Research on SO42-/ZrO2 Solid Superacid Catalyst and Catalyzed FFA Estrification in the Biodiesel sources

生物柴油主要成分为长链脂肪酸甲酯（FAME），是绿色的可再生能源，是传统石化柴油的优良替代燃料。但制备生物柴油的原料中大都含有较多的游离高级脂肪酸，需要酯化反应脱除高级脂肪酸，使油脂能够符合下一步碱催化酯交换反应生产生物柴油的要求。本文采用SO42-/ZrO2固体超强酸代替硫酸作为催化剂，以甘油为酯化剂，进行高级脂肪酸的酯化反应，分别研究了以ZrO(NO3)2和ZrOCl2为锆源的前体Zr(OH)4制备，考察了硫酸根的引入，硫酸浓度，浸渍量，煅烧温度等条件对SO42-/ZrO2固体超强酸在高级脂肪酸酯化反应中的催化活性的影响。结合XRD、SEM、TG、NH3-TPD、IR、拉曼等分析表征手段，...The main component of biodiesel is the long-chain fatty acid methyl esters(FAME), which is a kind of green renewable energy and the excellent alternative fuel of traditional petroleum diesel. However, the raw materials for preparing biodiesel always contain much free fatty acid(FFA), which should be removed by esterification. In this dissertation, solid superacid SO42-/ZrO2 has employed as catal...学位：工学博士院系专业：化学化工学院化学工程与生物工程系_工业催化学号：2062006015327

Preparation of Morphology-Tuned γ-MnO_2 and Catalytic Performance for the Liquid-Phase Oxidation of Toluene

通过在回流法制备流程中引入CTAb(十六烷基三甲基溴化铵)、PEg6000(聚乙二醇6000)及P123(聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物)等表面活性剂对γ-MnO2催化剂进行形貌控制,同时采用X射线衍射(Xrd)、扫描电镜(SEM)、n2吸附(bET)、热重分析(TgA)、O2程序升温脱附(O2-TPd)以及H2程序升温还原(H2-TPr)等技术对不同形貌γ-MnO2的结构、氧脱附及还原性能进行表征,并考察了其在常压和无溶剂条件下甲苯选择性氧化反应体系的催化特性.同时,对于陈化时间对形貌的影响作用进行了考察.结果表明:不同形貌的γ-MnO2的氧化还原特征及催化活性存在显著差异,其中在经PEg6000进行修饰的γ-MnO2中含有较多的阴离子空位及混合价态,因此有助于分子氧在表面的活化,具有较高的表面比活性;而经P123进行表面修饰的γ-MnO2成晶结构规整、比表面积大,对甲苯液相直接氧化反应则表现出最佳的质量比活性,甲苯转化率达18.1%,含氧化合物总选择性为87.4%,其中苯甲酸的选择性达到73.2%.Introducing surfactants including hexadecyltrimethylammonium bromide (CTAB),macrogol 6000 (PEG6000),and poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) triblock copolymer (P123) into the refluxing aqueous crystal nucleus slurry yielded morphology-tuned microcrystalline γ-MnO2.γ-MnO2 and the influence of surfactant modification were investigated by X-ray diffraction (XRD),scanning electron microscopy (SEM),N2 adsorption (BET),thermogravimetry analysis (TGA),O 2 temperature programmed desorption (O2-TPD),and temperature programmed H2 reduction (H 2-TPR).Surfactants led to differences in γ-MnO2 morphology,surface area,oxygen desorption behavior and reducibility.The effect of reflux time on catalyst morphology is discussed.The catalytic performance of γ-MnO2 during the solvent-free atmospheric oxidation of toluene was evaluated.PEG6000 modified γ-MnO2 exhibited the highest catalytic activity judging by surface area because of a greater mixed valency and more anion vacancies.The greatest mass specific activity was obtained for P123 modified γ-MnO2 with the largest surface area.Optimized reaction conditions yielded an 18.1% toluene conversion,and 87.4 and 73.2% total selectivity and selectivity for benzoic acid,respectively.国家重点基础研究发展规划项目(973)(2010CB226903)资助~

在福建东南沿海局部地域献血员中检出HTLV-I

[目的 ]进一步阐明福建沿海 HTL V小流行区 HTL V- 的地理分布特点及毒株的基因类型。 [方法 ]对福建东南沿海莆田地区献血员以国产双抗原夹心法 EL ISA试剂筛选 ,对 EL ISA阳性血清用 Western blot(WB)进行确证。对抗体确证阳性者 ,采集外周血分离淋巴细胞用巢式 PCR扩增 HTL V- env区 gp46片段进行序列分析鉴定病毒亚型。 [结果 ]从 1998年 10月至 2 0 0 0年 4月止 ,共检测 45 6 4份标本 ,结果确证出 16例 HTL V- 抗体阳性者 ,感染率为 0 .35 %。HTL V- 抗体阳性者主要分布在某村献血人群中 ,并具有区域集中的特点。笏石秀屿一带某村献血员中感染率高达 4.7%。7例代表性毒株经病毒序列分析为 HTL V- C亚型 (COSMOPOL ITAN)。[结论 ]福建东南沿海某村献血员中发现 HTL V- 流行。提出在对某一地区人群进行 HTL V筛选时 ,既要注意整个地区“面”的筛查 ,又要注重某个村镇“点”的调查

Spatial distribution and correlation of environmental factors andchlorophyll a concentrations in the Bohai Sea during the summer of 2013

通过对2013年7月渤海海域26个站点温度、盐度、营养盐及叶绿素a(Chl a)浓度的空间分布特征及其相关性进行了分析,发现:受渤海水深和夏季陆源河流输入影响,近岸水域表现出明显的高温、低盐与高营养盐特征,且垂直变化特征不显著;在水深较深的辽东湾湾口和渤海海峡,海水呈现明显的层化现象,表层水温高于中底层,而表层盐度与营养盐浓度则低于中底层。营养盐结构分析表明,渤海夏季磷酸盐浓度存在显著的绝对与相对限制,而受河流输入影响,硅酸盐的相对限制得到显著缓解。表层Chl a浓度的高值区位于滦河及复州河河口附近海区,中层与底层的高值区则出现在滦河与黄河口附近。Chl a浓度与环境因子的相关性分析表明,盐度..

死亡受体5胞外区域的重组、表达及活性鉴定

目的构建死亡受体5(deathreceptor5,DR5)胞外区域(eDR5)的表达载体,表达纯化重组蛋白并鉴定其生物特性。方法通过重叠PCR获得DR5胞外段编码序列,构建pET-22b(+)/DR5表达载体,转化大肠杆菌BL21(DE3),IPTG诱导表达,Ni2+柱亲和纯化,SDS-PAGE、直接ELISA鉴定纯化产物的纯度和特异性,用MTT法检测eDR5蛋白阻断DR5单克隆抗体FMU1.5和TRAIL诱导人胶质瘤细胞株U343(高表达DR5)、U373(低表达DR5)细胞凋亡的作用。结果获得了DR5胞外段编码序列,目的蛋白在上清及包涵体中都有表达,表达量占菌体总蛋白的30%以上,纯化的重组蛋白纯度达95%以上,蛋白产量达9mg/ml。ELISA结果表明所纯化蛋白为eDR5。eDR5蛋白可部分阻断FMU1.5和TRAIL诱导人胶质瘤细胞株U343细胞凋亡的作用,其阻断率与DR5表达相关。结论死亡受体5胞外段基因的成功重组、表达及纯化,为进一步的功能研究奠定了基础

CaO as a Solid Base Catalyst for Transesterification of Soybean Oil

用不同的前驱物合成了三种CaO催化剂,并以X射线衍射(XRD)、扫描电子显微镜(SEM)、程序升温脱附(TPD)等方法加以表征.这些CaO被用作大豆油(SBO)经酯交换制取脂肪酸甲酯(FAME),即生物柴油的催化剂,由方解石制备的氧化钙(Cal(N))表现了最好的SBO酯交换活性.检测发现CaO的酯交换活性与它们的碱性强度密切相关,当暴露于CO2气氛下,显著降低了CaO的酯交换催化活性(Raman光谱测试显示当置CaO于常温空气中,其表面形成的CaCO3和Ca(OH)2将阻止CaO继续参与SBO的酯交换反应).CO2的毒化颇受制于CaO前驱体种类,Cal(N)比来自文石的CaO(即Ara(N))有更好的抗CO2毒化能力;这些受损的CaO催化活性可部分复原.提出了CaO催化剂受CO2毒化及其再生的机理,同时讨论了SBO酯交换活性相到底是CaO固体表面,拟或溶解了的CaO的问题.Three different calcium oxide catalysts were synthesized from different precursors and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and temperature-programmed desorption (TPD). They were used as catalysts in the transesterification of soybean oil (SBO) for the production of fatty acid methyl esters (FAME), namely biodiesel. Calcium oxide from calcite (Cal(N)) showed the highest activity towards the transesterification of SBO. The transesterification activity of CaO was found to be highly related to the basicity of the catalysts. The catalytic activity of CaO greatly decreased when CaO was exposed to CO2. (Raman spectroscopic studies demonstrated that the formation of CaCO3 and Ca(OH)2 on the surface of CaO when CaO was exposed to room air prevented CaO from participating in the transesterification of SBO). The degree of poisoning was highly dependent on the type of precursors with Cal(N) more resistant to CO2 poisoning than CaO from aragonite (Ara(N)). Deactivated CaO catalysts could be partially regenerated. A mechanism was proposed to explain the poisoning and regenerating processes. Furthermore, whether the solid phase of CaO or dissolved CaO was the active species in the transesterification of SBO was also investigated.教育部生物质能源重大项目(教技司(2007)29号文);; 固体表面物理化学国家重点实验室资

甲酸甲酯氢解制甲醇铜基催化剂上吸附物种的现场红外光谱表征

应用原位红外光谱的方法，在反应现场条件下，研究了促进型甲酸甲酯（ＭＦ）氢解制甲醇铜铬催化剂上的化学吸附物种．结果表明，在ＭＦ氢解反应条件下，工作态催化剂上主要的化学吸附物种和反应中间物种是ＣＨ３Ｏ－ＣＨＯ…Ｈ－Ｏ（ａ）（１７５１，２７３０，１４５５ｃｍ－１）、ＣＨ３Ｏ－ＣＨＯ…Ｃｕ＋（ａ）（１６５４，２７３０，１４５５ｃｍ－１）、ＣＨ３Ｏ－ＣＨＯ…Ｃｒ３＋（ａ）（１５５２，２７３０，１４４５ｃｍ－１）和ＯＣＨ３（３０１２，２９４６，１４５５ｃｍ－１）．结合对该催化剂活性位本质的探讨，推断了甲酸甲酯氢解制甲醇的主要反应途径

Mechanism of geniposide in improving free fatty acid metabolism in rats with non-alcoholic fatty liver disease

观察栀子苷改善非酒精性脂肪性肝病的效果,从游离脂肪酸探讨栀子苷调节非酒精性脂肪性肝病的作用机制。健康雄性Wistar大鼠40只,随机分为4组:正常组、模型组、栀子苷组和血脂康组,每组大鼠10只,正常组大鼠给予正常大鼠饲料喂养,其余3组大鼠均采用高脂饲料喂养以诱导非酒精性脂肪性肝病,造模时间为8周,从第5周起至第8周末,栀子苷组和血脂康组分别灌服相应的药物。记录大鼠体重、肝湿重、脂肪质量;用相应方法检测肝组织TG,FFA,FAS,AMPK,ACCase及Malonyl-Co A含量,血清CHO,LDL-C的含量,血清AST,ALT的活性;观察肝脏组织肉眼及病理变化(HE染色法)。结果显示,与正常组相比,模型组大鼠的体重;肝湿重;脂肪重;血清CHO,LDL-C,ALT,AST;肝组织TG,FFA,FAS,ACCase及Malonyl-Co A含量皆显著升高(P<0.01);肝组织AMPK活性显著降低(P<0.01),肝组织肉眼外观及病理切片脂肪变性明显,并出现炎症损伤;与模型组相比,栀子苷组大鼠体重、脂肪质量、肝组织FFA含量、血清ALT,AST活性均显著降低(P<0.01),肝湿重,肝组织TG,FAS,ACCase及Malonyl-Co A含量明显降低(P<0.05),肝组织AMPK活性明显增多(P<0.05),肝脏肉眼外观及病理学表现均有所改善;与模型组相比,血脂康组大鼠的肝湿重、脂肪质量、肝组织TG,FFA和血清LDL-C水平明显降低(P<0.05);与血脂康组相比,栀子苷组大鼠的体重、脂肪质量、肝组织FFA含量均显著降低(P<0.01),其他方面无明显差异。结果表明,栀子苷具有显著的改善高脂饮食诱导的大鼠非酒精性脂肪性肝病的药理效应;其改善大鼠非酒精性脂肪性肝病的游离脂肪酸代谢是通过调节"AMPK-ACCase-Malonyl-Co A-FFA"轴来实现的。To observe the effect of geniposide on non-alcoholic fatty liver disease( NAFLD),and discuss the mechanism of geniposide for NAFLD from the aspect of free fatty acid,forty healthy Wistar male rats were randomly divided into normal group,model group,geniposide and Xuezhikang group. The rats in normal group were fed with normal diets,and the rats in other 3 groups were given with high-fat diet for 8 weeks to induce the NAFLD models. From the week 5 to end of week 8,the rats in geniposide and Xuezhikang group were intervened with corresponding medicines. The body weight,liver wet weight,and fat weight of the rats were recorded.Visual and pathological changes in hepatic tissues were observed with HE staining. The contents of TG,FFA,FAS,AMPK,ACCase and Malonyl-Co A in hepatic tissue,contents of CHO and LDL-C in serum and activities of AST and ALT in serum were detected by using corresponding methods. The results showed that the body weight,liver wet weight,and fat weight of the rats,CHO,LDL-C,ALT and AST levels in serum,TG,FFA,FAS,ACCase and Malonyl-Co A levels in hepatic tissues of the rats in model group were significantly higher than those in normal group( P < 0. 01),while AMPK activity was significantly lower than that of the normal group( P < 0. 01),with obvious visual and pathological steatosis in hepatic tissues,and inflammatory injury occurred in model group. Compared with the model group,body weight of the rat,fat weight,levels of FFA in hepatic tissues,ALT and AST activities in serum,liver wet weight,TG,FAS,ACCase and Malonyl-Co A levels were significantly decreased in geniposide group( P < 0. 01),while the AMPK activity in hepatic tissues was significantly increased( P < 0. 05),with improvement in visual and pathological performance.Compared with the model group,liver wet weight,fat weight,TG and FFA levels in hepatic tissues,and LDL-C level in serum were significantly decreased in Xuezhikang group( P < 0. 05). Compared with Xuezhikang group,the body weight of rat,fat weight and FFA level in hepatic tissues were significantly lower in geniposide group( P < 0. 01),but with no significant difference in other aspects. These findings indicated that geniposide was highly effective in improving the pharmacological effect of NAFLD induced by highfat diet,and the mechanism was achieved through AMPK-ACCase-Malonyl-Co A-FFA axis.国家自然科学基金项目(81274155;81503529);; 福建省自然科学基金项目(2014J01374);; 福建省高等学校新世纪人才计划项目;; 厦门市科技计划项目(3502Z20134020);; 福建省中医药科研项目(WZPW201308

Effect of geniposide on the lipid metabolism and inflammatory injury of nonalcoholic fatty liver disease in the hamster

目的:观察栀子苷对高脂饮食诱导的金黄地鼠非酒精性脂肪性肝病模型脂质代谢、肝组织病理变化及炎症损伤的影响,并与栀子进行比较,以明确栀子抗脂肪肝作用的效应成分。方法:24只雄性金黄地鼠按随机数字表法分为正常组、模型组、栀子组和栀子苷组。实验后观察肝组织病理学变化,并检测肝组织Tg含量、血清Tg、CHO含量及AlT、AST活性。结果:与模型组比较,栀子组、栀子苷组肝Tg含量、血清Tg、CHO含量及AlT、AST活性均显著降低,且栀子苷对AlT、AST活性的降低作用优于栀子。结论:栀子苷与栀子对高脂饮食诱导的地鼠脂肪肝均有显著干预作用,且栀子苷抗炎症损伤作用优于栀子。Objective: To observe geniposide's effect on lipid metabolism,hepatic tissue pathological change and inflammatory injury of golden hamsters with nonalcoholic fatty liver disease( NAFLD),caused by high fat diet.Compare the geniposide's effect with gardenia to make clear the effective components in Gardenia that can resist fatty liver.Methods: 24 male golden hamsters were averagely divided into control group,model group,gardenia group and geniposide group.The experiment was based on building the model,and then observe hamsters 'general condition and pathological change of hepatic tissue,examine the content of hepatic tissue TG,serum TG,CHO and the activity of ALT,AST.Results: In gardenia group and gardenoside group,The content of hepatic tissue TG,serum TG,CHO and the activity of ALT,AST are significantly lower than the model group.Besides,gardenoside can lower the activity of ALT,AST better than gardenia.Conclusion: Both gardenoside and gardenia have notable intervention effects on hamsters' NAFLD caused by HFD and gardenoside have better effects on resisting inflammatory injury than gardenia,which suggested that gardenoside was the primary effective component in resisting NAFLD.国家自然科学基金面上项目(81274155); 厦门市重大科技计划项目(3502Z20100006