluxed with excess methanol or ethanol to obtain dimethyl thiodiglycolate (Ia) or diethyl thiodiglycolate (Ib) using stannous chloride as catalyst. The optimum conditions were SnCl2)=4.0％ and reflux time 3 h, and their yields were 93.5% or 96.4%, respectively. Compound Ia or Ib reacted with glyoxal trimer dehydrate to give thiophene-2, 5-dicarboxylic acid through condensation and hydrolyzation in the presence of potassium hydroxide. The optimal reaction conditions were n (dimethyl thiodiglycolate or diethyl thiodiglycolate) : n (glyoxal trimer dehydrate) : n (potassium hydroxide)＝1: 0.4: 4.4 and reflux time 5 h in cyclohexane. The yields of thiophene-2, 5-dicarboxylic acid were 89.3%~90.0%.

Abstract:Hybrid sol-gel films were deposited on tinplate substrates from sol prepared by hydrolysis and condensation reaction of 3-methacryloxypropyltrimethoxysilane (KH570) and tetraethylorthosilicate (TEOS), followed by radical polymerization with ethylene glycol methacrylate phosphate (EGMP). The influence of the amount of EGMP on performance of the coating was investigated. Fourier transform infrared spectra (FTIR) was applied to characterize sols, scanning electron microscopy (SEM) was used to investigate the morphology of the hybrid coatings, , adhesion tests were used to examine the adhesion of coating the corrosion behavior was investigated using potentiodynamic scan (PDS) and neutral salt spray test (NSST). The results shows that organic-inorganic network has been formed, the surface of coating is dense and smooth, the adhesion degree of coating is 1, the best protection was achieved when the amount of KH570 four times to the molar number of EGMP in the coating.

Abstract:Pyridinium 4-Toluenesulfonate ionic liquid (IL) was synthesized in water by a one-step synthetic method. The ionic liquid was characterized by infrared spectrum (IR), nuclear magnetic resonance spectrum (NMR) and Thermal analysis (TG-DTA). Friedel-Craft acylation of β-Methoxynaphthalene using acetic anhydride as acylation reagent was then studied as a probe reaction. The effect of catalytic activities of the ionic liquid and reaction conditions on the catalytic reaction were researched. The results indicated that, under the optimal reaction conditions, namely nacetic anhydride: nβ-Methoxynaphthalene=1.5:1, mIL : mβ-Methoxynaphthalene= 2.53, reaction temperature at 150°C for 5h, the conversion of β-Methoxynaphthalene was up to 58.88 % and the selectivity towards 2-methoxy-1-acetonaphthone reached to 98.28 %. The ionic liquid could be recycled and reused for several times without significant loss of activity. The product has been separated, purified and confirmed by infrared spectrum, nuclear magnetic resonance spectrum and thermal analysis. Two products of the reaction were identified.

Abstract:Graphene oxide (GO) was modified by polyamide-amine dendrimers (PAMAMs) via a grafting-from method, and then the GO/PAMAMs were characterized by Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA) and transmission electron microscopy (TEM). The effects of the solution pH, the adsorption time, temperature and the initial concentration of Cu(II) adsorption onto GO/PAMAMs were studied. The kinetics and thermodynamics of Cu(II) adsorption were investigated with the Lagergren pseudo-first-order and pseudo-second-order kinetic model, Langmuir and Freundlich isotherm models were applied to simulate the experimental data. The experimental data showed that the adsorption process of Cu(II) onto GO/PAMAMs can be described with the Lagrangian pseudo-second-order kinetics model, indicating the adsorption process is chemisorption mainly. The experimental data of isotherm followed both the Langmuir isotherm model and the Freundlich model, which indicated that the adsorption was monolayer. The thermodynamics parameters of Gibbs free energy change (ΔG), enthalpy changes (ΔH) and entropy change (ΔS) were calculated and found to be positive, indicating that the adsorption of Cu(II) onto GO/PAMAMs was endothermic, non-spontaneous and entropic-adding.

Abstract:The room temperature self-crosslinking emulsions of waterborne fluorinated polyurethane- acrylate(WFPUA)were synthesized using in-situ surfactant-free emulsion爌olymerization爓ith acrylic monomers as the solvent, and the diacetone acrylamide(DAAM) and adipic dihydrazide(ADH) were introduced into the WFPUA emulsions for the cross-linking system. The structure and the physical properties of the WFPUA were investigated by FT-IR, TEM and AFM. Meanwhile, the fluorine content and the impact of the ratio of DAAM and ADH were studied. The results show that，when the fluorine content reached 8%，DAAM:ADH=1:1, the static water angle would reach 110.5?water absorption also are reduced to 8.8%. tensile stress are increased from 18.12MPa to 28.55MPa. Moreover, the results of TG spectra show that the cross-linking system of DAAM and ADH help to improve the thermal stability of the latex film.

Abstract:Several novel Schiff base macrocyclic compounds of Thiotriazinone were synthesized from cyanuric chloride, diethylamine p-nitrophenol, 1,2-dibromoethane, salicylaldehyde, p-hydroxybenzaldehyde, vanillin and isovanillin by high dilution method, and their structures were characterized by IR, 1H NMR and ESI/MS techniques. The studies on the UV-Vis absorption spectroscopies show that Schiff base 5 have a selective recognition for Fe3+.

Abstract:This paper investigates the effects of fumed silica (FS) and precipitated silica (PS) on rheological behaviors of Carbopol gel. The elasticity modulus, yield stress, and thixotropy of Carbopol gel can be improved efficiently with the addition of either FS or PS. When the nanosilica concentration was less than 4%, the particle size is smaller and more uniform for FS-modified gel than PS-modified gel, leading to a more dramatically enforced rheological properties for the former; when the nanosilica concentration was increased from 4% to 8%, PS forms large agglomerates and therefore improves rheological properties. Results of fourier transform infrared spectroscopy (FT-IR) and scanning electron microscope (SEM) show that FS has more hydroxyls on its surface than PS as well as better dispersion in water. Different interaction ways of FS and PS with Carbopol were related to various surface properties.

Abstract:A series of dihydromyrcenol-type trisiloxane surfactants(Sxy) were synthesized by hydrosilylation from 1,1,1,3,5,5,5-Heptamethyltrisiloxane and dihydromyrcenol-polyether catalyzed by Pt-PMVS. The structures of the products were characterized by means of FT-IR and 1H-NMR. We studied their surface and interface properties, compared with the marketing available trisiloxane surfactant BD-3077. The results showed that Sxy could reduce the surface tension of water down to 23 mN/m, a little higher than BD-3077(21 mN/m). The cloud point of S36, S39 and S312 solution(mass fraction 0.5%) were higher than 85 ℃. Sxy showed better stability in hydrolysis resistant experiments than BD-3077.

Abstract:The core-shell latex was synthesized with P(MMA-MAA-BA) as hydrophilic core and P(St-AN-DVB) as hydrophobic hard shell by core-shell emulsion polymerization process, and the covering latex with hollow structure was acquired by post-treatment with alkali. Elements such as MAA acount,core/shell ratio(mass ratio of core monomer and shell monomer, the same below) were traversed which effected hollowness and opacity ability of hollow latex. Structure and morphology of hollow latex particles were characterized by TEM and SEM. The results shown that, when MAA account was 30%(mass fraction) of core monomer and core/shell ratio was 1:6, the latex particles had around 50% hollowness and best opacity ability, and water-based ink therefrom could obtain the best overall performance.

Abstract:5,5-Thiobis-(2-(2-hydroxy -3,5 -di -tert -butylphenyl)-2H-benzotriazole)which have a benzotriazole and a disulfide bond was synthesized from 2-(2-hydroxy-3，5-di-tert-butyl)-5-chloroazimino-benzene and n-butyl mercaptan alkali metal salt，with 1-Methyl-2-pyrrolidinone in the absence of solvent .The structure was characterized by 1HNMR, FTIR, FABMS. The UV spectra were measured,the maximum UV absorption wavelength is 364nm, as compared with the ordinary commercial UV absorber wavelength is 353nm, and it has a very high molar absorptivity, up to 55000 L/(mol挠洀) in the maximum absorption wavelength, which is 2 times than the commercial UV absorber. It can protect plastics, coatings and person's skin from ultraviolet (320～400nm) damage. Has a wide application value.

Abstract:Using 2-acrylamido-2-methyl propane sulfonic acid(AMPS) as organic monomer, attapulgite(APT) and carboxymethylcellulose (CMC) as composite components, novel eco-friendly carboxymethyl cellulose-g-poly(2-acrylamido-2-methyl propane sulfonic acid)/attapulgite (CMC-g-PAMPS/APT) superabsorbent composites were synthesized by means of microwave irradiation. The effects of APT content on swelling rate, water retention and reswelling capability were systematically investigated. The chemical structure and thermal stability of superabsorbent composites were characterized by XRD and TG. The results showed that CMC and APT participated in grafting copolymerization reaction. The reaction occurs only in the APT surface,and monomer is not inserted into the APT interlayer.The swelling rate, water retention and thermal stability and reswelling capability of the superabsorbent composites could be remarkably enhanced by introducing a proper amount of APT.

Abstract:To endow microporous polypropylene membrane (MPPM) antimicrobial capability, a versatile method was developed to quaternize MPPM surface. Firstly, acrylic acid (AA) was grafted on the MPPM surface via UV irradiation, and subsequent chemical binding of polyethyleneimine(PEI) by activation of carbodiimide. Then, the primary and secondary amine groups on macromolecular chains of PEI were tertiary aminated with propylene epoxide. The surface of MPPM was quaternized by the reaction between tertiary amine of PEI and benzyl chloride. Fourier transform infrared spectroscopy (FTIR), x-ray photoelectron spectroscopy (XPS), fluorescein disodium salt coloration and static water contact angle were used to characterize the quaternized membranes. The antibacterial capabilities of the quaternized membranes for E. coli and S. aureus were investigated via plate counting method. The results indicated that the quaternized membranes exhibited strong antimicrobial capability for both E. coli and S. aureus, and antimicrobial capability can be enhanced by increasing the density of positive charge on the surface of quaternized membranes or contact time.

Abstract:Monodispersed silver nanoparticles (Ag NPs) in controllable size were prepared by solution chemical reduction with glucose as the reducing agent and chitosan as the stabilizing agent. The effects of the concentration of reducing agent, stabilizing agent and silver nitrate, temperature, pH value and reaction time etc. on the nucleation and subsequent development of Ag NPs were evaluated by means of ultraviolet-visible spectrophotometry, X-ray diffraction and transmission electron microscopy. Monodispersed silver nanoparticles with diameter of 3? nm、6? nm and 9? nm were obtained respectively as a result.

Abstract:Abstract: The sensing behaviors of a rhodamine derivative RhB-NSal bearing a –NO2 group for Cu2+ in dry acetonitrile and aqueous acetate buffer media were investigated. In each medium, significant absorption and fluorescence enhancements accompanied by an instant color change were observed for RhB-NSal upon addition of Cu2+. RhB-NSal binds with Cu2+ forming a 1:1 stoichiometric complex with an association constant of 6.72 × 104 and 4.23 × 104 L/mol, respectively. RhB-NSal displayed high selectivity for Cu2+ over other ions except that Fe3+ and Bi3+ ions induce a little interference. In dry acetonitrile, Cu2+ results in remarkable spectroscopic enhancements of RhB-NSal with a detection limit of 0.49 μmol/L for Cu2+, exhibiting higher sensitivity than that of an analogue bearing no substituent on its phenol ring. In aqueous solution, RhB-NSal likewise displays a high selectivity but a lower sensitivity for Cu2+ than that in acetonitrile, with a detection limit of 14.98 μmol/L, still more sensitive than RhB-Sal in absorption. By virtue of these properties, RhB-NSal could be used as a promising candidate of an “Off-On” fluorescent and colorimetric chemosensor for Cu2+ in different media.

Abstract:The rheological behaviors of a pH-switchable wormlike micelles system formed by Sodium Oleate/Triethylamine Hydrochloride were investigated by rheology method. Though steady-state and dynamic rheological measurements, it was found that at 30℃, when the pH value is cycled between 8.20 and 9.40,the viscosity of the NaOA(0.12mol稬-1)/ Et3NHCl(0.2mol稬-1) solutions vares without any deterioration to its response more than three times between 3 and 27649 mPa稴,and also its rheological behavior complies with Maxwell model. These pH-stimuli rheological properties were attributed to the effect of pH on the interaction between NaOA and counterions Et3NH . Upon decreasing pH, the micellar surface charge density was decreased due to lowing of counterions Et3NH ionic strength, leading the micelles grow continuously .while upon decreasing pH to 8.64, flocculation occurs due to the attractive interactions between adjacent micelles. However, on increasing pH to 9.40, the micellar structures were destroyed due to counterions Et3NH desorbing from the surface of the wormlike micelles.

Abstract:OBJECTIVE To isolate, purify and identify the structures of related impurities from biotransfomated calcifediol. METHODS After vitamin D3爁ermentation broth was crudely extracted, high-pressure preparative chromatography was adopted to isolate calcifediol repeatedly, acquiring high purity related impurities from calcifediol. When the impurities reached a certain purity, through DAD Scanning, Mass Spectrometry and Nuclear Magnetic Resonance, the structure of chemical compound was identified. RESULTS After purification, 97.5% purity of impurity item was obtained. After structure identification, the impurity is (5Z,7E)-9,10-ring opening 5,7,10(19)-triene-3b,24-diol which means that 24-hydroxy vitamin D3 is the isomer of calcifediol. CONCLUSION The results of this study provide the basis for the establishment of quality standard of biotransfomated calcifediol as active pharmaceutical ingredients. Meanwhile, they also provide impurity reference for subsequent experiental work.

Abstract:Artificial wastewater which contained sulfadiazine (SD) was electrochemically degraded by intermediate products (•OH and active chlorine) with metallic oxide coatings (DSA) as anode, and titanium plate as cathode in an undivided electric tank. The results indicated that: 1) The removal rate of SD was 100 % after 10 minutes treatment, and the TOC concentration significantly decreased after 4 hours; 2) After 4 h treatment, the removal rates of TOC at pH 3, 4, 8, 8.5, 10 and 12 were 29 %, 46 %, 55 %, 61 %, 52 % and 47 %, respectively, the peak of removal rate appeared at 8.5; 3) The removal rate of TOC could be enhanced through increasing the current density and the NaCl concentration, decreasing the initial SD mass concentration. The optimal treatment process was determined as follows: the pH value of 8.5; the NaCl concentration of 0.025 mol•L−1; the current density of 20 mA•cm−2; the initial SD mass concentration of 100 mg/L. The TOC removal rate could be 66% after 4 h treatment under this reaction conditions according to this research.

Abstract:With anthracene as raw material, three novel nucleating agents AMH, AMHD and AGMA of anthracene series compounds were synthesized. Thermal stability of them was individually investigated by using thermogravimetric analysis (TGA). X-ray diffraction (XRD) and polarized light microscopy (PLM) characterized the crystalline morphology of modified isotactic polypropylenes (iPP). The crystallization behavior of iPP was studied with the aid of differential scanning calorimetry (DSC). The mechanical properties of iPP were also tested. The results manifested that AMHD and AGMA could both reinforce nucleation of α-crystalline iPP, while AMH could induce the production of β-iPP. Not only did these three nucleating agents enhance the crystallization temperature (Tc) and crystallinity (Xc) of iPP effectively, but they also improved the mechanical properties of iPP, which the Xc of iPP/AMHD raised by 3.75%. Compared with pure iPP, the impact strength of iPP/PHD increased by 5.60 kJ/m2, while the tensile strength of iPP/AMHD by 18.02%, and the flexural strength of iPP/AMHD was up to 53.22 MPa.

Abstract:In this work, acrylic emulsion was chosen as the shell material to prepare 2,3-epoxy-2-methyl-1,4-naphthoquinone (ME) microcapsules. Transmission electron microscopy (TEM) and nano-particle size analyzer were used to characterize 2,3-epoxy-2-methyl-1,4-naphthoquinone microcapsules. The results showed that the average particle size of ME microcapsules (core-shell mass ratio was 1:7) was 323.5nm, the release rate of ME fom the coating film prepared using it was steady and the antifouling property of the coating film was excellent.

Abstract:Versatile imidazo[1,2-a]pyridine carboxylic acid 1 could be prepared in five steps from commercially available 2-amino pyridine. Alkylation/cyclization with Methyl bromopyruvate, followed by selective chlorination with NCS and tandem Suzuki cross-coupling/hydrolysis, affords cyclopropane 1. The studies on the Suzuki cross-coupling/hydrolysis reaction conditions and catalysts were also carried out.

Abstract:Tert-butyl hydroperoxide and di-tert-butyl peroxide were synthesized by oxidation of tert-butyl alcohol with hydrogen peroxide using 12-phosphotungstic acid as catalyst. The effects of temperature，reaction time，mass of catalyst，dosage ratio of raw materials on the reaction were investigated in the ways of single factor and orthogonal design methods. Under the conditions that the molar ratio of tert-butyl alcohol to hydrogen peroxide is 0.7：1，the molar ratio of tert-butyl alcohol to phosphotungstic acid is 299:1，the reaction temperature at 83℃ and the reaction time with 3 h，the conversion of tert-butyl alcohol could reach to more than 95%，the yield and selectivity of tert-butyl hydroperoxide are 75.9% and 79.6%，respectively.

Abstract:The enantiomerically pure (S)-N,N-dimethyl-1-ferrocenylethylamine was racemized by a free radical process, with the catalyst of thiol and the initiator of azodiisobutyronitrile (AIBN). The effect of reaction conditions on racemization was optimized by experiments. The results showed that (S)-N,N-dimethyl-1-ferrocenylethylamine could be completely racemized under the following reaction conditions: the molar ratio of (S)-N,N-dimethyl-1-ferrocenylethylamine to thiol and AIBN was 1:1.2:0.6, AIBN was added dropwise in 18 h, and the reaction mixture was refluxed in toluene. Besides, the catalyst of a novel crosslinked mercaptopolystyrene resin was synthetized, and the e.e.% of the racemate could be reduced to 12% with tentative research on the catalytic effect.