Enantiomeric Separation of S-Epichlorohydrin and R-Epichlorohydrin by Capillary Gas Chromatography with FID Detector

The aim of this study was to develop a simple and derivatization free method for the Quantification of S-Epichlorohydrin in R-Epichlorohydrin by using a gas chromatography coupled with flame ionization detector (FID). Enantiopure epichlorohydrin was a valuable epoxide key starting material for preparing optically active Rivaroxaban. The enantiomeric separations of S-Epichlorohydrin and R-Epichlorohydrin were achieved on Gamaa-Dex-225 (30 meters × 0.25 mm I.D, 0.25 μm) column with a total run time of 30 min. Nitrogen was used as a carrier gas with constant pressure 25.0 psi. The critical experimental parameters such as, column selection, flow rate, injection volume and diluent were studied and optimized. Excellent correlation coeffient between peak responses and concentrations was >0.9998. The recoveries of S-Epichlorohydrin spiked in R-Epichlorohydrin were in the range from 98.2% to 102.8%. Limit of quantitation for S-Epichlorohydrin was sufficiently lower than limits specified by ICH. The method has validated as per International Conference on Harmonization (ICH) guidelines. A precise, accurate, linear and robust Gas Chromatography method was developed for the quantification of S-Epichlorohydrin in R-Epichlorohydrin for Rivaroxaban.

Efficient Solvent-free Synthesis of Chloropropene Carbonate from the Coupling Reaction of CO_2 and Epichlorohydrin Catalyzed by Magnesium Porphyrins as Chlorophyll-like Catalysts

Highly efficient solvent-free coupling reaction of carbon dioxide(CO2)and epichlorohydrin catalyzed by meso-tetraphenyl porphyrin magnesium(MgTPP)in the presence of triethylamine as co-catalysts is reported.As a chlorophyll-like catalyst,MgTPP showed excellent activity for the coupling reaction of CO2 and epichlorohydrin to chloropropene carbonate,in which the turnover number could reach up to 9200.Moreover,different factors including the amount of catalyst,reaction temperature,pressure and time were systematically investigated and the optimal reaction conditions were obtained(epichlorohydrin 50 mmol,MgTPP 5.0×10- 3mmol,triethylamine 6.25×10-3 mmol,140°C,1.5 MPa,8 h).A plausible two-pathway mechanism for the coupling reaction of CO 2and epichlorohydrin is proposed to propound the catalysis of MgTPP.

Rapid and Efficient Adsorption Removal of Reactive Blue 4 from Aqueous Solution by Cross-Linked Microcrystalline Cellulose–Epichlorohydrin Polymers: Isothermal, Kinetic, and Thermodynamic Study

In this study, we modified microcrystalline cellulose by cross-linking it with epichlorohydrin to obtain a rapid and efficient adsorbent for the removal of Reactive Blue 4 dye from aqueous solution. Evidences of the cross-linking of the microcrystalline cellulose were obtained by Fourier transform infrared spectroscopy, X-ray diff raction, Brunauer–Emmett–Teller analysis, thermogravimetric analysis, and scanning electron microscopy. We investigated the eff ects of adsorbent dosage, p H, initial dye concentration, temperature, and contact time on the dye adsorption capacity. The results showed that the adsorption equilibrium time was just 20 min and the maximum adsorption capacity was 69.79 mg/g. The adsorption isotherm data fitted the Langmuir isotherm model well, and the adsorption kinetics data followed the pseudo-second-order kinetic model. The results of the thermodynamic analysis suggest that the adsorption process was spontaneous and exothermic. Recyclability experiments demonstrated the good reusability of this adsorbent. Electrostatic interaction was found to dominate the adsorption process.

A NOVEL APPROACH TO SYNTHESIZE CHITOSAN BEADS CROSSLINKED BY EPICHLOROHYDRIN

The present investigation describes a novel method for preparing spherical chitosan particles based on crosslinking with epichlorohydrin. Certain amount of pre-crosslinking agent was added to form chitosan gels by traditional inverse phase suspension polymerization. Then the gels were crosslinked by epichlorohydrin at basic condition to obtain chitosan beads. The effects of reaction conditions, such as crosslinking time, the amount of crosslinking agent and the NaOH concentration, on the physical properties of the chitosan beads were investigated. The beads were found to have more amino groups in the polymer chains than the beads crosslinked by glutaraldehyde. The capacity for copper ions is as high as 40mg/g. The beads have good mechanical strength and can be reused.

AFFINITY CHROMATOGRAPHY PURIFICATION OF UROKINASE WITH EPICHLOROHYDRIN ACTIVATED AGAROSE MATRIX

1 INTRODUCTIONIn literature,most matrices of affinity chromatography for urokinase(EC 3.4.99.26)purification were prepared by cyanogen bromide activation.However,theseadsorbents usually suffered from the drawback of leakage of the ligand,particularly inalkaline medium,because of the instability of the isourea linkage between the ligandand the spacer or agarose.Moreover,the positively charged imido group of theN-substituted isourea derivative and the hydrophobicity of the spacers might promotenonspecific adsorption.On the contrary,the adsorbents prepared by the method

STUDIES ON THE POLYMERIZATION OF β-CYCLODEXTRIN WITH EPICHLOROHYDRIN

Different proportions of β-cydodextrin and epichlorohydrin were used to prepare a group of β-cyclodextrin polymers. The relationship between the reaction extent and the molar ratios of reactants was discussed according to the results of ~1H-NMR, ^(13) C-NMR spectra and elemental analysis. Especially, high resolution ~1H-NMR spectra were usd for studying the reaction active sites and the extent of reaction. The solubility of oil soluble drugs in water was largely improved in the presence of water-soluble β-cyclodextrin polymer.

NEW CATALYTIC SYSTEMS FOR THE FIXATION OF CO_2 Ⅲ.INFLUENCE OF ADDITIVES AND REACTION MEDIUM ON THE COPOLYMERIZATION OF CARBON DIOXIDE-EPICHLOROHYDRIN IN THE PRESENCE OF Nd (P_(204))_3-Al(i-Bu)_3

Copolymerization of carbon dioxide with epichlorohydrin was successfully carried out by usingNd(P_(204))_3-Al(i-Bu)_3 as catalyst (P_(204))=(RO)_2 POO--,R=CH_3 (CH_2),CH(C_2H_5) CH_2--). Addi-tion of carbonyl compounds into the catalyst decreased the carbon dioxide content of the copoly-mer to some extent. Compared to nonpolar solvents, ethereal and moderate polar solvents werefavourable to obtaining higher carbon dioxide content copolymer. The coincidence of these resultswith the assumed copolymerization scheme clearly indicated that the copolymerization proceeds via coordinate anionic mechanism.

THE POLYMERIZATION OF EPICHLOROHYDRIN WITH Nd(i-oPr)_3-Al(i-Bu)_3 SYSTEM

Epichlorohydrin (ECH) was polymerized with a rare earth catalytic system: Nd (i-OPr)_3-Al (i-Bu)_3. The effects of Al/Nd molar ratio, solvents, the polymerization time and temperature,the aging time and temperature of the catalyst preparation were studied. The results showed thatat a low Al/Nd molar ratio (4) of the Nd(i-OPr)_3-Al(i-Bu)_3 system ECH polymerized at a lowtemperature (248K) with a high conversion. The average molecular weight ofpolyepichlorohydrin (PECH) ranged from 1×10~5 to 3×10~5.

Rare Earth Polymer Complex Catalyst for Ring Opening Polymerization of Epichlorohydrin

novel complex composed of chitosan(CS) and neodymium(Nd ) was preparedand the ring opening polymerization of epichlorohydrin(ECH) with a new catalyticsystem comprising this new rare earth polymer complex(CS . Nd) has been suc-cessfully carried out for the first time. It has been found that the new catalytic sys-tem composed of CS . Nd-AI (i-Bui,-methyl benzoxylate( Ⅲ) is an excellent cata-lyst for the polymerization of epichlorohydrin which shows a catalytic activity 60times higher tlian that of conventional rare earth catalyst. Under the following re-action conditions : Nd - 1 ×10￣(-6) mo1/g monomer, A1/Nd= 60 molar ratio , Ⅲ/A1=-0. 6 molar ratio, the monomer conversion and PECH molecular weight are as highas 92.9% and 28. 2 × 10￣5 respectively and the polymer prepared has a low crys-tallinity. The kinetics investigation revealed that the polymerization has a short in-duction period of several minutes and the rate of polymerization is of first orderwith respect to the monomer concentration and the catalyst concentration. The acti-vation energy of the polymerization reaction was found to be 25. 5 kJ/mol which islower than that of conimon rare earth catalvst.

Keap1/Nrf2信号通路在非小细胞肺癌氧化应激机制中的作用

目的检测非小细胞肺癌(NSCLC)组织中Kelch样环氧氯丙烷相关蛋白-1(Keap1)、核因子E2相关因子2(Nrf2)蛋白表达水平,分析其与临床病理参数、氧化应激指标的相关性,为临床治疗提供潜在靶点。方法选取2017年4月至2020年4月郑州市第三人民医院收治的100例NSCLC患者为研究对象,免疫组化法检测并比较癌组织、癌旁组织中Keap1、Nrf2蛋白表达水平;比较不同临床病理参数患者Keap1、Nrf2蛋白表达水平;比较不同Keap1、Nrf2蛋白表达患者血清超氧化物歧化酶(SOD)、诱导型一氧化氮合酶(iNOS)、丙二醛(MDA)水平,并采用Spearman法分析SOD、i NOS、MDA与临床病理参数的相关性,采用Pearson法分析SOD、iNOS、MDA与Keap1、Nrf2蛋白水平的的相关性;比较不同Keap1、Nrf2蛋白表达患者的生存率。结果癌组织、癌旁组织Keap1蛋白阳性率分别为77.00%、53.00%,Nrf2蛋白阳性率分别为74.00%、45.00%,Keap1蛋白OD值分别为0.41±0.07、0.33±0.05,Nrf2蛋白OD值分别为0.39±0.06、0.31±0.06,癌组织Keap1、Nrf2蛋白阳性率及OD值明显高于癌旁组织,差异均有统计学意义(P<0.05);Keap1蛋白阳性表达与病理分级、T分期呈正相关(r=0.569、0.574,P<0.01),Nrf2蛋白阳性表达与病理分级、T分期呈正相关(r=0.527、0.539,P<0.01);Keap1蛋白阳性者、阴性者的血清SOD水平分别为(86.78±9.14)U/m L、(115.07±12.13)U/m L,MDA水平分别为(4.42±0.82)mmol/L、(3.24±0.56)mmol/L,i NOS水平分别为(22.74±4.31)U/m L、(15.59±3.02)U/mL,Nrf2蛋白阳性者、阴性者血清SOD水平分别为(84.94±9.12)U/mL、(117.06±12.37)U/mL,MDA水平分别为(4.48±0.85)mmol/L、(3.21±0.52)mmol/L,iNOS水平分别为(23.02±4.28)U/mL、(15.64±3.10)U/mL,Keap1、Nrf2蛋白阳性者血清SOD水平明显低于阴性者,MDA、iNOS水平明显高于阴性者,差异均有统计学意义(P<0.05);Keap1、Nrf2蛋白表达与SOD呈负相关(r=-0.612、-0.614,P<0.01),与MDA、iNOS呈正相关(r_(Keap1)=0.609、0.614,P<0.01;r_(Nrf2)=0.610、0.608,P<0.01);Keap1、Nrf2蛋白阳性表达者3年生存率为85.71%、83.78%,明显低于阴性表达者的95.65%、100.00%,差异均有统计学意义(P<0.05)。结论NSCLC组织中Keap1、Nrf2蛋白表达水平升高,且与病理分级、T分期密切相关,该信号通路活化可参与氧化应激反应过程,且对预判患者预后具有一定临床意义。

液液萃取-气相色谱质谱法测定水质中的环氧氯丙烷

比较了不同前处理方法进行水质中环氧氯丙烷的测试,其中液液萃取的前处理方法简单可靠,方便易行,适合复杂基质水样的测定。同时比较了气相色谱仪不同检测器对环氧氯丙烷(ECH)的响应值,其中质谱检测器对ECH的响应值最高。液液萃取-气相色谱质谱法测定水质中的环氧氯丙烷,该方法的检出限为0.6μg/L,测定下限为2.4μg/L。对海水、地表水、工业污水样品加标浓度为0.001 mg/L、0.02 mg/L、0.2 mg/L进行平行6次测定,结果的相对标准偏差分别为6.9%、2.7%和6.3%,加标回收率分别为93.5%、99.0%和99.6%,非常适合各类水质ECH的监测。

一种壳聚糖改性产物的制备工艺及其产品吸附性能的研究

以壳聚糖(CTS)为母体,加入冰醋酸溶解得到CTS溶液,以无水乙醇为致孔剂,制备多孔壳聚糖微球,将制得的CTS微球与环氧氯丙烷(ECH)交联,制备出羟丙基壳聚糖微球(HPCTS),对产物进行红外光谱和电镜扫描性能表征。通过红外光谱图分析可以看出,ECH与CTS进行了交联反应。比较CTS和HPCTS的电镜扫描图片,发现HPCTS表面因为交联反应而形成大量多孔结构,增加了大量可供吸附重金属离子的空穴,使得HPCTS比交联前的表面积有了大幅提高。通过单因素实验,研究了制备HPCTS的工艺参数,在较优工艺参数下制备的产物交联度可达75.23%,产品具有良好的可再生性。

环氧氯丙烷生产工艺的研究现状

综述了环氧氯丙烷传统生产工艺的改进及新工艺开发方面的研究现状,分析了不同工艺路线的优缺点,重点介绍了甘油法和氯丙烯直接环氧化法制环氧氯丙烷的催化剂体系和生产工艺情况。甘油法由于可有效利用生物质资源、生产工艺流程简单,是继丙烯高温氯化法之后较为成熟的生产工艺;氯丙烯直接环氧化法作为绿色的环氧氯丙烷合成工艺,其研究重点要放在低成本催化剂的设计和工艺的集成降耗上。

HS-SPME-GC/MS法测定生活饮用水中环氧氯丙烷

目的建立自动顶空固相微萃取-气相色谱质谱法测定生活饮用水中环氧氯丙烷。方法采用80μm DVB/Carbon WR/PDMS固相微萃取头,在250 r/min振摇条件下,35℃平衡15 min、顶空萃取15 min,250℃解析5 min,经DB-624色谱柱分离,质谱仪检测,外标法定量。结果环氧氯丙烷在0.2~2.0μg/L范围内线性良好(r=0.9992),方法检出限为0.03μg/L,定量限为0.09μg/L,相对标准偏差为2.2%~4.6%,加标回收率为95.3%~102.8%。结论本法操作简便,可用于生活饮用水中环氧氯丙烷的测定。

甲醛与环氧氯丙烷交替共聚物制备及其表征

采用自制的三氟化硼-二苯基亚砜复合物催化剂,以三聚甲醛与环氧氯丙烷通过阳离子开环聚合的方法共聚合成出一种新型甲醛与环氧氯丙烷交替共聚物,并探究了不同反应条件对共聚结果的影响。采用了傅里叶红外光谱、核磁共振谱、凝胶渗透色谱等对所得共聚物的结构进行了表征。结果表明,该聚合反应在甲醛与催化剂摩尔比例为50:1、甲醛与环氧氯丙烷摩尔比例为1:1、反应时间为8 h、反应温度为25℃的条件下进行反应产率可达到84.52%。由凝胶渗透色谱结果表明,该条件下共聚物的Mn=3.60×10^(3),分子量分布指数PDI=1.32。傅里叶红外光谱、核磁共振谱分析的结果表明,该共聚物为交替共聚物。

益气活血降浊汤配合丁苯酞对TIA患者的疗效及机制

[目的]探讨益气活血降浊汤配合丁苯酞治疗短暂性脑缺血发作(TIA)的临床疗效和初步机制。[方法]选取南阳市第一人民医院2022年1月—2023年3月收治的120例TIA患者为研究对象,随机分为三组,各40例。对照1组予以丁苯酞,对照2组予以益气活血降浊汤,观察组予以益气活血降浊汤配合丁苯酞,治疗2个月。治疗2个月后比较三组临床疗效、不良反应发生率。比较治疗前及治疗1个月、2个月三组ABCD2评分、美国国立卫生研究院卒中量表(NIHSS)评分及血清生物化学指标[可溶性CD40配体(sCD40L)、脂蛋白相关磷脂酶A2(Lp-PLA2)、高敏C反应蛋白(hs-CRP)]水平、外周血Kelch样环氧氯丙烷相关蛋白1(Keap1)-核因子E2相关因子2(Nrf2)/抗氧化反应元件(ARE)信号通路相关蛋白(Keap1、Nrf2、ARE)水平及血流动力学指标[血流平均流速(Vm)、平均血流量(Qm)、脑血管阻力(R)]。[结果]观察组临床总有效率显著高于对照1组、对照2组(P<0.05),但两对照组之间比较差异无显著性(P>0.05);相较于治疗前,三组治疗1个月、2个月ABCD2评分和NIHSS评分呈显著下降趋势,且观察组下降幅度较对照1组、对照2组大(P<0.05),但两对照组比较差异无显著性(P>0.05);相较于治疗前,三组治疗1个月、2个月sCD40L、Lp-PLA2、hs-CRP呈显著下降趋势,且观察组下降幅度显著大于对照1组和对照2组(P<0.05);相较于治疗前,三组治疗1个月、2个月Keap1蛋白呈显著下降趋势,且观察组下降幅度较对照1组、对照2组大(P<0.05),但两对照组比较差异无显著性(P>0.05);相较于治疗前,三组治疗1个月、2个月Nrf2蛋白和ARE蛋白呈显著升高趋势,且观察组升高幅度较对照1组、对照2组大(P<0.05),但两对照组比较差异无显著性(P>0.05);相较于治疗前,三组治疗1个月、2个月Qm、Vm呈明显升高趋势,R呈显著下降趋势,且观察组Qm、Vm明显较对照1组、对照2组高,R显著较对照1组、对照2组低(P<0.05)。[结论]益气活血降浊汤配合丁苯酞较丁苯酞、益气活血降浊汤单独治疗TIA疗效更佳,它可改善神经功能、脑血流动力学,抑制炎症反应,且具有一定安全性,其作用机制与调节Keap1-Nrf2/ARE信号通路相关。

四氢呋喃和环氧氯丙烷交替共聚醚的合成研究

以四氢呋喃和环氧氯丙烷为原料,以四氟硼酸二氟氧硼二苯基锍为引发剂,制备四氢呋喃–环氧氯丙烷交替共聚醚。通过傅里叶变换红外光谱和核磁共振波谱等表征方法,确定所得共聚醚为交替共聚醚。通过差示扫描量热分析得到交替共聚醚的玻璃化转变温度为–63℃。制备的交替共聚醚的特性黏度为25.8 dL/g。最佳反应条件为:反应温度20℃,反应时间8 h,四氢呋喃与环氧氯丙烷的摩尔比为1:1,单体与引发剂的摩尔比为200:1。

The block copolymerization of isoprene with epichlorohydrin by rare earth coordination catalyst

The block coordination copolymerization of isoprene （Ip） with epichlorohydrin （ECH）has not been reported yet. Deore once studied the anionic type copolymerization ofdiene with ethylene oxide by naphthalene-potassium catalyst and obtained the solid polymerelectrolytes. Based on the coordination polymerization of Ip and ring-openingpolymerization of alkene oxide by rare earth catalysts, we first studied the blockcopolymerization of Ip and ECH in the presence of rare earth coordination catalysts:RE(P204)3-Al （i-Bu）3-halide. The block copolymer which has high molecular weight with

岩藻黄素对小鼠非酒精性脂肪性肝病的修复作用

目的:探究岩藻黄素对高脂饮食诱导的C57BL/6小鼠非酒精性脂肪性肝病(non-alcoholic fatty liver disease,NAFLD)的修复作用及其机制。方法:将52只C57BL/6小鼠随机分成4组,正常组14只,其余为实验组,实验组给予8周的高脂饮食喂养之后,再分为模型组、岩藻黄素低剂量和高剂量组,给予灌胃6周,每日1次。每周记录小鼠的体质量,第14周结束时小鼠禁食12 h后全部处死。后续分别测定各组小鼠血清中谷草转氨酶(aspartate aminotransferase,AST)、谷丙转氨酶(alanine aminotransferase,ALT)活力,总胆固醇(total cholesterol,TC)、甘油三酯(triglyceride,TG)、低密度脂蛋白胆固醇(lowdensitylipoproteincholesterol,LDL-C)、高密度脂蛋白胆固醇(highdensitylipoproteincholesterol,HDL-C)、游离脂肪酸、脂联素和瘦素含量;检测肝脏组织匀浆液中超氧化物歧化酶(superoxide dismutase,SOD)、谷胱甘肽(glutathione,GSH-Px)、丙二醛(malondialdehyde,MDA)、过氧化氢酶(catalase,CAT)、白细胞介素-1β、白细胞介素-6和肿瘤坏死因子α含量;透射电镜下观察肝脏的组织病理学变化并采用蛋白免疫印迹法检测肝脏中5’-单磷酸腺苷活化蛋白激酶(adenosine 5’-monophosphate-activated protein kinase,AMPK)、核因子红系2相关因子2(nuclear factor erythroid2-related factor 2,Nrf2)和Toll样受体4(toll-like receptors 4,TLR4)信号通路蛋白表达情况。结果:与模型组相比,岩藻黄素组中的TC、TG、LDL-C、ALT、AST显著降低(P<0.05),HDL-C显著升高(P<0.05),且降低了瘦素水平,增加了脂联素分泌,GSH-Px、SOD、CAT升高(P<0.05),MDA降低(P<0.05),且炎症因子的水平降低。苏木精-伊红染色、油红O染色、糖原染色和透射电镜结果显示岩藻黄素组肝脏组织学结构好转,趋近于正常组。蛋白免疫印迹法结果显示岩藻黄素治疗可上调AMPK信号通路中磷酸化5’-单磷酸腺苷活化蛋白激酶和过氧化物酶体增殖物激活受体α、磷酸化乙酰辅酶A羧化酶、肉碱脂酰转移酶1,下调固醇调节元件结合蛋白-1c、脂肪酸合酶表达;抑制Kelch样环氧氯丙烷相关蛋白1/Nrf2信号通路中Keap-1的水平,提高Nrf2及其下游抗氧化蛋白血红素氧合酶1、NAD(P)H-醌氧化还原酶1和谷氨酸-半胱氨酸连接酶的表达水平;下调TLR4信号通路中TLR4蛋白的表达,抑制髓样分化因子88、磷酸化人核因子κB抑制蛋白α和磷酸化核因子κB蛋白(p65)的表达。结论:岩藻黄素可通过调节脂质代谢、减少氧化应激和调节炎症等途径修复高脂饮食诱导的小鼠非酒精性脂肪性肝病。

双季铵盐表面活性剂制备的教学实验设计

将由环氧氯丙烷制备双季铵盐表面活性剂的反应设计为适合本科生实验教学的基础实验。实验包括制备、纯化和检测三个步骤。以N,N-二甲基十二烷胺、浓盐酸和环氧氯丙烷为原料,在正丙醇溶剂中回流反应4 h制备双季铵盐表面活性剂。溶剂通过减压蒸馏去除,粗产物在丙酮中通过结晶的方法纯化,得到的双季铵盐产物通过测熔点的方法验证纯度。对实验条件进行了优化。该实验设计具备重复性、科学性和可行性。实验内容具有综合性、简易性和新颖性的特点,对培养学生的动手能力、实践能力、综合能力及创新思维很有帮助。