含有杂环基侧链的新型聚硅氧烷

含有功能性基团的聚硅氧烷的研究一直是有机硅化学中十分活跃的研究领域之一。当含N、S等杂环引入聚硅氧烷链中后，由于杂环基的生理活性、催化活性及光电特性，因而含不同杂环基团的聚硅氧烷（POS）可分别用作催化剂、光电材料、医学材料等。当用作药物载体时，可提高药物的利用率和靶向性，也可降低某些药物的毒性。含环糊精侧基、冠醚侧基的POS亦可应用于气相色谱固定相、相转移催化剂。本文对近年来有关侧链含有吡啶、咪唑等杂环及环糊精基团等功能性侧基的聚硅氧烷结构、合成、及应用作一详细的评述并进行了展望。     

Effect of substituents (NH2, OH, F) on structures and stability of lithofluorosilylenoids

Isomeric structures and energies of three kinds of lithofluorosilylenoids, R₂SiLiF (R = NH₂, OH, F) were studied using theab initio molecular orbital theory. The calculations show that thermal stability of the three-membered ring structures of these three kinds of silylenoids decreases in the order of substituents NH₂ > OH > F because of the conjugation between NH₂, OH or F and Si atom. The interaction of substituents R with Li atom makes R₂SiLiF have a structure with two Li-A-Si-F (A = N, O, F) four-membered rings, which is the most stable of the isomers of each of three kinds of silylenoids and whose stability decreases in the order of substituents F > OH > NH₂. Inductive effect of substituents influences the thermal stability of the linear structure of silylenoids.     

Effect of substituents (NH_2,OH,F) on structures and stability of lithofluorosilylenoids

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Theoretical study of the thermal rearrangement of chloromethylsilanes, and its mechanism

The thermal rearrangement reactions of chloromethylsilane, (chloromethyl)dimethylsilane, and (chloromethyl)vinylsilane have been studied by use of the density functional theory method at the B3LYP/6-311G(d, p) level. The structures of the reactants, transition states, and the products were determined and fully optimized. The geometries of the different stationary points and the harmonic vibrational frequencies were calculated at the same level. The results showed that thermal rearrangement of the chloromethylsilanes occurred via one pathway. The chlorine atom migrated from the carbon atom to the silicon atom, and the hydrogen atom migrated simultaneously from the silicon atom to the carbon atom through a double-three-membered-ring transition state, forming methylchlorosilane, trimethylchlorosilane, and vinylmethylchlorosilane. The energy barriers of the three rearrangements calculated at the B3LYP/6-311G(d, p) level were 217.4, 201.6, and 208.7 kJ mol^?1, respectively. The effects of alkyl substituents on silicon atom are discussed. Changes of thermodynamic functions, equilibrium constant, and reaction rate constant were calculated in accordance with Eyring transition-state theory over the temperature range 400–1,500 K.     

Thermoresponsive Copolymer/SiO2 Nanoparticles with Dual Functions of Thermally Controlled Drug Release and Simultaneous Carrier Decomposition

The preparation of thermoresponsive drug carriers with a self‐destruction property is presented. These drug carriers were fabricated by incorporation of drug molecules and thermoresponsive copolymer, poly(N‐isopropylacrylamide‐co‐acrylamide), into silica nanoparticles in a one‐pot preparation process. The enhanced drug release was primarily attributed to faster molecule diffusion resulting from the particle decomposition triggered by phase transformation of the copolymer upon the temperature change. The decomposition of the drug carriers into small fragments should benefit their fast excretion from the body. In addition, the resulting drug‐loaded nanoparticles showed faster drug release in an acidic environment (pH 5) than in a neutral one. The controlled drug release of methylene blue and doxorubicin hydrochloride and the self‐decomposition of the drug carriers were successfully characterized by using TEM, UV/Vis spectroscopy, and confocal microscopy. Together with the nontoxicity and excellent biocompatibility of the copolymer/SiO₂ composite, the features of controlled drug release and simultaneous carrier self‐destruction provided a promising opportunity for designing various novel drug‐delivery systems.     

北江干流沉积物重金属污染生态风险评价

通过北江干流水体沉积物重金属含量,研究其典型污染物的潜在生态风险。采集了北江干流韶关至清远段7份沉积物样品,经混酸消解后,以电感耦合等离子体质谱仪测定沉积物中重金属含量,并对沉积物重金属分布特征进行了分析。同时利用Hakanson的潜在生态危害指数（RI）评价模式,对北江干流沉积物重金属生态风险进行了评价。评价结果表明,北江干流沉积物中重金属综合生态危害程度均表现为很高级别,其生态危害因子Pb、Cd已成为北江干流突发性水污染事故潜在预警因子。     

加速溶剂萃取-气相色谱-串联质谱法测定茶叶中10种吡唑和吡咯类农药的残留量

建立了加速溶剂萃取(ASE)-气相色谱-串联质谱(GC-MS/MS)法用于测定茶叶中10种吡唑和吡咯类农药残留。ASE萃取压力为1.03×107 Pa,萃取温度为100 ℃,萃取时间为5 min,萃取溶剂为乙酸乙酯-正己烷(1:1, v/v)。萃取循环1次,萃取液浓缩后用Envi-Carb/PSA固相萃取小柱净化,乙酸乙酯-正己烷(1:1, v/v)洗脱。洗脱液浓缩后,用正己烷定容,供GC-MS/MS测定,外标法定量。方法的准确度和精密度均符合残留分析要求。方法的定量限(LOQ)分别为唑螨酯0.003 mg/kg、氟虫腈硫化物0.001 mg/kg、氟虫腈0.002 mg/kg、氟虫腈砜化物0.005 mg/kg、溴虫腈0.002 mg/kg、氟硅唑0.006 mg/kg、野燕枯0.001 mg/kg、吡草醚0.001 mg/kg、吡螨胺0.0003 mg/kg、唑虫酰胺0.005 mg/kg。方法的灵敏度能满足各国有关农药的残留限量要求。     

Supramolecular Silicone Elastomers with Healable and Hydrophobic Properties Crosslinked by “Salt‐Forming Vulcanization”

In this article, supramolecular silicone elastomers with self‐healing function were first prepared by simple and controllable “salt‐forming vulcanization” of polyaminopropylmethylsiloxane with acids. Their structures and micrographs were verified by Fourier transform infrared spectra, Small‐angle X‐ray scattering experiments and atomic force microscope. The experimental results showed that the ion‐association complexes were formed during vulcanization, and the obtained elastomers displayed self‐healing and good mechanical properties even if the cross‐linking agent was excessed. The thermogravimetric analysis showed that the elastomers crosslinked by inorganic acid were stable under high temperature. Unexpectedly, bionic structures were observed in the elastomers, which further changed the hydrophobicity of the surfaces of the elastomers physically. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 903–911     

Photophysical Properties of Sol–gel derived Luminescent Silicone Hybrids Synthesized via Facile Amino‐Ene Reaction

Novel luminescent silicone hybrids (LSHs) containing lanthanide ions were prepared via different sol–gel processes. The precursor, dimethyl ester‐functionalized silane, was synthesized via a facile amino‐ene reaction. The coordinated assembly of the ester ligands and lanthanide ions (Eu³⁺, Tb³⁺ and Dy³⁺) occurred. The ester ligands were immobilized onto the Si‐O network backbone during the preparation of the silicone hybrid materials. The particle size can be controlled to ca 50 nm by adjusting the solvent ratio. The obtained materials were characterized by Fourier transform infrared, ¹H nuclear magnetic resonance spectroscopy (NMR), ¹³C NMR, ²⁸Si NMR, X‐ray diffraction, X‐ray photoelectron spectroscopy, thermogravimetric analysis, high‐resolution scanning electronic microscopy and luminescent (excitation and emission) spectroscopy. The coordination state and photophysical performance of the compounds were studied in detail. The terbium‐ and europium‐containing materials show sharp green and red emissions, respectively, which indicate that efficient intramolecular energy transfer took place in these LSHs.     

From Polymer to Monomer: Cleavage and Rearrangement of Si‐O‐Si Bonds after Oxidation Yielded an Ordered Cyclic Crystallized Structure

Polymerization reactions are very common in the chemical industry, however, the reaction in which monomers are obtained from polymers is rarely invesitgated. This work reveals for the first time that oxone can break the Si‐O‐Si bond and induce further rearrangement to yield an ordered cyclic structure. The oxidation of P1 , which is obtained by reaction of 2,2′‐1,2‐ethanediylbis(oxy)bis(ethanethiol) (DBOET) with 1,3‐divinyl‐1,1,3,3‐tetramethyldisiloxane (MM^Vi), with oxone yielded cyclic crystallized sulfone–siloxane dimer ( P1‐ox ) after unexpected cleavage and rearrangement of the Si‐O‐Si bond.