利用偏酐残渣合成苯多酸酯类增塑剂的高附加值应用研究

本文将偏三甲苯制备偏苯三酸酐产生的偏酐重组分(黑渣)与甲醇经过酯化反应得到一系列甲酯,然后对甲酯进行精馏分离,将得到的二甲酯和三甲酯与2-乙基己醇进行酯交换得到二(2-乙基)己酯和(2-乙基)辛酯。进行分离后获得两种偏苯三甲酸三(2-乙基)己酯和一种均苯三甲酸三(2-乙基)己酯。将两种不同的偏苯三甲酸三(2-乙基)己酯和均苯三甲酸三(2-乙基)己酯以及正常合成的偏苯三甲酸三(2-乙基)己酯与常见增塑剂增塑的PVC薄膜的热稳定性、力学性能和相容性等应用性能进行对比。结果表明,偏苯三甲酸三(2-乙基)己酯和均苯三甲酸三(2-乙基)己酯具有良好的增塑性能和热稳定性。

苯多酸酯类增塑剂的合成

苯多元羧酸酯类增塑剂具有分子量较大、粘度大、闪点高、挥发性低、耐抽出、迁移性小等大分子聚合物类增塑剂的优点，同时也具有单体增塑剂的优点；此外，它还具有聚酯增塑剂的优点，并且相容性、加工性、低温性都好。由于它具有较高的热稳定性，因此，不仅可作为一般的主增塑剂在民用产品使用，而且能用于专用产品。

Catalytically altering the redox pathway of sulfur in propylene carbonate electrolyte using dual-nitrogen/oxygen-containing carbon

Carbonate electrolytes are one of the most desirable electrolytes for high-energy lithium-sulfur batteries(LSBs)because of their successful implementation in commercial Li-ion batteries.The low-polysulfide-solubility feature of some carbonate solvents also makes them very promising for overcoming the shuttle effects of LSBs.However,regular sulfur electrodes experience undesired electrochemical mechanisms in carbonate electrolytes due to side reactions.In this study,we report a catalytic redox mechanism of sulfur in propylene carbonate(PC)electrolyte based on a compari-son study.The catalytic mechanism is characterized by the interactions between polysulfides and dual N/O functional groups on the host carbon,which largely prevents side reactions between polysulfides and the carbonate electrolyte.Such a mechanism coupled with the low-polysulfide-solubility feature leads to stable cycling of LSBs in PC electrolyte.Favorable dual N/O functional groups are identified via a density functional theory study.This work provides an alternative route for enabling LSBs in carbonate electrolytes.

钒矿提制高纯钒系产品及清洁生产技术

传统提钒工艺中最难控制处理的就是氨气排放和废水处理。本工艺从钒矿采矿冶炼开始,直接提取偏钒酸铵NH4VO3及多钒酸铵(NH4)2V6O16,制成高纯五氧化二钒等系列产品,采用多酸酯和无定型白炭黑技术,使废水中的重金属和杂质得到有效处理,确保氨气(NH3)制铵(NH4)返回源头,循环使用,废水实现零排放,循环使用,经应用在原矿和精细加工两个企业分别测试及批量生产,钒系产品纯度达99.5%~99.99%。

Nano-porous Composites Based on Liquid： Synthesis, Characterization, Esterification Heteropolyacid Functionalized Ionic and Catalytic Performance in

Fhnctionalized ionic liquid samples （bmim-PW12） were synthesized by 1-butyl-3-methyl- imidazolium bromide （bmimBr） and 12-phosphotungstic heteropolyacid （PW12）. The samples were annealed at 100-450 ℃ and were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscope, thermal gravity-DTG, brunauer emmett teller, and NHa-temperature programmed desorption. The results showed that the bmim-PW12 samples were crystal and maintained intact Keggin structure. The organic parts of those samples were partly decomposed at a temperature more than 350 ℃. The sample annealed at 400 ℃ exhibited nano-porous structure, strong acidity, and excellent catalytic activity on the esterification of n-butanol with acetic acid. The higher ester yield was obtained when the mass ratio of catalyst over the reactants amount was 5% for bmim-PW12 catalyst annealed at 400 ℃.

Study on Antithrombotic and Antiplatelet Activities of Low Molecular Weight Fucoidan from Laminaria japonica

The antithrombotic and antiplatelet effects of two fucoidan fractions with low molecular weight and different sulfate content from Laminaria japonica were compared in order to examine the influence of chemical character on their antithrombotic activity and the possible mechanism. Both LMW fucoidan fractions exhibited favorable antithrombotic activity in an Fecl3-induced arterial thrombosis. The antithrombotic activity of LMW fucoidan was related with decrease of TXB2 and whole blood viscosity and hematocrit. LMW fucoidan showed a correlation between anticoagulant, antiaggregant and antithrombotic effects in vivo. For LMW fucoidan, antithrombotic activity required high dose of 5-10 nmol kg-1, concomitantly with increase in anticoagulant activity and inhibition of platelet aggregation. Administration of LMW fucoidan significantly promoted the 6-keto-PGF1α content and decreased the TXB2 content, indicating its inhibition of tissue factor pathway and regulation of metabolism of arachidonic acid. By comparison, highly sulfated fucoidan LF2 with Mw 3900 seemed to be a more suitable choice for antithrombotic drug for its antithrombotic activity accompanied with specific inhibitory activity on platelet aggregation, low anticoagulant activity and low hemorrhagic risk in vivo.

Recent advances in fixation of CO_(2) into organic carbamates through multicomponent reaction strategies

Carbon dioxide(CO_(2)) is the main greenhouse gas and also an ideal C1 feedstock in organic synthesis because it is abundant,nontoxic,nonflammable,and renewable.The synthesis of organic carbamates using CO_(2) as a phosgene alternative has attracted extensive attention because of the importance of carbamates in organic synthesis and in the pharmaceutical and agrochemical industries.In recent decades,many multicomponent reaction strategies have been designed for constructing different types of organic carbamate molecules.Most of these methods rely on the in situ generation of carbamate anions from CO_(2) and amines,followed by reactions with other coupling partners.Synthetic strategies for acyclic carbamates include nucleophile‐electrophile coupling,nucleo‐phile‐nucleophile oxidative coupling,difunctionalization of unsaturated hydrocarbons,and C–H bond functionalization.Strategies for the synthesizing cyclic carbamates include carboxylative cyclization of in situ‐generated unsaturated amines and difunctionalization of unsaturated amines with CO_(2) and other electrophilic reagents.This review summarizes the recent advances in the synthesis of organic carbamates from CO_(2) using different multicomponent reaction strategies.Future perspectives and challenges in the incorporation of CO_(2) into carbamates are also presented.

In-vitro anticoagulant activity of fucoidan derivatives from brown seaweed Laminaria japonica

Fucoidan, a group of sulfated heteropolysaccharides, was extracted from Laminaria japonica, an important economic alga species in China. The anticoagulant activity of fucoidan and its derivatives (including sulfated, phosphorylated, and aminated fucoidan) was examined using in-vitro anticoagulant systems. The correlation between chemical variations within the fucoidan group and anticoagulant activity was determined. The in-vitro anticoagulant properties of fucoidan and its derivatives were determined by measuring activated partial thromboplastin time (APTT), prothrombin time (PT), and thrombin time (TT). The results indicate anticoagulant activity in all samples using APTT and TT assays; however, only the fucoidan derivatives affected the PT assay. Thus, the fucoidan derivatives were able to inhibit both intrinsic and extrinsic blood coagulants. Fucoidan (FPS) and its derivatives presented better anticoagulant activity than low molecular weight fucoidan (DFPS) and its derivatives, suggesting that molecular weight and proper conformation are contributing factors for anticoagulant activity of polysaccharides. Amino groups have a positive charge and can thus change the charge density of fucoidan. Accordingly, among the tested samples, aminated fucoidan (NF) was the most active reflecting the importance of charge density for anticoagulant activity. Available data obtained using in-vitro models suggest that the sulfate content, sulfate/total-sugar ratio, molecular weight, and the substituted group of fucoidan are important factors for anticoagulant activity but that the influence of sulfate, phosphate and amino groups on anticoagulant activity was different.

Beneficial effects of fucoidan in patients with chronic hepatitis C virus infection

AIM:To evaluate the effects of fucoidan,a complex sulfated polysaccharide extract from marine seaweed,on hepatitis C virus(HCV) RNA load both in vitro and in vivo.METHODS:HCV-1b replicon-expressing cells were cultured in the presence of fucoidan obtained from Cladosiphon okamuranus Tokida cultivated in Okinawa,Japan,and quantified the level of HCV replication.In an open-label uncontrolled study,15 patients with chronic hepatitis C,and HCV-related cirrhosis and hepatocellular carcinoma were treated with fucoidan(0.83 g/d) for 12 mo.The clinical symptoms,biochemical tests,and HCV RNA levels were assessed before,during,and after treatment.RESULTS:Fucoidan dose-dependently inhibited the expression of HCV replicon.At 8-10 mo of treatment with fucoidan,HCV RNA levels were significantly lower relative to the baseline.The same treatment also tended to lower serum alanine aminotransferase levels,and the latter correlated with HCV RNA levels.However,the improved laboratory tests did not translate into significant clinical improvement.Fucoidan had no serious adverse effects.CONCLUSION:Our findings suggest that fucoidan is safe and useful in the treatment of patients with HCVrelated chronic liver diseases.Further controlled clinical trials are needed to confirm the present findings.

Microanalysis and preliminary pharmacokinetic studies of a sulfated polysaccharide from Laminariajaponica

A rapid, sensitive and reproducible high performance liquid chromatography （HPLC） method with post-column fluorescence derivatization has been developed to determine the amount of low-molecular- weight sulfated polysaccharide （GFS） in vivo. The metabolism of GFS has been shown to fit a two component model following its administration by intravenous injection, and its pharmacokinetic parameters were determined to be as follows： half-time of distribution phase （t1/2α）=11.2±2.93 min, half-time of elimination phase （tl/2α）=98.20±25.78 min, maximum concentration （Cmax）=110.53 gg/mL and peak time （Tmax）=5 min. The pharmacokinetic behavior of GFS was also investigated following intragastric administration. However, the concentration of GFS found in serum was too low for detection, and GFS could only be detected for up to 2 h after intragastric administration （200 mg/kg body weight）. Thus, the bioavailability of GFS was low following intragastric administration because of the metabolism of GFS. In conclusion, HPLC with post-column derivatization could be used for quantitative microanalysis and pharmacokinetic studies to determine the presence of polysaccharides in the serum following intravenous injection.

Green and efficient epoxidation of methyl oleate over hierarchical TS-1

The epoxidation of methyl oleate(MO)was conducted in the presence of aqueous H2O2 as the oxidant and hierarchical TS-1(HTS-1)as the catalyst;the catalyst was synthesized using polyquaternium-6 as the mesopore template.The effects of various parameters,i.e.,H2O2/C=C molar ratio,oxidant concentration,amount of the catalyst,reaction temperature,and time,were systematically studied.Furthermore,response surface methodology(RSM)was used to optimize the conditions to maximize the yield of epoxy MO and to evaluate the significance and interplay of the factors affecting the epoxy MO production.The H2O2/C=C molar ratio and catalyst amount were the determining factors for MO epoxidation,wherein the maximum yield of epoxy MO reached 94.9%over HTS-1 under the optimal conditions.

A novel long-chain acyl-derivative of epigallocatechin-3-O-gallate prepared and purified from green tea polyphenols

Lipophilic tea polyphenols (LTP) were prepared by catalytic esterification of green tea polyphenols (GTP) with hexadecanoyl chloride. A novel long chain acyl derivative of epigallocatechin 3 o gallate (EGCG) was first isolated from purification of LTP by high speed countercurrent chromatography (HSCCC) using a solvent system composed of n hexane ethyl acetate methanol water (1:1:1:1, v/v). The molecular structure of the acyl derivative, Epigallocatechin 3 O gallate 4′ O hexadecanate , was elucidated by means of elemental analysis, IR, 1H NMR and MS spectra.

Chiral BINAP-based hierarchical porous polymers as platforms for efficient heterogeneous asymmetric catalysis

Two vinyl‐functionalized chiral2,2'‐bis(diphenylphosphino)‐1,1'‐binaphthyl(BINAP)ligands,(S)‐4,4'‐divinyl‐BINAP and(S)‐5,5'‐divinyl‐BINAP,were successfully synthesized.Chiral BINAP‐based porous organic polymers(POPs),denoted as4‐BINAP@POPs and5‐BINAP@POPs,were efficiently prepared via the copolymerization of vinyl‐functionalized BINAP with divinyl benzene under solvothermal conditions.Thorough characterization using nuclear magnetic resonance spectroscopy,thermogravimetric analysis,extended X‐ray absorption fine structure analysis,and high‐angle annular dark‐field scanning transmission electron microscopy,we confirmed that chiral BINAP groups were successfully incorporated into the structure of the materials considered to contain hierarchical pores.Ru was introduced as a catalytic species into the POPs using different synthetic routes.Systematic investigation of the resultant chiral Ru/POP catalysts for heterogeneous asymmetric hydrogenation ofβ‐keto esters revealed their excellent chiral inducibility as well as high activity and stability.Our work thereby paves a path towards the use of advanced hierarchical porous polymers as solid chiral platforms for heterogeneous asymmetric catalysis.

Diapause Regulation in the Moth Sesamia nonagrioides （Lepidoptera： Noctuidae）

Insects enter in diapause in response to diverse environmental cues. During diapause, insects arrest their development and many genes are down-regulated while a small number of genes uniquely expressed at this time. This review aims to present available data regarding the regulation of diapause in the moth Sesamia nonagrioides （Lepidoptera： Noctuidae）. Studying the transcriptional regulation of several genes （five heat shock proteins, two storage proteins and one juvenile hormone esterase） showed that these genes may play various roles in the diapause programming. The results show that SnoHsp19.5 gene was consistently expressed, while SnoHsp20.8 was down-regulated in deep diapause and was up-regulated at the termination of diapause. SnoHsc70 may play important roles in assisting protein conformation during specific stages of diapause. SnoHsp83 displays a similar pattern to SnoHsc70 under diapause conditions, when extra larval moults occur, indicating that could be involved in the developmental process that occurs between two moults. Expression of two SnoSP1 and SnoSP2 hexamerin genes was also observed throughout diapause. And the results lead us to the conclusion that larval diapause of S. nonagrioides is associated with continuous synthesis and accumulation of storage proteins. In addition, the transcript level of the carboxylesterase SnoJHER was higher in non-diapausing larvae than in diapausing ones. During the fifth instar of the non-diapausing and the ninth instar of the diapausing larvae, SnoJHER mRNAs reached higher expression levels on the days close to each larval molt.

Synthesis of Polymethacrylates Used as Multifunctional Lubricating Oil Additives

In this paper, four kinds of polymethacrylates(PMAs) used as multifunctional additives were synthesized from quaternary C1—C14 methacrylate, among which sample 4 exhibited relatively better performance. According to the methacrylate ratio of sample 4, the optimized reaction conditions of PMA were explored by orthogonal experiments comprising 4 factors and 3 levels, and the optimized reaction conditions covered an initiator dosage of 0.8 %, a molecular weight regulator dosage of 0.4%, a reaction temperature of 95 ℃ and a reaction time of 8.5 h. When the optimized PMA samples were used to formulate the 75W/90 automotive gear base oil, they exhibited improved shear stability and good low temperature property. In comparison with foreign commercial polymethacrylate GP, the optimized PMA samples exhibited better thickening ability, similar shear stability and slightly weak low temperature property, with their performance being the same as GP's on the whole. The slight difference in the performance between the optimized PMA and GP was attributed to the difference of chain length of copolymers and the distribution of relative molecular mass between them.

Identification of Blood Serum Lipid Compositions Isolated from Diabetic PatientsmType II Treated with Polyherbs by Capillary Gas.Chromatography

This study included treatment of diabetic patients--type II with a polyherbs containing Nigella sativa, Trigonell foenum-graceum, Cyperus rotundus, Teucrium polium divided into two groups, first group was taken herbs with chemical treatment （drugs） and the other group which used herbs only. These groups were compared with healthy persons as a control group. Separation of the lipid component containing in the serum of two groups under study for diabetes mellitus patient--type lI before and after treatment with polyherbs by patients were performed. The separation of the components of different kinds of lipid parts like cholesterol ester （CE）, triglyceride and phospholipids, in the blood using thin layer chromatography （TLC） and capillary gas chromatography （CGC）. The results of this study for ester cholesterol part of serum patients show that there was a significant increase in the percentage of saturated fatty acid （SFA） and monounsaturated fatty acid （MUFA） before the treatment of the two groups compared to the control group and a significant decrease was observed in the percentage of these fatty acid after the treatment by polyherbal mixture than the percentage before treatment. Also, the results for the same part of ester cholesterol serum were showed a significant decrease in percentage of polyunsaturated fatty acid （PUFA） in the two groups of diabetes mellitus patients in comparison with the control group and there were a significant increase observed in PUFA percentage after the treatment. For triglyceride part in serum lipid, the results of this study were shown that there was a significant increase in percentage of SFA and PUFA before treatment in comparison with control group and after treatment for three months of the two groups of patients, shows a significant decrease in SFA but an increase in the percentage of PUFA was observed than that observed before treatment, also, there was a significant decrease in MUFA before treatment comparison with control group, while there was a significant increase which was observed after treatment in a percentage for the two groups of triglyceride part in serum lipid. The results indicated that there was a significant decrease in percentage of SFA before and after also in MUFA after the treatment in both groups compared with control and a significantly increase in PUFA percentage was also shown for phospholipids part in the serum.

Pest Management of Storage Pests Using Extracts of Afrostyrax lepidophyllus against Sitophilus zeama＇（s, Tribolium castaneum and Rhyzopertha dominica

The use of botanical pesticides in pest management during storage against insects is often encouraged because synthetic insecticides produce multiple side-effects on human health and environment. Insecticidal activity of the hexane, dichloromethane, ethyl acetate and methanol extracts of bark ofAfrostyrax lepidophyllus was tested on Sitophilus zeama~：~, Tribolium castaneum and Rhy-opertha dominica. The mortality rate was measured variable. The results of analysis showed that the mortality rate has a very highly significant variation following extracts, doses, insects and time considered （P 〈 0.001）. Extracts with ethyl acetate and hexane of A. lepidophyllus are effective against S. zeamais at the highest doses （1 g/10 mL and 0.5 g/10 mL of solvent）. These effective extracts werc characterized by gas chromatography coupled with mass spectrometry. Molecules such as thiocyanic acid, ethyl ester： dimetbylditbiophosphinic acid and other were characterizated. These results may consolidate traditional use ofA. lepidophylh^s in pest management.

Preparation and Properties of Tung Oil-Based Polyurethane

Tung oil-based polyols were synthesized by the esterification and transesterification between Tung oilbased anhydride and butanediol. The hydroxyl values of the polyols prepared were tested and discussed. Polyurethane was prepared by using Tung oil-based polyols and/or poly(propylene glycol) as polyols and by using isophorone diisocyanate as isocyanate. The effect of the ratio of Tung oil-based polyols to poly(propylene glycol) on the properties of polyurethane prepared was investigated by the water resistance, alcohol resistance and hardness tests. The results show that Tung oil-based polyols are effective to improve the hardness, water resistance and alcohol resistance of polyurethane.

Esterification of Free Fatty Acids in Waste Cooking Oil by Heterogeneous Catalysts

Waste cooking oil(WCO) is becoming the most promising alternative feedstock to produce biodiesel due to its low cost in China. In this study, NKC-9 ion-exchange resin and H-beta zeolite were selected as heterogeneous catalysts in the WCO esterification process and their esterification characteristics were compared by orthogonal experiments. NKC-9 resin showed higher activity and achieved a higher final conversion compared with H-beta zeolite under the same reaction conditions. Reusability experiments showed that NKC-9 resin still exhibited high activity after 5 runs. The effects of the mole ratio of alcohol to oil, reaction time, reaction temperature and the catalyst dose were investigated by multifactor orthogonal analysis. The influence of the free fatty acid(FFA) content was also investigated, and the result showed that the esterification rate could be as high as 98.4% when the FFA content was 6.3wt%.

COMPARISON OF ENERGY RESERVES AND UTILIZATION IN LIPOSCELIS BOSTRYCHOPHILA POPULATIONS SELECTED FOR TOLERANCE TO CONTROLLED ATMOSPHERE

One population of Liposcelis bostrychophila Badonnel (CA selected) was exposed to a controlled atmosphere(CA) (35% CO 2+1% O 2, balance N 2) for 30 generations. Another population (control) was reared under natural atmospheric conditions. Reserves of triacylglycerol, polysaccharides and free amino acids were evaluated in adults of the CA selected and the control populations in generations F 15 and F 30 The utilization rate of triacylglycerol and polysaccharides in the CA exposure were also determined in generation F 30. The results indicate that the reserves of triacylglycerol and polysaccharides increased significantly during selection for CA tolerance; the higher the tolerance level, the greater the reserves. A total of 15 free amino acids constituents were detected in both populations. The total amino acid content in the CA selected population was obviously higher than that in the control population. Exposure of this population to a controlled atmosphere was associated with a steady utilization of reserves. In contrast, the unselected population responded to the controlled atmosphere by accelerated utilization of triacylglycerol and polysachharides. Comparison of utilization rates during CA exposure showed that triacylglycerol is the main energy source, and polysaccharides contribute only a small extent to the metabolic energy supply.