Controllable Synthesis of Cellulose Esters by Homogeneous Transesterification and Its Application

随着石油、煤炭等不可再生资源的日益枯竭，为了满足社会经济可持续发展的需要，以纤维素生物质为原料制备高附加值化工品及燃料的研究逐渐成为人们研究的热点。本文以多种来源的纤维素为原料，以N，N-二甲基乙酰胺/氯化锂（DMAc/LiCl）为溶剂体系，建立一种温和快速均相酯交换可控制备纤维素酯的方法，改进了纤维素在DMAc/LiCl体系中的溶解过程，优化了酯交换反应制备工艺，分析了纤维素酯类产物特征，探索了一种SEC测定纤维素分子量的方法，为纤维素酯的后续研究及应用提供理论基础和依据。 研究微晶纤维素在DMAc/LiCl体系中的溶解特性，分析了溶剂交换条件及氯化锂含量等对纤维素溶解过程的影响。通过研究...Driven by the growing fear of the depletion of oil, coal and other non-renewable resources, and the global need to focus on renewable and earth-abundant resources, high value-added cellulose-based functional materials and polymers are now spotlighted once again and widespread concerned. A series of studies were carried out in this dissertation on the mild and rapid methods of cellulose esters prep...学位：工学博士院系专业：能源学院_能源化工学号：3242013015402

少数民族地区金融支持经济发展的实证研究

新疆南疆三地州由于自然环境恶劣、生态环境脆弱、交通闭塞、资源匮乏、农业生产基础条件差等诸多原因,导致经济发展水平明显落后于新疆其它地区,成为阻碍新疆经济加快发展的瓶颈地区。文章从金融支持的视角,回顾了近十年来南疆三地州经济发展的现状,分析了金融支持南疆三地州经济发展的症结,提出了金融支持南疆三地州经济发展的政策建议,为金融有效支持南疆三地州的经济发展提供参考。国家社会科学基金项目(08XJL007);世川良一优秀青年研究基金资助项目(XJU-SYLLF09026

Synthesis and characterization of cellulose acetate with high degree of substitution from miscanthus

以芒草为原料,用Na OH/H_2O_2溶液体系预处理制备芒草纤维,在冰醋酸环境下,以浓硫酸为催化剂与醋酸酐酯化制备芒草醋酸纤维素。优化了预处理条件:温度、时间、次数和酯化条件:催化剂量、温度、时间、醋酸酐量,最佳条件下制备出的芒草纤维的纤维素、半纤维素和木质素的质量分数分别为75.3%、17.3%、5.1%,制备出芒草醋酸纤维素的取代度DS=2.8,特性黏度[η]=1.24 d L/g,达到美国联邦贸易委员会指南认定的三醋酸纤维素标准。利用扫描电镜(SEM)和热分析(TG、DSC)对制得样品进行表征。结果表明,可以利用Na OH/H_2O_2水溶液体系预处理芒草原料制备芒草纤维,并进一步酯化制备出高取代度的醋酸纤维素。A procedure for synthesizing cellulose acetate with high degree of substitution from miscanthus biomass is developed. The miscanthus fiber is prepared by pretreatment of miscanthus biomass with Na OH / H_2O_2,which is then reacted with acetic anhydride in an acetic acid solvent to synthesize cellulose acetate by using concentrated sulfuric acid as catalyst. The effects of the pretreatment factors( such as pretreatment temperature,time and number of times) and the esterification factors( such as catalyst volume,reaction temperature,reaction time and acetic anhydride volume) are studied. Under the optimal conditions,the contents of cellulose,hemicellulose and lignin for prepared miscanthus fiber are75. 3%,17. 3% and 5. 1%,respectively. The degree of substitution( DS) and the intrinsic viscosity( [η ]) of the obtained miscanthus cellulose acetate are 2. 8 and 1. 24 d L / g,respectively. The miscanthus biomass,fiber and cellulose acetate are characterized by SEM,TG and DSC. This study shows that cellulose acetate with high degree of substitution can be prepared from miscanthus biomass pretreated with Na OH / H_2O_2.国家自然科学基金(21303142;31170067);; 福建省中青年教师教育科研项目(JA14010);; 厦门市海洋经济发展专项资金项目(14GZP59HJ29);; 福建省海洋高新产业发展专项项目(闽海洋高新[2014]25号);; 厦门大学校长基金(20720150090

几种典型羟基化多溴联苯醚和多溴联苯的合成、纯化及鉴定

通过耦合、氧化和溴化等基本有机化学反应,合成并纯化了几种典型羟基多溴联苯醚和多溴联苯.通过C18半制备高效液相色谱柱对反应粗成品进行分离与纯化,以气相色谱-质谱和氢谱核磁共振对产物进行结构鉴定与表征.结果表明,合成制备的产物与目标物一致,纯度达99%以上.国家自然科学基金(21277124;21477115)资

Formation of hydroxylated polybrominated diphenyl ethers and polychlorinated dibenzo-p-dioxins via goethite-catalyzed oxidation of bromophenols

探究了针铁矿催化转化溴酚(2,4-dbP或2,4,6-TbP)生成羟基化多溴联苯醚(HO-PbdES)和溴代二噁英(Pbdd/fS)的可能性.结果表明,针铁矿可以在常温和干反应条件下有效地催化转化溴酚化合物生成HO-PbdES和Pbdd/fS.反应16 d,97.3%的2,4-dbP被针铁矿氧化转化,其中2.4%被转化为2′-OH-bdE-68,2.8%被转化为2,2′-OH-bb-80,0.2%被转化1,3,8-Trbdd,0.4%被转化为2,4,6,8-TEbdf.同样的反应时间内,98.7%的2,4,6-TbP被针铁矿氧化转化,反应产物可能为2′-OH-bdE-121、4′-OH-bdE-121、1,3,6,8-TEbdd和1,3,7,9-TEbdd.根据检测到的产物,提出了针铁矿氧化转化溴酚的可能途径.The formation of hydroxylated polybrominated diphenyl ethers( HO-PBDEs) and brominated dibenzop-dioxins, dibenzofurans( PBDD/ Fs) from goethite-catalyzed oxidation of bromophenols( BPs, e.g., 2, 4-DBP and 2, 4, 6-TBP) was investigated.Results showed that goethite readily catalyzed the conversion of 2,4-DBP and 2,4,6-TBP to HO-PBDEs and PBDD/ Fs under dry conditions and at ambient temperature.In 16 d, 97.3% of 2,4-DBP was converted and the yields of 2′-OH-BDE-68, 2,2′-OH-BB-80, 1,3,8-TrBDD and 2,4,6,8-TeBDF were 2.4%, 2.8%,0.2% and 0.4%, respectively.Similarly, 98.7% of 2,4,6-TBP was transformed and the possible reaction products were 2′-OH-BDE-121, 4′-OH-BDE-121, 1,3,6,8-TeBDD and 1,3,7,9-TeBDD.The possible formation pathways for the goethite-catalyzed oxidation of bromophenols were proposed.国家自然科学基金(21277124;21477115)资

Therapeutic effects comparison between platelet-rich plasma and sodium hyaluronate intra-articular injection in treatment of knee osteoarthritis

目的关节腔内注射自体富血小板血浆（PRP）与透明质酸钠（SH）,观察并比较其疗效。方法于2012年2月至12月,漳州市解放军第175医院骨科收治的81例Kellgren-Lawrence（KL）分级标准为Ⅱ、Ⅲ级膝关节骨关节炎的患者,年龄48～60岁,平均（52.6±3.6）岁;男性27例,女性53例;左膝38例,右膝43例。K-L分级标准,Ⅱ级47例,Ⅲ级34例,按就诊顺序序贯随机平行分为SH组（40例）和PRP组（41例）,分别采用SH和PRP关节腔内注射进行治疗。治疗前和治疗后3、6、9、12个月对患者进行随访并进行美国西部Ontario与Mc Master大学骨关节炎指数（WOMAC）评分评估,两组间各时间点WOMAC评分比较采用t检验,两组内各时间点WOMAC评分比较采用重复测量方差分析;分别于治疗前和治疗后12个月进行膝关节磁共振检查,评价关节腔内积液的吸收情况。结果治疗前及治疗后3个月PRP组WOMAC评分[（48.42±4.95）分,（25.38±5.12）分]和SH组[（47.17±5.12）分,（25.17±5.09）分]比较,t值分别为-0.625和0.413,差异无统计学意义（P均〉0.05）;治疗后6、9、12个月PRP组WOMAC评分[（21.44±4.73）分,（20.54±4.46）分,（16.53±7.35）分]和SH组[（25.87±5.16）分,（27.22±4.21）分,（29.63±8.21）分]比较,PRP组低于SH组,t值分别为-2.765、-3.447和-4.657,差异具有统计学意义（P均〈0.05）,治疗后12个月复查磁共振,可见PRP组的关节积液吸收例数高于SH组,差异有统计学意义（P〈0.05）。结论膝关节腔内注射自体PRP,临床效果优于透明质酸钠,中长期疗效好。Objective To compare the efficacy of platelet rich plasma （PRP） and sodium hyaluronate （SH） intra-articular injection in the patients with knee osteoarthritis of grade Ⅱand Ⅲ. Methods A total of 81 patients with knee osteoarthritis of grade Ⅱ and Ⅲ （ Kellgren-Lawrence standard） were randomly assigned to the PRP and SH group. All 81 patients were treated in the 175th hospital of PLA, Zhangzhon, with the average age of （52.6 ± 3.6） years. There were 27 males and 53 females. Forty cases in SH group and 41 cases in PRP group had got the complete follow-up. Both the two groups adopted 4 ml of 5% lidocaine for intra-articular injection. All the patients were prospectively evaluated before the treatment and at the 34 , 6th , 9th and 12th month after the treatment by the Western Ontario and McMaster Universities （WOMAC） osteoarthritis index. The swelling subsiding knee was observed. Between the two groups WOMAC scores were compared using t test at each time point, within the groups the scores were compared by repeated measures analysis of variance. The absorption of accumulated fluid in the joint cavity was observed and compared by MRI before and 12 months after the treatment. Results No serious adverse event was detected in the two groups. According to the follow-up evaluations, both the groups presented clinical improvements. The comparison between the two groups showed no statistically significant difference before therapy and three months after the treatment （ t =- 0. 625, 0. 413, P 〉 0. 05 ）. Six months, nine months and 12 months after the treatment, WOMAC score in the PRP group[ （21.44 ±4. 73）, （20. 54 ± 4. 46） ,（16. 53 ± 7. 35 ） pointsl were lower than the SH group[（25.87 ±5.16）, （27.22 ±4.21）, （29. 63 ± 8.21 ） points] ; the difference was statistically signifieant（ t = - 2. 765, - 3. 447, - 4. 657, P 〈 0. 05 ）. Conclusion PRP intra-artieular injection in the treatment of knee osteoarthritis of gradeⅡ and Ⅲ may be more suitable compared to南京军区医学科技创新重点课题项目（15ZD027

金属固溶体热膨胀系数的CALPHAD计算模型

基于计算相图方法(CALPHAD方法),借鉴经典热容模型,通过增加额外的磁性项参数,构建了包含铁磁-顺磁转变的金属固溶体热膨胀系数的CALPHAD计算模型。结合Ni-Fe二元合金的实验结果,采用Levenberg-Marquardt法对模型参数进行了评估,优化得到了300～1200 K范围内Ni-Fe二元金属固溶体热膨胀系数的相互作用参数。采用得到的模型参数,对Ni-Fe二元金属固溶体的热膨胀系数进行了计算,计算结果准确地描述了Ni-Fe二元金属固溶体在居里温度附近的尖锐峰。随着Fe含量的增加,居里温度处的峰值减小,热膨胀曲线由峰状变成谷状,与实验值吻合。该计算模型可以准确计算任意Fe含量<50%(质量分数)的Ni-Fe二元金属固溶体的热膨胀系数。国家重点研发计划项目(2017YFB0701603,2016YFB0701401)福建省自然科学基金项目(2016J01256)国家自然科学基金青年基金项目(51601161

Microwave synthesis of fullerenes from chloroform

Zheng, LS (通讯作者), Xiamen Univ, Dept Chem, State Key Lab Phys Chem Solid Surface, Xiamen 361005, Peoples R ChinaFullerenes C-60 and C-70 were synthesized continuously via microwave plasma from chloroform at low pressure argon atmosphere, and identified in toluene extracts of soot, using high-performance liquid chromatography coupled with atmospheric pressure chemical ionization mass spectrometry and diode-array spectrophotometric detection. Yield of C-60 (0.3%-1.3%) and C-70 (0.1%-0.3%) and their ratio depend on the temperature gradient and the collision probability. Besides fullerenes, a series of perchlorinated carbon clusters were found in the synthesis products. Since frameworks of the products are fragments of fullerenes, the further investigation of this process may lead to a better knowledge of the formation mechanisms of fullerenes. (C) 1999 American Institute of Physics. [S0003-6951(99)03944-3]

The Report about Present Condition and Plan of Student Support Services on Medical and Pharmaceutical Campus : in Relation with the Obligation of Caring for Student\u27s Safety by University

富山大学杉谷（医薬系）キャンパスは、医療系2学部4学科のみからなる。従来、暗黙理に、医師・医療職を目指すに十分な能力とモチベーションをもった学生のみが在籍し、学生支援は必要ないものと理解されてきた。そのため、学生支援を担う部署や教員組織は存在していなかった。かつて学生支援は、医薬系学生課（現医薬系学務グループ）職員、保健医学教員など、その必要性をいちはやく認識した一部の教職員によって個人的に行われていた。杉谷キャンパスの学生支援体制には不備があり、大学としての安全配慮義務の履行や、学生の修学環境保全に、支障をきたしている。支援職種は単一部署に配置すべきである

Formation of buckminsterfullerene and its perchlorinated fragments by laser ablation of perchloroacenaphthylene

通讯作者地址: Zheng, LS (通讯作者), Xiamen Univ, Dept Chem, State Key Lab Phys Chem Solid Surface, Xiamen 361005, Peoples R China 地址: 1. Xiamen Univ, Dept Chem, State Key Lab Phys Chem Solid Surface, Xiamen 361005, Peoples R China 学科类别: Chemistry, Physical; Physics, Atomic, Molecular & Chemical IDS 号: 343CF ISSN: 1089-5639 DOI: 10.1021/jp0012395Perchloroacenaphthylene(C12Cl8), a perchlorinated polycyclic hydrocarbon composed of two hexagons and a pentagon, was ablated by a pulsed laser beam in a vacuum. The products created from the laser ablation were characterized by high-performance liquid chromatography coupled with atmospheric pressure chemical ionization mass spectrometry and rapid-scan ultraviolet spectrophotometric detection. Buckminsterfullerene C-60 and various perchlorinated carbon clusters have been observed among the products. The observation is helpful for understanding the formation mechanisms of fullerenes and suggests that the Pentagon Road scheme is feasible with the involvement of chlorines