硅酸钠与有机硅氧烷前驱体合成有机官能化硅基介孔材料

采用有机硅氧烷（RTES）与硅酸钠（Na2SiO3)共水解缩聚合成有机官能化的 MSU型硅基介孔材料，当前驱体中RTES和硅酸钠的摩尔比为0.1:0.9时合成了R－ MSU（R＝甲基，氨基）分子筛，通过现代分析技术证明有机官能团均进入材料骨架 。选用CH3－MSU合成体系，考察了合成温度、前驱体与模板剂摩尔比及前驱体中有 机硅氧烷含量等反应参数对材料织构性能的影响，发现通过简单地调节反应参数， 能较好地控制材料的结构和表面特性。     

大分子植酸-聚有机硅倍半氧烷的合成及性能

采用溶胶-凝胶方法, 无需小分子酸催化剂, 利用硅烷化植酸的反应活性和酸催化活性, 与硅烷单体共水解缩聚, 在聚有机硅倍半氧烷分子链上原位接枝植酸, 合成了分子量大于50000的大分子植酸-聚有机硅倍半氧烷. 用GPC, 13C NMR, 29Si NMR, XPS, Raman光谱, SEM及电化学测试等分析手段进行表征, 对比不同酸催化植酸-聚有机硅倍半氧烷(PAP), 单宁酸-聚有机硅半氧烷(TAP), 盐酸-聚有机硅半氧烷(HCP)的结构和性能, 发现植酸-聚有机硅倍半氧烷上的螯合基团与金属表面的活性基团反应而键合, 在金属表面形成致密的保护膜, PAP与TAP和HCP比较具有优异的防腐性能.     

有序的介观尺寸生物SiO2针的合成

生物体利用生物矿化作用,在有机分子模板上协同合成有种间差异的生物SiO2材料。具有精确形态可控的固态SiO2结构是在蛋白和多糖生物分子诱导下,在水相、中性pH和室温等温和反应条件下形成的,然而,利用化学合成方法,使SiO2的前体分子聚合形成具有一定模式结构的SiO2则需要极端的pH值或表面活性剂诱导。在人工培养条件下施用硅酸钠(Na2SiO3)时,在芦荟植物叶刺内,以细胞壁为模板生物矿化合成微米尺寸有序SiO2材料。X-ray(EDX)能谱分析显示一根硅针中含有Si,O和C元素,表明Si(OH)4吸收进入植物体内后Si-OH与细胞壁多糖和糖蛋白上的羟基(OH)组分,通过界面分子识别、细胞水平调控和再加工作用,聚合形成了有序的无定形(电子衍射确定)SiO2针状结构体。     

含二苯甲酮基的有机硅光引发体系

在UV照射下,用含巯基的有机硅化合物与聚甲基乙烯基硅氧烷加成硫化虽有专利报道,但该反应体系是以二苯甲酮类化合物作为光敏剂。当我们进行这方面研究时,发现二苯甲酮与有机硅氧烷预聚物相容性差,从而影响光加成反应的速度。为了改善光敏剂与有机硅预聚物的相容性,本文合成了具二苯甲酮基团的环状有机硅氧烷及其高聚物作为光敏剂。     

有机官能团对硅基MSU-X织构性能的影响

采用有机硅氧烷(RTES)与硅氧烷(TEOS)共水解缩聚合成了有机官能化的MSU-1中孔材料(R=甲基,苯基,乙烯基,脲丙基)。当前驱体中RTES与TO64EOS的摩尔比为0.1:0.9时合成R10-MSU-1分子筛,通过现化分析技术证明BA所选有机官能团均能进入分子筛骨架,而且在相同摩尔数的各数有机硅氧烷存在下,由于其反应速率、空间位阻的不同使其对骨架的缩聚程度、孔道和表面性质有不同的影响。利用SAXS实验技术对所合成R10-MSU-1材料结构表面以及由于有机官能团的存在对无机骨架产生的影响进行了研究。SAXS较强的散射强度分布对Porod定理形成负偏离,表明孔和基体之间有明显的界而层存在,并求得界面层的平均厚度。实验证明有机基团的均匀分布于孔道表面而形成有机界面层。SAXS测试还显示上述分子筛呈质量分形特征,其形成过程可能为非平衡非线性的聚集机制。     

聚有机硅倍半氧烷的合成及其在涂层材料中的应用

聚有机硅倍半氧烷由于具有优异的力学、电学、光学性能,近年来被广泛应用作涂层材料以提高其热稳定性、耐腐蚀性、耐磨性、耐刮伤性、绝缘性等。介绍了聚有机硅倍半氧烷的合成方法及其在涂层材料中的应用。     

含安息香醚的硅氧烷合成及性能研究

在紫外光引发聚合过程中,安息香醚在光敏有机硅预聚物中相容性较差,从而影响聚合物光敏固化速度。为了改进其相容性,曾有文献报道合成含安息香醚的有机硅氧烷的有关工作。我们采用七甲基环四硅氧烷与α-烯丙基安息香醚(Ⅰ_(a,b))加成的方法,合成了未见报道的以碳硅键合安息香乙醚或丁醚为侧基的环状有机硅氧烷(Ⅱ_(a,b)),将其开环聚合得到相应的线型聚有机硅氧烷(Ⅲ_(a,b)),通过~1H NMR、IR、UV和元素分析对Ⅰ_(a,b),Ⅱ_(a,b)和Ⅲ_(a,b)的化学结构进行了表征,并研究了紫外光照射下Ⅰ_(a,b)、Ⅱ_(a,b)和Ⅲ_(a,b)对聚甲基γ-(甲基丙烯酰氧)丙基硅     

采用共缩聚法制备含手性Mn(Ⅲ)salen结构的有序介孔有机硅材料

将含手性Mn(Ⅲ)salen结构的桥连有机硅烷在十六烷基三甲基溴化铵为模板剂的条件下,与正硅酸乙酯按不同比例共缩聚,合成一系列含手性Mn(Ⅲ)salen结构的有序介孔有机硅(PMOs)材料,并对其进行XRD、FT-IR和热重表征。分别考察了静态法(釜中110℃晶化)与动态法(80℃搅拌晶化)合成对材料结构的影响,结果表明,采用动态法合成能够在较高的有机硅烷投料量下得到更为有序的PMOs材料。     

含羧基聚有机硅氧烷—PEO复合物与LiCF3SO3复合膜的离子传导性

本文研究了含羧基聚有机硅氧烷——PEO复合物与LiCF_3SO_3复合膜的离子传导性能。实验结果表明,利用PEO与含羧基聚有机硅氧烷复合的方法能进一步提高含羧基聚有机硅氧烷—Li~+固体电解质膜的离子传导性。此复合膜在室温下的离子导电率可达10~(-5)S cm~(-1)。本文还研究了复合膜中所用PEO的分子量、PEO用量,LiCF_3SO_3含量、交联剂用量及温度对复合膜离子传导性的影响。     

杯芳烃交联聚硅氧烷热稳定性能研究

聚有机硅氧烷是一类主链由硅-氧键连接而成,侧链为有机基团的聚合物,兼具有机聚合物和无机聚合物的特性,性能优异,尤以卓越的耐高温性能而著称,在大气中于-50~250℃可以长期使用[1].为了进一步提高聚有机硅氧烷的热稳定性,主要有以下几种方法,(1)添加各种耐热性添加剂,或可与聚     

对丙烯腈聚合有高活性的催化体系

铵甲基配合物;对丙烯腈聚合有高活性的催化体系;苯甲酚钠;萘酚钠;季铵盐;催化聚合     

Two extended structures constructed from sandwich-type polyoxometalates functionalized by organic amines

Two new compounds constructed from tetra-Ni-substituted sandwich-type polyoxometalates functionalized by organic groups, (NH(4))(2)[Ni(4)(enMe)(8)(H(2)O)(2)Ni(4)(enMe)(2)(PW(9)O(34))(2)].9H(2)O (enMe = 1,2-diaminopropane) (1) and Na(2)[H(6)N(2)(CH(2))(6)](2){Ni(4)[H(4)N(2)(CH(2))(6)](2)(H(2)PW(9)O(34))(2)}.7H(2)O (2), have been successfully synthesized under hydrothermal conditions. Single-crystal X-ray diffraction analysis is carried out on these two compounds (1 and 2), which both crystallize in the triclinic system. Compound 1 represents the first example of a 2D layer structure consisting of the sandwich-type polyoxoanions with six supporting [Ni(enMe)(2)](2+) moities and two organic functionalized groups. Compound 2 exhibits a 1D chain-like structure based on sandwich-type polyoxoanions and sodium cations, which are further connected into a 2D layer structure via hydrogen-bonding interactions between the 1,6-hexanediamine molecules and the sandwich-type [Ni(4)(H(4)N(2)(CH(2))(6))(2)(H(2)PW(9)O(34))(2)](6-) polyoxoanions. A magnetic study of the two compounds indicates that intramolecular ferromagnetic Ni-Ni interactions exist in the tetranuclear metal cluster.     

Syntheses, derivatives, solubility, and interfacial properties of 2-methyl-2-polyfluoroalkenyloxymethyl-1,3-propanediols: potential building blocks for syntheses of amphiphatic macromolecules

2-Hydroxymethyl-2-methyl-1,3-propanediol (A) was reacted with (Me(3)Si)(2)NH and toluenesulfonyl chloride (TsCl) to give mainly CH(3)C(CH(2)OSiMe(3))(3) (1), and CH(3)C(CH(2)OTs)(3) (2), respectively. With allyl bromide, the products were CH(3)C(CH(2)OCH(2)CH[double bond]CH(2))(2)(CH(2)OH) (3) and CH(3)C(CH(2)OCH(2)CH[double bond]CH(2))(CH(2)OH)(2) x H(2)O (4). The reactions of 4 with perfluoroalkyl iodides (R(f)I) were catalyzed by Cu(I)Cl to form 2-methyl-2-polyfluoroalkenyloxymethyl-1,3-propanediols: (R(f)CH=CHCH(2)OCH(2))C(Me)(CH(2)OH)(2) [R(f) = C(4)F(9) (5), C(8)F(17) (6), and (CF(2)CF(2))(4)OCF(CF(3))(2) (7)]. Reduction of 5 and 6 with hydrogen gave two new 2-methyl-2-polyfluoroalkyloxymethyl-1,3-propanediols, 8 and 9. The sodium salt of 9 was reacted with allyl bromide or acetyl chloride to form (C(8)F(17)CH(2)CH(2)CH(2)OCH(2))C(Me)(CH(2)OX)(CH(2)OH)(2) [where X = CH(2)CH=CH(2) (10) or C(O)CH(3) (12)] and (C(8)F(17)CH(2)CH(2)CH(2)OCH(2))C(Me)(CH(2)OX)(2) [where X = CH(2)CH[double bond]CH(2) (11) or C(O)CH(3) (13)]. Reaction of tolenesulfonyl chloride with 7 gave the monotosylate, 14, as the sole product. With 4-trifluoromethylbenzyl bromide, the sodium salt of 4 gave (4-CF(3)C(6)H(4)CH(2)OCH(2))C(Me)(CH(2)CH[double bond]CH(2))(CH(2)OH) x H(2)O (15). The compounds were characterized by NMR ((1)H, (13)C, (19)F, (29)Si), GC-MS, and high-resolution MS or elemental analyses. UV evidence was obtained for partitioning of 9, 12, 14, and 15 between perfluorodecalin and n-octanol. The test compounds acted as surfactants by facilitating the solubility of phenol and Si(CH[double bond]CH(2))(4) in perfluorodecalin. The single-crystal X-ray structure of 8 was also obtained. It crystallized in the monoclinic space group P2(1)/c, and unit cell dimensions were a = 24.966(2) A (alpha = 90), b = 6.1371(6) A (beta = 100.730(2)), and c = 10.5669(10) A (gamma = 90).     

Functionalized carbosilane dendritic species as soluble supports in organic synthesis

A new methodology, which is compatible with the use of reactive organometallic reagents, has been developed for the use of carbosilane dendrimers as soluble supports in organic synthesis. Hydroxy-functionalized dendritic carbosilanes Si[CH2CH2CH2SiMe2(C6H4CH(R)OH)]4 (G0-OH, R = H or (S)-Me) and Si[CH2CH2CH2Si[CH2CH2CH2SiMe2(C6H4CH(R)OH)]3]4 (G1-OH, R = H or (S)-Me) were prepared and subsequently converted into the esters Si[CH2CH2CH2SiMe2(C6H4CH(R)OC(O)CH2Ph)]4 (R = H or (S)-Me) and Si[CH2CH2CH2Si[CH2CH2CH2SiMe2(C6H4CH(R)OC(O)CH2C6H4 R')]3]4 (R = H and R' = H or R = (S)-Me and R' = H or R = H and R' = Br). As an example the latter compound was functionalized under Suzuki conditions. The functionalized carboxylic acid was obtained in high yield after cleavage from the dendritic support. Moreover, the ester functionalized dendrimers were converted to the corresponding zinc enolates followed by a condensation reaction with an imine to a beta-lactam in excellent yield and purity. Furthermore, it was demonstrated that a small combinatorial library of beta-lactams could be prepared starting from a carbosilane dendrimer functionalized with different ester moieties. These results show that carbosilane dendrimers can be applied as soluble substrate carriers for the generation of low molecular weight organic molecules. In combination with nanofiltration techniques, separation and recycling of the dendrimers can be realized.     

Structural and functional characteristics of rhenium clusters derived from redox chemistry of the triangular [ReIII3(mu-Cl)3] core unit

The present study investigates structural and functional aspects of the redox chemistry of rhenium(III) chloride [Re3Cl9] (1) in aqueous and organic solvents, with emphasis on the dioxygen-activating capabilities of reduced rhenium clusters bearing the Re3(8+) core. Dissolution of 1 in HCl (6 M) generates [Re3(mu-Cl)3Cl9]3- (2a), which can be isolated as the tetraphenylphosphonium salt (2b). Anaerobic one-electron reduction of 1 by Hg in HCl (6-12 M) produces [(C6H5)4P]2[Re3(mu-Cl)3Cl7(H2O)2].H2O (3), the structure of which features a planar [Re3(mu-Cl)3Cl3] framework (Re3(8+) core), involving two water ligands that occupy out-of-plane positions in a trans arrangement. Compound 3 dissociates in the presence of CO, yielding [(C6H5)4P]2[ReIII2Cl8] (4) and an unidentified red carbonyl species. In situ oxidation (O2) of the reduced Re3(8+)-containing cluster in HCl (6 M) produces quantitatively 2a, whereas oxidation of 3 in organic media results in the formation of [(C6H5)4P]4[(Re3(mu-Cl)3Cl7(mu-OH))2].2CH2Cl2 (5). The structure of 5 reveals that two oxygen ligands (hydroxo units) bridge asymmetrically two Re3(9+) triangular clusters. The origin of these hydroxo units derives from the aquo ligands, rather than O2, as shown by 18O2 labeling studies. The hydroxo bridges of 5 can be replaced by chlorides upon treatment with Me3SiCl to afford the analogous [(C6H5)4P]4[(Re3(mu-Cl)3Cl7(mu-Cl))2].10CH2Cl2 (6). The reaction of 5 with Hg in HCl (6 M)/tetrahydrofuran regenerates compound 3. Complexes 1-3 exhibit nitrile hydratase type activity, inducing hydrolysis of CH3CN to acetamide. The reaction of 3 with CH3CN yields [(C6H5)4P]2[Re3(mu-Cl)3Cl6.5(CH3CN)1.5(CH3C(O)NH)0.5] (7), the structure of which is composed of [Re3(mu-Cl)3Cl7(CH3CN)2]2- (7a) and [Re3(mu-Cl)3Cl6(CH3CN)(CH3C(O)NH)]2- (7b) (Re3(8+) cores) as a disordered mixture (1:1). Oxidation of 7 with O2 in CH3CN affords [(C6H5)4P]2[Re3(mu-Cl)3Cl7(CH3C(O)NH)].CH3CN (8) and small amounts of [(C6H5)4P][ReO4] (9). Compound 8 is also independently isolated from the reaction of 2b with wet CH3CN, or by dissolving 5 in CH3CN. In MeOH, 5 dissociates to afford [(C6H5)4P]2[Re3(mu-Cl)3Cl8(MeOH)].MeOH (10).     

Preliminary investigation of the simultaneous detection of sugars,ascorbic acid,citric acid,and sodium benzoate in non-alcoholic beverages by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) was used for the simultaneous detection of sugars, ascorbic acid, citric acid, sodium and/or potassium benzoate in non-alcoholic beverages, with meso-tetrakis(pentafluorophenyl)porphyrin (MW 974) as a matrix. Using potassium hydroxide as dopant, fructose/glucose was detected as the potassiated molecule at m/z 219, whereas potassiated sucrose, [Sucrose. K](+), was detected at m/z 381. Using sodium hydroxide as dopant, the fructose and sucrose ions were detected at m/z 203 and 365, respectively. Citric acid generated multiple ions at m/z 269, 307, and 345, which were assigned to [Citricbond;H+2K](+), [Citricbond;2H+3K](+), and [Citricbond;3H+4K](+), respectively. However, a stored methanolic solution of citric acid produced additional ions at m/z 283, 297, and 321, which were attributed to [Citricbond;2H+CH(3)+2K](+), [Citricbond;3H+2CH(3)+2K](+), and [Citricbond;3H+CH(3)+3K](+), respectively, due to esterification that took place during storage. The limits of detection in water were: ascorbic acid, 0.30 wt%; citric acid, 0.5 wt%; and sodium benzoate, 0.001 wt%. In the beverage formulations, the limits of detection were: ascorbic acid 0.3 wt%, citric acid 0.3 wt%, and sodium benzoate 0.02 wt%. Spiking a water or beverage solution that contained ascorbic and/or citric acid with less than 0.6 wt% of tartaric acid lowered the detection limits of ascorbic and citric acids to 0.2 wt%. This study demonstrates the potential for using MALDI-TOFMS in the quality control analyses of non-alcoholic beverages, particularly with regard to the detection of low molecular weight organic acids in commercial beverage formulations.     

pH值对廉价硅源合成MSU-1的影响

以硅酸钠为硅源、脂肪醇聚氧乙烯醚非离子表面活性剂C12-15H25-31O(CH2CH2O)9H (记为A(EO)9) 为模板剂,采用二步法合成MSU-1,在较宽的pH值范围里 (0.78～9.59),系统考察pH值的影响.对产物进行XRD和低温N2吸脱附表征.结果表明,随pH值升高,产物的孔道有序度先提高后降低;比表面、孔容均是先增大后减小,pH为1.98时,合成产物的比表面、孔容最大 (分别高达1202m2/g、0.83cm3/g);孔壁厚度随pH值呈波浪形变化,并对以上结果给予解释.     

Tunable N-substitution in zwitterionic benzoquinonemonoimine derivatives: metal coordination, tandemlike synthesis of zwitterionic metal complexes, and supramolecular structures

Full details on a very efficient transamination reaction for the synthesis of zwitterionic N,N-dialkyl-2-amino-5-alcoholate-1,4-benzoquinonemonoiminium derivatives [C6H2(=NHR)2(=O)2] 5-16 are reported. The molecular structures of zwitterions 5 (R=CH3) in 5.H2O, 13 (R=CH2CH2OMe), 15 (R=CH2CH2NMe2), and of the parent, unsubstituted system [C6H2(=NH2)2(=O)2] 4 in 4.H2O have been established by single-crystal X-ray diffraction. This one-pot preparation can be carried out in water, MeOH, or EtOH and allows access to new zwitterions with N-substituents bearing functionalities such as -OMe (13), -OH (9-12), NR1R2 with R1 = or not equal R2 (14-16) or an alkene (8), leading to a rich coordination chemistry and allowing fine-tuning of the supramolecular arrangements in the solid state. As previously described for 15, which reacted with Zn(acac)2 to afford the octahedral Zn(II) complex [Zn[C6H2(NCH2CH2NMe2)O(O)(NHCH2CH2NMe2)]2] (20), ligands 13 and 16 with coordinating "arms" afforded with Zn(acac)2 the 2:1 adducts [Zn[C6H2(NCH2CH2X)O(=O)(NHCH2CH2NX)]2] 19 (X=OMe) and 21 (X=NHEt), with N2O4 and N4O2 donor sets around the octahedral Zn(II) center, respectively. Furthermore, zwitterions 15 and 16 reacted with ZnCl2 to give the stable, crystallographically characterized Zn(II) zwitterionic complexes [ZnCl2[C6H2(NCH2CH2NR1R2)O(=O)(NHCH2CH2NHR1R2)]] 22 (R1=R2=Me) and 23 (R1=Et, R2=H) by means of an unprecedented, tandemlike synthesis in which 1) the two pendant amino groups of the organic benzoquinonemonoimine zwitterionic precursor favor metal coordination and proton transfer and 2) the saturated linker prevents pi-conjugation between the charges. The nature of the structural arrangements in the solid state for both inorganic (20, 22, 23) and organic (5, 9, 13, and 15) molecules is determined by subtle variations in the nature of the N-substituent on the zwitterion precursor.     

Sequential protonation and methylation of a hydride-osmium complex containing a cyclopentadienyl ligand with a pendant amine group

Complex OsH{eta5-C5H4(CH2)2NMe2}(P(i)Pr3)2 (1) reacts with 1 equiv of trifluoromethanesulfonic acid (HOTf) and trifluoromethanesulfonic acid-d1 (DOTf) to produce the dihydride and hydride-deuteride complexes, [OsHE{eta5-C5H4(CH2)2NMe2}(P(i)Pr3)2]OTf (E = H (2), D (2-d1), respectively. Treatment of 2 and 2-d1 with a second equivalent of HOTf gives [OsHE{eta5-C5H4(CH2)2NHMe2}(P(i)Pr3)2][OTf]2 (E = H (3), D (3-d1) as a result of the protonation of the nitrogen atom. While the hydride and deuteride ligands of 2, 2-d1, 3, and 3-d1 do not undergo any H/D exchange process with the solvent, in acetone-d6, the NH proton of 3 and 3-d1 changes places with a deuterium atom of the solvent to yield [OsHE{eta5-C5H4(CH2)2NDMe2}(P(i)Pr3)2][OTf]2 (E = H (3-Nd1), D (3-d2)). Complex 3-Nd1 can also be obtained from the treatment of complex 2 with DOTf in dichloromethane. No exchange process between the hydride and the ND positions in 3-Nd1 or between the deuteride and NH positions in 3-d1 has been observed. Treatment of 3-Nd1 and 3-d1 with sodium methoxide results in a selective reaction of the base with the ammonium group to regenerate 2 and 2-d1, respectively. Complex 1 also reacts with methyl and methyl-d3 trifluoromethanesulfonate (CH3OTf and CD3OTf, respectively) to give [OsH{eta5-C5H4(CH2)2NMe2CE3}(P(i)Pr3)2]OTf (E = H (4), D (4-d3)) as a result of the addition of the CE3 (E = H, D) group to the nitrogen atom. Complex 4 has been characterized by an X-ray diffraction analysis. It reacts with a second molecule of CH3OTf or CD3OTf to produce [OsH{eta5-C5H4(CH2)2NMe3}{CH2CH(CH3)P(i)P2}(P(i)Pr3)[OTf]2 (5). Similarly, complex 4-d3 reacts with a second molecule of CH3OTf or CD3OTf to yield [OsH{eta5-C5H4(CH2)2NMe2CD3}{CH2CH(CH3)P(i)P2}(P(i)Pr3)[OTf]2 (5-d3). In acetonitrile, complex 5 evolves to an equilibrium mixture of the acetonitrile adducts [Os{eta5-C5H4(CH2)2NMe3}(NCCH3)(P(i)Pr3)2][OTf]2 (7) and [Os{eta5-C5H4(CH2)2NMe3}(NCCH3)2(P(i)Pr3)][OTf]2 (8). In methanol or methanol-d4, complex 4 is not stable and loses trimethylamine to give the vinylcyclopentadienyl derivatives [OsHE(eta5-C5H4CH=CH2)(P(i)Pr3)2]OTf (E = H (9), D (9-d1)) as a result of the protonation or deuteration of the metallic center and a subsequent Hofmann elimination. Protonation of 4 with HOTf gives the dihydride-trimethylammonium derivative [OsH2{eta5-C5H4(CH2)2NMe3}(P(i)Pr3)2][OTf]2 (10). Treatment of 9 with sodium methoxide produces OsH(eta5-C5H4CH=CH2)(P(i)Pr3)2 (11).