N_2和O_2纯转动拉曼光谱(PRRS)的温度特性

计算了N2 和O2 的PRRS ,讨论了其温度特性。提出通过测量N2 和O2 的PRRS计算大气温度的方法。     

TDI三聚体的合成研究

以一种碱金属羧酸盐K-1000作为甲苯二异氰酸酯(TDI)三聚反应的催化剂合成了以TDI三聚体为主要成分的多异氰酸酯固化剂。对合成工艺条件进行了探讨。结果表明,将反应温度控制在35℃,催化剂K-1000用量为0.06%时,用苯甲酰氯作为阻聚剂可得到性能基本稳定的TDI三聚体产品。     

(2-甲基丙烯酰氧乙基)三甲基氯化铵-丙烯酰胺反相微乳液共聚合研究

采用SPAN-OP复合乳化剂和K_2S_2O_8-Na_2SO_3氧化还原引发剂,进行(2-甲基丙烯酰氧乙基)三甲基氯化铵-丙烯酰胺的反相微乳液共聚合。测得单体的竞聚率r_(DM·MC)=1.11±0.16,r_(AM)=0.53±0.08。在单体总浓度为20—40％(wt),引发剂浓度为0.01—0.05％,乳化剂浓度为10—18％,聚合温度为299K的条件下,得到共聚反应动力学方程:R_p=k[M]~(1.07)[I]~(0.52)[E]~(0.90),文中对上述结果做了解释。     

Mechanism of UV photoreactivity of alkylsiloxane self-assembled monolayers

A molecular level understanding of the photoreactivity of self-assembled monolayers (SAMs) becomes increasingly important as the spatial resolution starts to be limited by the size of the resist and the spatial extent of the photochemical reactions in photoresist micropatterning. To this end, a number of surface characterization techniques were combined to understand the reactive agents, reactive sites, kinetics, and reaction pathways in the UV photoreactivity of octadecylsiloxane (ODS) SAMs. Quantitative analysis of our results provides evidence that ground state atomic oxygen is the primary reactive agent for the UV degradation of ODS SAMs. UV degradation, which follows zero-order kinetics, results in the scission of alkyl chains instead of the siloxane headgroups. Our results suggest that the top of the ODS SAMs is the preferential reactive site. Using a novel, highly surface sensitive technique, fluorescence labeling of surface species, we identified the presence of submonolayer quantities chemical functional groups formed by the UV degradation. These groups are intermediates in a proposed mechanism based on hydrogen abstraction.     

Synthesis of 2,3,9,10,16,17,23,24-Octaalkynylphthalocyanines and the Effects of Concentration and Temperature on Their (1)H NMR Spectra

The syntheses of 3,4- and 4,5-diiodophthalonitriles are described. Coupling of the latter compound with Pd(PPh(3))(2)Cl(2) and 1-octyne, 1-heptyne, 1-hexyne, 1-pentyne, and 3,3-dimethyl-1-butyne gave a series of 4,5-dialkynylphthalonitriles. Hydrogenation of 4,5-bis(1-pentynyl)phthalonitrile and 4,5-bis(3,3-dimethyl-1-butynyl)phthalonitrile gave 4,5-dipentylphthalonitrile and 4,5-bis(3,3-dimethylbutyl)phthalonitriles. Condensation of the dialkynylphthalonitriles with lithium 1-pentoxide in 1-pentanol gave 2,3,9,10,16,17,23,24-octaalkynylphthalocyanines, while intervention of the intermediate dilithium phthalocyanines with zinc acetate gave the related zinc(II) phthalocyanines. (1)H NMR spectroscopy of these octaalkynylphthalocyanines exhibited large chemical shifts (1-2 ppm) of the internal and aromatic protons at concentrations ranging from 10(-)(2) to 10(-)(5) M and at temperatures from 27 to 147 degrees C. The effects of aggregation phenomena are discussed. The importance of reporting concentration and temperature values for NMR spectra of phthalocyanines is stressed.     

Methods for generating protein molecular ions in ToF-SIMS

One of the greatest challenges in mass spectrometry lies in the generation and detection of molecular ions that can be used to directly identify the protein from the molecular weight of the molecular ion. Typically, proteins are large (MW > 1000), nonvolatile, and/or thermally labile, but the vaporization process produced by many mass spectrometry techniques including time-of-flight secondary ion mass spectrometry (ToF-SIMS) is inherently limited to generating ions from smaller compounds or fragments of the parent molecule, making the identification of proteins complex. The application of specific molecules to aid in the generation of high molecular weight ions in ToF-SIMS has been recognized for some time. In this study we have developed a matrix-SAM substrate preparation technique based on the self-assembly of a matrix-like molecule, mercaptonicotinic acid (MNA), on gold. We then compare this substrate with two existing ToF-SIMS sample preparation techniques, cationized alkane thiol and matrix-enhanced SIMS (MESIMS). The results of this study illustrate that while there is a range of methods that can be used to improve the molecular ion yield of proteins in ToF-SIMS, their efficacy and reproducibility vary considerably and crucially are linked to the sample preparation and/or protein application methods used. Critically, the MNA modified substrate was able to simultaneously induce molecular ions for each protein present in a multicomponent solution, suggesting that this sample preparation technique may have future application in proteomics and DNA analysis.     

Development of chiral heteroleptic magnesium amides; asymmetric deprotonations mediated by six-membered metallocyclic amidomagnesium naphtholates

A series of enantioenriched six-membered metallocyclic amidomagnesium naphtholates were prepared and used to probe the structure–reactivity/selectivity relationships of heteroleptic magnesium base complexes within asymmetric deprotonation reactions. An effective complex was identified and applied within enantioselective enolisation processes, delivering good levels of enantioselectivity and also revealing key structural requirements for achieving such selectivity.     

二烯丙基二甲基氯化铵—丙烯酰胺反相乳液聚合的动力学特征研究

采用油酸失水山梨醇酯（ＳＰＡＮ）－壬基酚聚氧化乙烯醚（ＯＰ）复合乳化剂与Ｋ２Ｓ２Ｏ８－Ｎａ２ＳＯ３氧化还原引发剂，进行二烯丙基二甲基氯化铵－丙烯酰胺反相乳液共聚合，测得单体的竞聚率为γＤＡＤＭＡＣ＝０．１４±０．１１，γＡＭ＝５．０５±０．６６；在单体浓度为２５─４５％，引发剂浓度０．０６—０．１％，乳化剂浓度为５—９％，聚合温度３０３Ｋ条件下，得到了共聚反应动力学方程：Ｒｐ＝ｋ［Ｍ］０．６８［Ｉ］１．３１［Ｅ］０．７３，文中对上述结果做了解释．     

不确定信息处理及在归纳学习中的应用

信息的不确定性是由于模糊性、随机性、不完全性、不精确性等因素造成的,不确定性信息在现实世界中广泛存在.关于这方面的研究主要集中在模糊性这种不确定性上.我们课题组在此领域的研究已经持续20余年,概括起来讲,早期的研究兴趣在于模糊(非可加)测度与积分的理论建立,主要研究了传统的可加测度与积分理论到非可加情况的推广;尔后的兴趣转向为如何用数值方法确定非可加测度;近期的研究兴趣在于从已有数据中获取模糊控制规则以及具有模糊表示的归纳学习问题.近10年的研究曾得到了多项基金项目资助,出版专著3部,发表学术论文100余篇,30余篇被SCI收录,20余篇被EI收录,省级以上奖励3项.以下是我们近期研究工作的一个总结,主要包括模糊决策树归纳;基于模糊信息的决策表简化;产生模糊规则的扩张矩阵算法;模糊归纳学习在其他领域中的应用;基于示例学习的模糊控制等.     

Fluorescence detection of surface-bound intermediates produced from UV photoreactivity of alkylsiloxane SAMs

Detection and quantification of submonolayer coverage surface species is not trivial. We have developed a novel method sensitive to surface-bound chemical functional groups as low as 10(11) molecules/cm(2) by specific covalent attachment of fluorescent chromophores. This enables the intermediates of the UV photochemistry of alkylsiloxane self-assembled monolayers to be identified.