2,4-二吡啶基方酸衍生物非线性光学性质的从头算研究

采用HF/4-31G方法优化分子几何构型,在此基础上用CPHF研究了系列2,4-二吡啶基方酸衍生物的二阶非线性光学系数βvec,并对影响βvec的因素进行了探讨.结果表明:此类化合物均有很大的βvec,它们的非线性光学性质与其分子结构有着密切的关系.     

方酸衍生物的光敏性与结构关系的理论研究

The geometries of bis(4-dimethylaminophenyl)squaraine and its N and C-2 derivatives have been obtained by AMl and Gaussian 92.The relationship between their photosensitivties and geometries has been studied respectively. The linear relationships between oxidation Potential (EOX) of compounds 1-6 and their HOMO energy (EH), between the Photosensitivity (lgE0.5) of compound 1-5 and ΔET-GOX (the difference of the oxidation potential of charge-transporting material (CTM) and charge-generating material (CGM)), between lgE0.5 and ΔET-G (the difference of the HOMO energy of CGM and CTM) have been studied respectively by the least square fitting method. The result indicates that Eox and EH exhibit certain linearity (r=0.883), the correlation coefficient of lgE0.5 and ΔET-G (r=0.980) is greater than that of lgE0.5 and ET-GOX (r=0.883). It is concluded that the method of calculating the HOMO energy is better than that of detecting the oxidation potential during the study of QSAR of bis(4-dimethylaminophenyl)and its C-2 derivatives. According to the linear relationship obtained by AM1,bis(4-dimethylamino-2,6-fluorophenyl)squaraine has good photosensitivty.     

Fluorinated nitroxides as ESR probes of solvation

Some newly synthesized fluorinated nitroxides, such as t-butyl perfluoroalkyl nitroxides Bu^tN(O) R_f (R_f=CF₃, 5; C₂F₅, 6; n-C₃F₇, 7) and s-butyl perfluoroacyl nitroxides Bu^sN(O) COR_f (R_f=CF₃, 9; n-C₃F₇, 10) have been employed as ESR probes of solvation in different common organic solvents. In aprotic solvents, the measured a_N values for each of the nitroxyl probes show a linear correlation with the cybotactic polar solvent parameters E_T (Dimroth) and Z (Kosowar), i.e. a_N=bE_T+c, and a_N=b′Z+c′. The physical significance for the slope (b or b′), the slope×E_T or slope×Z, the extrapolated intercept on a_N axis, c or c′, are linked, respectively, to the sensitivity of a specific nitroxide toward solvation, the magnitude of the overall solvation effect on the a_N value, and the intrinsic a_N value of each nitroxide in the ideal gaseous state. The intercept on the a_N axis may also serve as a new measure of electronegativity for perfluoroalkyl groups, CF₃, C₂F₅, n-C₃F₇, and perfluoroacyl groups, CF₃CO, n-C₃F₇CO. In protic solvents, i.e. alcohols and carboxylic acids, however, a_N values of all the probes, kept almost no change with the increase in E_T and Z. Furthermore, the plots of a_N versus non-cybotactic solvent constants, such as dipolar moment (μ) and dielectric constant (ε), all show random variations.     

核壳型含氟丙烯酸酯共聚物的合成及性能

采用饥饿态半连续种子乳液聚合方法, 在十二烷基硫酸钠(SDS)/辛基苯基聚氧乙烯醚(TX-10)复合乳化剂的作用下, 分别选用甲基丙烯酸三氟乙酯(TFEM)、甲基丙烯酸六氟正丁酯(HFBM)和甲基丙烯酸十二氟庚酯(DFHM)为含氟单体, 合成以丙烯酸正丁酯(BA)、甲基丙烯酸甲酯(MMA)和含氟单体为原料的核壳型结构含氟丙烯酸酯共聚物乳液. FTIR, 1H NMR, TEM和DSC分析结果显示, 获得了BA/MMA/含氟单体的共聚物乳液, 且乳液具有明显的核壳结构. DSC, TGA和SEM-EDX的分析显示, 核壳型结构的共聚物具有优异的热力学稳定性能和成膜性能; 长侧链或短侧链含氟单体对共聚物的热稳定性影响不明显, 但侧链较长的含氟单体所获得的聚合物在成膜过程中更易向表面迁移, 更能体现含氟聚合物的优点.     

Fluorinated siloxane-containing waterborne polyurethaneureas with excellent hemocompatibility, waterproof and mechanical properties

Two series of polyurethaneurea (PUU) aqueous dispersions consisting of fluorinated siloxane segments were prepared from a high-molecular-weight (M_n = 8361) α,ω-dihydroxypoly[(3,3,3-trifluoropropyl)methylsiloxane] (PTFPMS), dimethylolpropionic acid, isophorone diisocyanate and ethylenediamine, with poly (tetramethylene oxide) and polycarbonate polyols as soft segments, respectively. These anionic aqueous dispersions were stable at the ambient temperature for more than 6 months, with particle sizes ranging from 45 to 98 nm. Both series of PUU films showed the excellent waterproof properties, i.e. the decrease in water absorption and surface energy upon the incorporation of PTFPMS segments. The phase mixing increased in the fluorinated siloxane-containing polyether-based PUUs and the phase separation increased first then decreased in the fluorinated siloxane-containing polycarbonate-based PUUs, with increasing PTFPMS content. All the PTFPMS-modified PUU films showed excellent mechanical properties. The polycarbonate-based PUU film consisting of 5 wt.% PTFPMS had a tensile strength of 60.7 MPa and a breaking elongation of 632%, owing to the increase in the ordered hydrogen bonding degree and the microphase-separation degree between the hard and soft segments in the system. In vitro hemolysis and dynamic clotting time measurements indicated that the thromboresistance was enhanced markedly with increasing PTFPMS content for both series of PUUs, which could be ascribed to the synergistic effect between the carboxylate groups and the PTFPMS segments migrating onto the surfaces of the films.     

Reactions of the Carbonyl Group in Fluorinated Ketones

The chemistry of polyfluorinated ketones has recently received a great deal of attention.

1 A. Ya. Yakoubovich, Usp. Chim. 25, 3 (1956).

2 H. P. Braendlin and E. T. McBee in: Advances in Fluorine Chemistry. Butterworths, London 1963, Vol. 3, p. 1.

3 The review by Braendlin and McBee [2] does not deal only with perfluorinated ketones; moreover, though published in 1963, it is already outdated. The papers discussed in [1,2] will not be reviewed in the present article.

. The carbonyl and imino groups of the fluorinated ketones and their imines react in many different ways. In particular, the electron-attracting perfluoroalkyl groups intensify the electrophilic properties and weaken the nucleophilic properties of the carbonyl group. The perfluoroalkyl group also hinders the heterolytic removal of the hydroxyl group from adducts by reducing the stability of the carbonium ion . The increased electrophilicity of the carbonyl group and the increased stability of the addition products leads not only to a change in reactivity in the characteristic ketone reactions, but also to numerous new reactions which are not observed with non-fluorinated ketones. Thus it is possible to synthesize a wide variety of fluoroorganic compounds from perfluorinated ketones.

4 We have been concerned mainly with hexafluoroacetone, since in addition to being the most readily available and simplest perfluorinated ketone, this is also a typical representative of this class of compounds.

.     

Mechanism of the interaction of color reagent 1, 3-N, N'-bis-4-(4'-nitro benzenediazo) phenyl squaraine with oxoacid anions

By AM1 method, the interactions between 1, 3-N, N′-Bis-4-(4′-nitro benzenediazo) phenyl squaraine (BNBPS) and several oxoacid anions have been studied on the basis of the proposed model. The mechanism of the color reactions is suggested and the answers to the question of whether or not BNBPS colorates with HCO_3~-, CO_3~(2-), NO_2~(-), NO_3~-, etc. are given. It is theoretically predicted that BNBPS might be used as the color reagent for SO_4~(2-).     

ATRP法合成含氟丙烯酸酯类聚合物的研究进展

含氟丙烯酸酯聚合物由于氟原子的改性作用而具有优异的表面特性,不仅稳定,具有很好的耐氧化和耐腐蚀性,而且具有较好的耐水、耐油及耐污性,可望在新材料的开发、理论研究和实际应用等方面获得广泛的应用.而原子转移自由基聚合(ATRP)又可为分子设计和合成提供很有效的途径,利用这种聚合可以获得预期结构和性能的含氟嵌段聚合物材料,充分发挥含氟元素的改性作用.本文综述了ATRP在丙烯酸氟烷基酯聚合物合成方面的应用,并介绍了国内外在此领域的研究状况.     

聚苯基（聚苄基）甲基硅氧烷的氟烷基化反应研究

通过苯基甲基二乙氧基硅烷和苄基甲基二乙氧基硅烷的缩合反应制备了聚苯基甲基和聚苄基甲基硅氧烷。研究了它们与含氟酰基过氧化物间的反应。经酸碱滴定及ＩＲ、＾１Ｈ ＮＭＲ和＾１９Ｆ ＮＭＲ光谱分析确证反应主要生成苯环上氟烷基取代产物。通过测定经氟烷基化后聚硅氧烷处理的玻璃表面的接触角，初步评价了氟烷基化率对其表现性能变化的影响。     

Fluorinated compounds for advanced IC interconnect applications: a survey of chemistries and processes

The semiconductor industry is now in the early stages of an unprecedented change in materials set for the integrated circuit (IC) interconnect structure. The traditional layers of aluminum conductors and silicon dioxide dielectrics are being replaced by copper thin films and a variety of low k candidates, respectively. In many cases, fluorine confers desirable properties on either the precursors or the final films. At the same time, fluorine presents some potentially adverse effects, which have led to a so-called “fear-of-fluorine” in interconnect applications. This paper will review the proposed uses of fluorinated compounds in the interconnect structures, covering both precursors and the resulting thin films. Both the status of technical studies, and the prospects for commercial implementation, will be addressed.     

A fluorescent and chemiluminescent difunctional mesoporous silica nanoparticle as a label for the ultrasensitive detection of cancer cells

A new kind of ultrabright fluorescent and chemiluminescent difunctional mesoporous silica nanoparticle (FCMSN) is reported. A luminescent dye, Rhodamine 6G or tris(2,2′-bipyridyl)dichlororuthenium(II) hexahydrate (Rubpy), is doped inside nanochannels of a silica matrix. The hydrophobic groups in the silica matrix avoid the leakage of dye from open channels. The amines groups on the surface of the FCMSN improve the modification performance of the nanoparticle. Because the nanochannels are isolated by a network skeleton of silica, fluorescence quenching based on the inner filter effect of the fluorescent dyes immobilized in nanochannels is weakened effectively. The Quantum Yield of obtained 90 nm silica particles was about 61%. Compared with the fluorescent core–shell nanoparticle, the chemiluminescence reagents can freely enter the nanoparticles to react with fluorescent dyes to create chemiluminescence. The results show that the FCMSN are both fluorescent labels and chemiluminescent labels. In biological applications, the NaIO₄ oxidation method was proven to be superior to the glutaraldehyde method. The amount of amino could affect the specificity of the FCMSN. The fluorescence microscopy imaging demonstrated that the FCMSN is viable for biological applications.     

含氟聚酰亚胺及其在微电子工业中的研究进展Ⅱ含氟聚酰亚胺在微电子工业中的应用

综述了近年来国内外在含氟聚酰亚胺(PI)研究及应用领域中的最新进展情况。主要从现代微电子工业对相关材料的性能要求、标准型聚酰亚胺材料所面临的挑战以及新型含氟聚酰亚胺在微电子工业中的应用等几个方面进行了详细的综述。重点阐述了中国科学院化学研究所305组近几年在这方面的研究进展情况。并指出为了推动我国微电子工业的发展，研制开发低成本、高技术含量的含氟聚酰亚胺材料具有十分重要的现实意义．     

高热稳定性氟化聚酰亚胺的合成及在热光开关中的应用

用一种新型超支化氟化聚酰亚胺(FHBPI)作为波导材料制备了聚合物热光开关. 采用DSC, TGA, 近红外吸收谱和原子力显微镜(AFM)等方法对FHBPI的热稳定性及光学特性进行了表征. 结果显示, FHBPI的玻璃化转变温度为189 ℃, 在空气中5%的热失重温度为596 ℃, 表明具有良好的热稳定性; 旋转涂膜法制备的FHBPI薄膜具有良好的成膜性; 薄膜表面粗糙度为0.54 nm; FHBPI在光通信波段有较小的吸收损耗, 适合制备低损耗的光波导器件; 用FHBPI-50为波导芯层材料, FHBPI-30为包层材料, 设计制作的热光开关响应上升时间为267.9 μs, 下降时间为254.1 μs.     

一种有助于稳定锂金属循环的富氟化位点框架结构

锂金属是下一代高能量密度二次电池的理想负极材料,然而它的应用仍然受制于较差的循环稳定性。近期,二维氟化界面被广泛用于改善锂金属负极的成核机制、沉积形貌和循环稳定性。本工作通过将体积缩小化的氟化石墨颗粒与锂离子传导网络结合,获得了一种富氟化位点的三维框架结构。实验结果证明此类三维氟化结构可显著提升锂金属负极在不同电流密度和容量下的循环稳定性,且优于二维氟化界面结构。通过本工作的研究,证明了相较于单纯的二维氟化界面,三维锂离子传导网络和富氟化位点的合理结合可以成为一种改进的界面结构用于锂金属负极保护,为高能量密度锂金属电池的负极保护提供了新的设计思路。     

方酸衍生物的光敏性与结构关系的理论研究

量子化学方法早已成功地运用于探索药物分子的定量构效关系（QSAR）[1，2]，然而通过查阅近十几年的CA，发现用该方法进行有机光导材料（OPC）的QSAR研究工作甚少［3，4］．据推测，造成这种情况的原因是，影响OPC的光导性能的因素太多．例如，化合物的纯度、电行产生层（CGL）厚度、电行产生材料（CGM）与高分子粘结剂的配比、颗粒大小、结晶度、堆积方式、从CGL到电荷传输层（CTL）的空穴注人效率等．这么多的影响因素无疑是量子化学方法研究OPC的难点．随着大量OPCat合成出来及OPC研究的逐步深入，采用量子化学方法探讨化…     

An enzymatic method for site-specific labeling of recombinant proteins with oligonucleotides

DNA was site-specifically conjugated to a substrate peptide of microbial transglutaminase fused to the N- or C-terminus of target proteins without the loss of the proteins' functions of interest.     

Fluorinated modification of hyperbranched polyesters used for improving the surface property of UV curing coatings

The commercial hyperbranched aliphatic polyols (Hn) were modified by thioglycolic acid (TA) and hexafluorobutyl acrylate (HFBA) or dodecafluoroheptyl methacrylate (DFHMA) to prepare a series of fluorinated hyperbranched polyesters. For comparison, a linear fluorinated polymer, poly(n-BMA-co-DFHMA), was synthesized through the copolymerization of n-butyl methacrylate (BMA) and DFHMA. The molecular structures were characterized by ¹H NMR spectroscopic analysis. The synthesized polymers were incorporated into UV-curable formulations as additives, and exposed to a UV lamp. After UV curing, the wettability of the films was investigated by contact angle measurement with water and 1-bromonaphthalene. The results showed that both the hydrophobicity and oleophobicity were greatly enhanced. Moreover, the fluorinated hyperbranched polymers possessed better water and oil repellency than the copolymer poly(n-BMA-co-DFHMA) at a very low concentration. The surface F/C ratio values of the cured films were detected by XPS analysis, and the film with TAH20-DFHMA showed the highest F/C ratio value, indicating its most efficient aggregation effect at the film surface.     

硬段侧链含有氟化双季铵盐的聚氨酯表面性能及抗菌性能分析

研究了硬段侧链含有氟化双季铵盐的系列聚氨酯(FQPUs)的表面性能和抗菌性能. 水接触角测试和表面自由能测试结果表明, 加入少量氟化双季铵盐扩链剂, 可以使聚氨酯表面富集氟碳链, 氟化双季铵盐聚氨酯表面自由能很低, 具有很好的抗黏附性能. 迁移到表面的两条氟碳链在常温下不会发生链反转, 使材料的抗黏附性能得以保持. 同时, 使材料表面形成一层疏水层, 减小材料的吸水率. XPS研究结果表明, 氟碳链的-CF₃位于材料的最外层, 材料的次表面是具有良好杀菌性能的双季铵盐, 这样形成了具有多重抗菌性能的表面. 另外, XPS研究结果表明, 材料表面化学结构与材料本体的微相分离结构相关. 抗菌性能测试结果表明, 氟化双季铵盐聚氨酯抗金黄色葡萄球菌的能力很强, 对于大肠杆菌的抗菌效果有所下降, 但相对于单季铵盐聚氨酯的抗菌效果有一定提高.     

Synthesis of Fluorinated Urchin-like Serried Hydroxyapatite with Improved Water Sorption-Solubility and Bioactivity for Dental Composites

Fluorine is present in the hydroxyapatite mineral in natural tooth enamel, which plays a key role in the prevention of dental caries. The aim of this study is to synthetize the fluorinated urchin-like serried hydroxyapatite(FnUHA) particles with different degrees of fluorine substitution and explore the effect of the fluorine element on the water absorption-solubility, mechanical strength, and biological activity of dental composites. The obtained FnUHA particles were further modified with 3-methacryloxypropyl trimethoxysilane(γ-MPS) to get the silanized FnUHA(SFnUHA) particles, which were then used as the reinforcement for dental composites. The morphology, compositional elements, and structure of the FnUHA were characterized by field-emission scanning electron microscopy(FE-SEM), transmission electron microscopy(TEM), X-ray photoelectron spectroscopy(XPS), X-ray diffractometer(XRD), and Fourier transform infrared spectrometer (FTIR), respectively. The mechanical properties of the SFnUHA reinforced composites with different filler loadings were measured with a universal testing machine. The results demonstrated that the 50%(mass fraction) SF5UHA filled composite exhibited the acceptable flexural strength and compressive strength, giving the respective improvements of 56.3% and 30.8% compared with those of the 50% SUHA filled composite. In addition, this composite also presented lower water absorption-solubility, better in vitro bioactivity, and excellent cell viability. Therefore, fluorinated hydroxyapatite is a promising filler to improve the mechanical properties and functionality of dental composites.