亚临界水条件下煤中汞的脱除

运用半连续反应装置对山西吴家坪煤中汞在亚临界水中的脱除规律进行了研究。考察了反应温度为290 ℃、320 ℃ 、350 ℃、 380 ℃，反应压力为5 MPa、10 MPa、15 MPa,萃取时间为10 min、30 min、60 min、100 min时对汞脱除率的影响。结果表明，在290 ℃～380 ℃，随着温度升高，汞脱除率明显增加；在5 MPa～15 MPa，压力越大，汞的脱除率也越大；在10 min～100 min，随着萃取时间的延长，汞脱除率增加；在380 ℃, 15 MPa, 1 h，汞的脱除率最大可达96％以上。     

芯片电泳推拉式压力进样方法

芯片电泳作为微流控分析系统的典型代表,广泛涉及材料、微加工方法、微液流控制、分离模式和检测方法等诸多方面.与传统分析系统一样,样品制备和引入也是微全分析系统实现样品到结果首先面临的问题.电进样一直是芯片电泳系统的主流进样方法.而传统毛细管电泳系统中与电进样同样经常使用的压力进样方法则很少用于芯片电泳系统.     

聚合酶链式反应微芯片系统用于微量生物样品的快速扩增检测

基于MEMS微加工技术设计和制作了一种集成微加热器和温度传感器的聚合酶链式反应（PCR）微芯片。PCR微芯片结构通过有限元模拟验证分析。该芯片在PCR扩增过程中具有良好的制热效率和热传递均匀性。在微型温度控制电路装置下进行热循环反应,芯片的温度起伏小于1℃／s,升降温速度分别达到5℃／s和3℃／s,30个热循环耗时30min。此系统已经用于GUS基因的扩增检测,获得了良好的结果,极大的缩短了热循环的时间,可用于微量生物样品的快速扩增检测。     

氢化燃烧法合成La1.5Ni0.5Mg17的工艺优化

采用正交实验设计方法安排实验，运用L9(3^4)优化氢化燃烧法合成La1.5Ni0.5Mg17的工艺，考察了施压制饼时间、合成保温时间、合成起始氢气压力、保温温度4个因素对储氢材料的储放氢容量和速率的影响，通过直观分析和方差分析得出优化的工艺为：保温温度903K，制饼施压时间40min，合成起始氢气压力为1MPa，合成保温时间1800min。此条件下合成储氢材料La1.5M0.5Mg17在573K的储放氢容量分别为：5．40和5．15％H(质量分数)；储放氢速率分别为：0．734和0.681％H／min。用XRD分析了材料吸氢和脱氢后的物相结构发现：用Ni适量取代La2Mg17中的La没有导致结构变化，存在的LaNi5，LaH3和La改善了材料的吸放氢速率。     

玻璃芯片上温控微阀的制备和微流体控制性能研究

聚N-异丙基丙烯酰胺(PNIPAAm)在临界温度(32 ℃)附近会发生敏锐的相变, 导致其体积和表面亲疏水性的突变. 利用这种由温度刺激引起的体积变化, 可以控制微通道内微流体的运动状态. 本文以2-羟基-2-甲基-1-苯基丙酮为引发剂, 水-乙醇混合体系为溶剂, 在玻璃芯片通道内局部区域以紫外光诱导聚合PNIPAAm整体柱塞, 制备温控微阀. 系统地考察了聚合条件对该阀的形态和性能的影响. 在此基础上, 建立了一个芯片上的集成化单温控阀流动注射分析模型, 利用镁离子与荧光探针O,O'-二羟基偶氮苯的螯合荧光反应, 表征温控微阀的控流效果. 结果表明, 所制作的微阀温控效果良好, 在微流控领域有应用前景.     

聚二甲基硅氧烷基质微流控芯片封接技术的研究

考察了聚二甲基硅氧烷(Polydimethylsiloxane,PDMS)预聚体与固化剂间的配比、固化温度及固化时间对PDMS芯片封接强度的影响,得出PDMS芯片封接的最佳条件基片和盖片所用PDMS预聚体与固化剂质量配比分别为10∶1与5∶1,固化温度为75℃,固化时间分别为35～50min和25～40min,封接后继续加热60min.在该条件下封接制作的微芯片历经半年50多次的分析、冲洗及抽液后未见明显损坏,足以满足一般分析任务的要求,并将芯片成功用于两种氨基酸的快速毛细管电泳分离.     

微流控芯片液-液萃取-气相色谱联用系统的研究

微流控芯片多相层流技术自Yager等^[1]首次报道以来,已广泛应用于芯片上无膜渗析、过滤和萃取等前处理过程.2000年,Kitamori等^[2]报道了基于多相层流原理的芯片上液-液萃取系统,利用在微通道内形成并行流动的有机相和水相层流体系,通过溶质在液流间的分子扩散作用完成无膜的萃取分离操作.     

基于3D打印技术的集成核酸提取芯片制备

基于固相萃取原理,设计并制作了一种集成核酸提取功能的微流控芯片,用于人体全血中脱氧核糖核酸(DNA)的提纯。芯片主要包括:混合微通道、裂解腔、DNA提取腔、DNA存储腔。采用3D打印技术制作出芯片模板,通过模板注塑成型、氧等离子体键合等工艺制作出微流控芯片。利用该芯片,可以在20 min内完成血液和试剂的顺序加载、快速混合、血细胞裂解、DNA的提取等操作,且试剂消耗量少。通过对所提DNA链上稳定表达的内参基因甘油醛-3-磷酸脱氢酶(GAPDH)进行PCR扩增,并对扩增产物进行熔解曲线分析,以验证所提取DNA的质量。     

集成核酸提取的实时荧光PCR微全分析系统

集成核酸提取的实时荧光PCR微全分析系统将核酸提取、PCR扩增与实时荧光检测进行整合,在同一块微流控芯片上实现了核酸分析过程的全自动和全封闭,具有试剂用量少、分析速度快、操作简便等优点。本研究采用微机械加工技术制作集成核酸提取微流控芯片的阳极模,使用组合模具法和注塑法制作具有3D通道的PDMS基片,与玻璃基底通过等离子体键合封装成集成核酸提取芯片。构建了由微流体速度可调节(0~10 mL/min)的驱动控制装置、温控精度可达0.1℃的TEC温控平台、CCD检测功能模块等组成的微全分析系统。以人类血液裂解液为样品,采用硅胶膜进行芯片上核酸提取。系统根据设置好的时序自动执行,以2 mL/min的流体驱动速度完成20μL裂解液上样、清洗;以1 mL/min的流体驱动速度完成DNA洗脱,抽取PCR试剂与之混合注入到反应腔。提取的基因组DNA以链上内参基因GAPDH为检测对象,并以传统手工提取为对照,在该系统平台上进行PCR扩增和熔解曲线分析实验。片上PCR扩增结果显示,扩增曲线明显,Ct值分别为25.3和26.9。扩增产物进行熔解曲线分析得到的熔解温度一致,均为89.9℃。结果表明,此系统能够自动化、全封闭的在微流控芯片上完成核酸提取、PCR扩增与实时定量分析。     

聚合酶链式反应微流控芯片的准分子激光制备和应用研究

摘要采用价格便宜的聚甲基丙烯酸甲酯(PMMA)代替价格昂贵的硅或玻璃作为聚合酶链式反应(PCR)微流控芯片的基片材料,采用柔性大且自动化程度高的准分子激光微加工方法代替加工工艺复杂的光刻化学腐蚀方法,在19 kV和18 mm/min的优化加工参数下,在48 mm×67 mm×1 mm的PMMA基片上制备出20个循环的PCR微流控芯片. 芯片微通道横截面呈梯形,底面光滑. 微通道宽104 μm,深56 μm,长2 060 mm,加工耗时约110 min. 该芯片和相同尺寸的盖片在160 N和105 ℃条件下通过热压经20 min键合在一起,键合强度为0.85 MPa. 键合后的芯片和温控系统集成在一起,采用比例积分微分(PID)方法得到的控温精度为±0.2 ℃,采用红外热像仪得到的相邻温区间的温度梯度分别为16.5和22.2 ℃,最后利用该芯片在对170 bp的DNA片段实现了体外扩增.     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.