氢离子选择性液膜超微电极的研制

本报道新的以三－十二烷基胺（ＴＤＤＡ）为载体和以对氯苯硼四－十二铵（ＥＴＨ２１９１）为载体的ｐＨ微电极膜，与原有的ＴＤＤＡ膜相比较，新的ＴＤＤＡ膜和ＥＴＨ２１９１膜制备更加容易，膜内阻从原有的２×１０＾１１Ω（１μｍ）下降到３．５×１０＾１０Ω（１μｍ），其中ＥＴＨ２１９１膜的动力学响应ｐＨ范围为１２～４．５，与原有的ＴＤＤＡ膜（ｐＨ范围为１２～５．５）比较，拓宽了１个ｐＨ，而且ＥＴＨ２１９１膜     

TS—1分子筛的合成

利用＾２９Ｓｉ和＾１ＨＮＭＲ方法研究了ＴＳ－１分子筛合成过程中正硅酸乙酯（ＴＥＯＳ）的水解行为，＾１ＨＮＭＲ结果表明，ＴＥＯＳ在四丙基氢氧化铵（ＴＰＡＯＨ）溶液中的水解速度快于在四乙基氢氧化铵（ＴＥＡＯＨ）中的水解速度，ＴＥＯＳ水解后的＾２９ＳｉＮＭＲ谱显示，ＴＥＯＳ在ＴＰＡＯＨ中水解产生的合硅酸根物种的分布与ＴＥＡＯＨ中的类似，都存在着单体、二聚、三聚及环聚等硅酸根物种的平衡，但ＴＥＯＳ－ＴＥＡ     

磷酸酯类阴离子表面活性剂的~（31）P－NMR波谱分析

用~（３１）Ｐ核磁共振波谱定性定量分析了烷基磷酸酯盐（Ｉ）和烷基聚氧乙烯醚磷酸酯盐（Ⅱ）中各含磷组分及其含量。研究了溶液ｐＨ值、氯化钠含量、样品浓度等对各组分~（３１）Ｐ化学位移的影响。探讨了影响定量准确度的因素；找出了最佳分析条件。     

丙烯酰胺和表面活性大单体共聚物的合成及其性能研究

首先合成表面活性大分子单体丙烯酸聚氧乙烯（２３）－十二烷基酯（ＡＡ－ＰＯＥＬＥ）,再通过与丙烯酰胺共聚合的方法得到在水溶性聚合物聚丙烯酰胺分子结构中引入疏水基团的共聚物改性ＰＡＭ。因ＡＡ－ＯＰＥＬＥ单体具有表面活性,所以共聚合时无需添加乳化剂。当改性ＰＡＭ中疏水基团含量为１．１０ｍｏｌ％时,其水溶液表现出独特的流变性和增稠性,着重讨论了改性ＰＡＭ作为乳胶增稠剂的性能。     

磷酸酯类阴离子表面活性剂的^31P—NMR波谱分析

用＾３１Ｐ核磁共振波谱定性定量分析了烷基磷酸酯盐（１）和烷基聚氧乙烯醚磷酸酯盐（２）中各含磷组分及其含量。研究了溶液ＰＨ值、氯化钠含量、样品深度等对各组分＾３１Ｐ化学位移的影响。探讨了影响定量准确度的因素；找出了最佳分析条件。     

1－苯基－3－甲基－4－（a－呋喃甲酰基）－5－吡唑酮与中性萃取剂协同萃取镱的研究

研究了１－苯基３－甲基－４－（呋喃甲酰基）－５－吡唑酮（ＨＡ）萃取镱及其分别与丁基辛基亚砜（ＢＯＳＯ）、戊基已基亚砜（ＰＨＳＯ）、乙基十二烷基亚砜（ＥＤＳＯ）、二苯亚砜（ＤＰＳＯ）和ＴＢＰ协同萃取镱的行为。协萃配合物的组成为ＹｂＡ＿３·Ｂ，ＨＡ的萃取平衡常数为—５．６４±０．０４，中性萃取剂的协萃能力比单独萃取时高３～４个数量级，协萃效果明显。     

季铵盐从氰化物溶液中萃取金的研究:基于氢键结构的萃合物模型

通过 Ｆｏｕｒｉｅｒ变换红外光谱（ＦＴ－ＩＲ）,扩展Ｘ射线吸收精细结构（ＥＸＡＦＳ）,等离 子发射（ＩＣＰ）和同位素示踪等方法对氯化甲基三烷基铵（Ｎ２６３）－磷酸三丁酯（ＴＢＰ）－正十二 烷和Ｎ２６３－异辛醇－正十二烷从ＫＡｕ（ＣＮ）_２水溶液中萃取金的机理进行了深入的研究．应 用高分辨红外光谱证实负载有机相中ＣＮ伸缩振动吸收随萃金体系中助萃剂的不同而不 同,并将负载有机相中Ａｕ（ＣＮ）_２~－与助萃剂的相互作用归因于氢键机制,认为萃金体系中 的萃合物模型为基于氢键的超分子体系     

多核Nd-Al双金属配合物对丁二烯的聚合 Ⅳ.烷基铝种类的影响

利用多核Ｎｄ－Ａｌ双金属配合物可单独引发双烯烃聚合的特点，考察了烷基铝种类对丁二烯加聚过程的影响，并与一般混合稀土催化体系进行了比较．烷基铝对活性体催化活性的影响与其用量有关，低ｎ（Ａｌ）／ｎ（Ｎｄ）值时，活性次序为：ＡｌＭｅ３，ＡｌＥｔ３，ＨＡｌＢｕｉ２＞Ａｌ（Ｃ８Ｈ１７）３＞ＡｌＢｕｉ３；高ｎ（Ａｌ）／ｎ（Ｎｄ）值时，活性次序相反：ＡｌＭｅ３，ＡｌＥｔ３，ＨＡｌＢｕｉ２＜Ａｌ（Ｃ８Ｈ１７）３＜ＡｌＢｕｉ３．烷基铝链转移作用强弱次序为：ＨＡｌＢｕｉ２≥ＡｌＥｔ３＞ＡｌＢｕｉ３＞ＡｌＭｅ３＞Ａｌ（Ｃ８Ｈ１７）３．根据聚丁二烯微观结构与其分子量的关系，可将烷基铝对聚丁二烯顺式含量的影响分为３类：（１）ＡｌＥｔ３和Ａｌ（Ｃ８Ｈ１７）３；（２）ＨＡｌ－Ｂｕｉ２和ＡｌＢｕｉ３；（３）ＡｌＭｅ３．所得结果有助于对稀土催化定向聚合过程的深入了解．     

以阳离子乳化剂进行丙烯酸丁酯－苯乙烯乳液共聚的动力学研究

采用十二烷基二甲基苄基氯化铵（１２２７）乳化剂，对丙烯酸丁酯（ＢＡ）－苯乙烯（Ｓｔ）进行乳液共聚，研究了影响聚合速度的各种因素，得出了聚合速率方程和表观活化能．     

聚N－烷基丙烯酰胺类凝胶及其温敏特性

 研制成功５种聚Ｎ－烷基丙烯酰胺类温敏凝胶：聚Ｎ－异丙基丙烯酰胺（ＰＮＩＰＡ），聚Ｎ－异丙基丙烯酰胺＋甲基丙烯酰胺（ＰＮＩＰＡ／ＭＡＡ），聚Ｎ，Ｎ－二乙基丙烯酰胺（ＰＮＤＥＡ），聚Ｎ－正丙基丙烯酰胺（ＰＮＮＰＡ），聚Ｎ，Ｎ－二乙基丙烯酰胺＋Ｎ－叔丁基丙烯酰胺（ＰＮＤＥＡ／ＮＴＢＡ），并系统研究了这些凝胶的温敏相交特性．以聚Ｎ－异丙基丙烯酰胺（ＰＮＩＰＡ）凝胶相交特性为基础的凝胶萃取过程对牛血清白蛋白和兰葡聚糖溶液的浓缩实验表明，凝胶萃取对于浓缩和制备贵重生化制品是很有效的．     

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%.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

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.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

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.