辐射合成聚丙烯酰胺,聚丙烯酸钠及其共聚物水凝胶微观结构…

用＾６０Ｃｏ－γ射线辐射合成了低交联度的聚丙烯酰胺、聚丙烯酸钠及丙烯酰胺－丙烯酸钠共聚物水凝胶，用扫描电子显微镜研究了水凝胶经过丙酮脱水的干态试样的微观结构特征。发现聚合物中丙烯酰胺与丙烯酸钠单体单元的比例对其微观结构影响很大，并且从聚合物链段之间存在氢键和静电排斥这两种对立作用力相对强度的角度，定性地阐述各水凝胶微观结构之间的差异。     

温度及pH敏感聚（丙烯酸）／聚（N—异丙基丙烯酰胺）互穿聚合物网络水凝胶的...

合成聚（丙烯酸）／聚（Ｎ－异丙基丙烯酰胺）互穿聚合物网络（ＰＡＡｃ／ＰＮＩＰＡ ＩＰＮ）水凝胶，具有温度及ｐＨ双重敏感特性。这种水凝胶在弱碱性条件下的溶胀率远大于酸性条件下的溶胀率。在酸性条件下，随着温度上升，凝胶的溶胀率也随之逐渐上升；而在弱碱性条件下，温度低于聚（Ｎ－异丙基丙烯酰胺）（ＰＮＩＰＡ）的较低临界溶解温度（ＬＣＳＴ）时，溶胀率也随着温度的上升而上升，而温度达到ＬＣＳＴ时，凝胶的溶胀率     

交联共聚丙烯酰胺—丙烯酸水凝胶溶胀态分子动力学的NMR驰豫研究

用反相悬浮聚合法制备了交联度分别为１０％、７．５％、５％、１％、０．５％及０．２５％的丙烯酰胺－丙烯酸交联共聚水凝胶，用＾１ＨＮＭＲ驰豫方法测定了水及聚合物主链上基团中质子的自旋－自旋驰豫时间并结合质子线型分析，     

丙烯酰胺-丙烯酸交联共聚凝胶结构与分子运动的~1H NMR自旋晶格弛豫研究

用1HNMR方法测定了交联度分别为10％,7.5％，5％，25％，1％，0．5％及0．25％的丙烯酰胺-丙烯酸与N，N’－亚甲基双丙烯酰胺交联共聚水凝胶中水及主链质子的化学位移谱及自旋晶格弛豫时间T1，并用BBP模型进行了讨论。结果表明，水和凝胶主链的质子线宽随交联度加大而明显增宽，只有在低交联度下，由空间立规度造成的精细分裂才能呈现出来；水凝胶体系中水自旋晶格弛豫时间T1随交联度加大而非单调地减小，寓示凝胶内部有较强的键合束缚水存在，并满足双相快交换模型。聚合物主链质子T1与水质子的T1弛豫行为相反，随交联度加大主链运动受限加强而使其运动减慢，反映了聚合物主链的大分子运动特征，发现主链（-CH-）与（－CH2－）质子T1之比可表征凝胶内部分子链运动的强弱；讨论了NMR弛豫与凝胶孔径结构的关联。     

N—异丙基甲基丙烯酰胺共聚热缩温敏水凝胶

从甲基丙烯腈与异丙醇反应制备了Ｎ－异丙基甲基丙烯酰胺（ＮＩＰＭ），研究了其以Ｎ，Ｎ＇－亚甲基双丙烯酰胺（ＭＢＡ）为交联剂在不同溶剂体系的聚合及所形成的水凝胶的性质。表明ＮＩＰＭ－ＭＢＡ凝胶具有热缩温敏性。在ＮＩＰＭ－ＭＢＡ体系引入丙烯酸钠、甲基丙烯酸钠等负离子单体时，凝胶的溶胀比明显增加，ＭＢＡ所占比例较少的体系，具有热缩、热胀双重性。     

水溶性聚合物和两亲聚合物：聚（丙烯酰胺－co－丙烯酸钠）－g－聚（β－胺基丙酸）接枝共聚物

合成了端丙烯酰胺基聚（β－胺基丙酸）大分子单体，用端基滴定法和１Ｈ－ＮＭＲ法测定了大分子单体的分子量，用＾１＾３Ｃ－ＭＮＲ和氢氧化钠水解法测定了支化度，在水溶液中用硫酸亚铁／异丙苯过氧化氢氧化还原引发体系引发丙烯酰胺，丙烯酸钠与聚（β－胺基丙酸）大分子单体的共聚反应，合成了聚（丙烯酰胺－ｃｏ－丙烯酸钠）－ｇ－聚（β－胺基丙酸）用１Ｈ－ＮＭＲ和滴定法测定了接枝共聚物的组成。溶液性质的数据表明，与部分     

交联网络和浓溶液中高分子链运动的NMR研究 Ⅱ质子自旋-自旋弛豫与凝胶和浓溶液体系中高分子链段运动

用自旋－自旋弛豫时间考察了线型聚苯乙烯溶液与溶胀交联聚丙烯酰胺－丙烯酸凝胶的质子弛豫行为。发现在溶胀交联体系中，不论交联度高低，聚丙烯酰胺－丙烯酸质子的弛豫时间弛豫都呈现出双指数衰减特征；而在线型溶液体系中，聚苯乙烯质子的弛豫时间弛豫符合单指数衰减特征。说明在线性聚苯乙烯溶液中，高分子的链段运动是一种均匀行为，而在溶胀交联聚丙烯酰胺－丙烯酸体系中，不论交联度高低，高分子链段运动始终存在快慢不同的两部分。     

P(NIPAAm-co-Aam)共聚凝胶和PAAc/P(NIPAAm-co-Aam) IPN凝胶的溶胀与释药性能

P(NIPAAm-co-Aam)共聚凝胶和PAAc/P(NIPAAm-co-Aam) IPN凝胶的溶胀与释药性能;N-异丙基丙烯酰胺;丙烯酰胺;丙烯酸;共聚;互穿聚合物网络;水凝胶;溶胀;释药     

丙烯酰胺—丙烯酸交联共聚凝胶结构与分子运动的^1HNMR自旋…

用＾Ｈ ＮＭＲ方法测定了交联度分别为１０％，７．％，５％，２．５％，１％，０．５％及０．２５％４ 丙烯酰胺－丙烯酸与Ｎ，Ｎ‘－亚甲基双丙烯酰胺交联共聚水凝胶中水及主链质子的化学位移谱及自旋晶格驰豫时间Ｔ１，并用ＢＢＰ模型进行了讨论。     

辉光放电电解等离子体引发合成丙烯酰胺-丙烯酸共聚物水凝胶及其对阳离子染料的吸附性能

以丙烯酰胺（AM）和丙烯酸（AA）为单体、N,N′-亚甲基双丙烯酰胺（MBA）为交联剂,在水溶液中利用辉光放电电解等离子体（GDEP）引发,一步制得丙烯酰胺-丙烯酸共聚物（P（AM-co-AA））水凝胶。用红外光谱（FT-IR）、扫描电镜（SEM）和热重分析（TGA）对P（AM-co-AA）水凝胶的结构、形貌和稳定性进行了表征。考察了放电电压、放电时间、MBA质量含量、AM质量分数以及中和度对P（AM-co-AA）水凝胶吸附孔雀石绿（MG）的影响,同时探讨了引发机理。结果表明,水凝胶对MG的最大吸附量为864mg/g。     

U(IV)/LN(III) unexpected mixed site in polymetallic oxalato complexes. Part II. Substitution of U(IV) for Ln(III) in the new oxalates (N2H5)Ln(C2O4)2·nH2O (Ln=Nd, Gd)

Two new hydrazinium lanthanide(III) oxalates, (N₂H₅)[Nd(C₂O₄)₂(H₂O)]·4H₂O (1) and (N₂H₅)[Gd(C₂O₄)₂(H₂O)]·4.5H₂O (2) have been prepared and their crystal structures determined by single-crystal X-ray diffraction. The crystal structures were solved by the direct methods and Fourier difference techniques, and refined by a least-squares method on the basis of F² for all unique reflections. Crystallographic data: 1, triclinic, space group , , b=9.762(4), , α=62.378(5), β=76.681(5), γ=73.858(5), Z=2, R₁=0.0335 for 172 parameters with 3430 reflections with I?2σ(I); 2, triclinic, space group , , b=9.51(3), , α=62.11(4), β=76.15(5), γ=73.73(5), Z=2, R₁=0.0325 for 172 parameters with 1742 reflections with I?2σ(I). The two isotypic structures are built from a three-dimensional (3D) arrangement of lanthanide and oxalate ions. The lanthanide atom is coordinated by eight oxygen atoms from four tetradentate oxalate ions and one aqua oxygen. Alternating lanthanide and oxalate ions form six-membered rings that delimit tunnels running down three directions and occupied by hydrazinium and water molecules. Starting from these lanthanide(III) compounds two isotypic mixed Ln(III)/U(IV) oxalates, (N₂H₅)_0.75[Nd_0.75U_0.25(C₂O₄)₂(H₂O)]·4.5H₂O (3) and (N₂H₅)_0.75[Gd_0.75U_0.25(C₂O₄)₂(H₂O)]·4H₂O (4), are obtained by partial substitution of Ln(III) by U(IV) in the nine-coordinated site, the charge excess being compensated by removal of monovalent ions from the tunnels. Finally, using Na⁺ gel, two mixed Ln(III)/U(IV) sodium oxalates, Na_0.5[Nd_0.5U_0.5(C₂O₄)₂(H₂O)]·3H₂O (5) and Na_0.65[Gd_0.65U_0.35(C₂O₄)₂(H₂O)]·4.5H₂O (6) have been obtained without any change in the 3D framework.     

U(IV)/Ln(III) unexpected mixed site in polymetallic oxalato complexes. Part I. Substitution of Ln(III) for U(IV) from the new oxalate (NH4)2U2(C2O4)5·0.7H2O

A new ammonium uranium (IV) oxalate (NH₄)₂U₂(C₂O₄)₅·0.7H₂O (1) and three mixed uranium (IV)-lanthanide (III) oxalates, (N₂H₅)_2.6U_1.4M_0.6(C₂O₄)₅·xH₂O (M=Nd (2) and M=Sm (3)), Na_2.56U_1.44Nd_0.56(C₂O₄)₅·7.6H₂O (4) and Na₃UCe(C₂O₄)₅·10.4H₂O (5), have been prepared. The crystal structures of compounds 1, 4 and 5 have been determined by single-crystal X-ray diffraction. The crystal structures were solved by the direct methods and Fourier difference techniques, and refined by a least square method on the basis of F² for all unique reflections. Compounds 2 and 3 are isotypic with 1. Crystallographic data: 1, hexagonal, space group P6₃/mmc, a=19.177(3), c=12.728(4) Å, Z=6, R₁=0.0575 for 52 parameters with 1360 reflections with I?2σ(I); 2, hexagonal, space group P6₃/mmc, a=19.243(4), c=12.760(5) Å, Z=6; 3, hexagonal, space group P6₃/mmc, a=19.211(3), c=12.274(4) Å, Z=6; 4, orthorhombic, space group Pbcn, a=18.79(3), b=11.46(1), c=12.77(2) Å, Z=4, R₁=0.0511 for 183 parameters with 3026 reflections with I?2σ(I); 5, monoclinic, space group C2/c, a=18.878(6), b=11.684(4), c=12.932(4) Å, β=95.97(1)°, Z=4, R₁=0.0416 for 213 parameters with 4060 reflections with I?2σ(I). The honeycomb-like structure of the five compounds is built from the same three-dimensional arrangement of metallic and oxalate ions. Similar hexagonal rings of alternating metallic and oxalate ions form layers parallel to the (001) plane that are pillared by another oxalate ion. Indeed, some torsions or rotations of the bridging oxalate ligands led to modifications of the network symmetry. The monovalent cations and the water molecules occupy the hexagonal tunnels running down the [001] direction. Starting from the uranium (IV) compound A₂U₂(C₂O₄)₅·0.7H₂O with A=NH₄⁺ (1), the mixed U(IV)/Ln(III) oxalates are obtained by partial substitution of U(IV) by Ln(III) in a ten-coordinated site, the charge deficit being compensated by intercalation of supplementary monovalent ions within the tunnels. The distortion of the arrangement in the [001] direction for the Na-containing compounds allows the accommodation of a greater number of water molecules that insure an octahedral coordination of the Na atoms.     

手性二噁唑啉吡啶铁和镍配合物的制备与表征

Tridentate bis(oxazolinylpyridine)(1) reacted with nickel chloride or ferrous chloride in anhydrous ethanol to form bis(oxazolinylpyridine) Nickel(Ⅱ) and Iron(Ⅱ) complexes. The stable solid complexes were characterized with IR， UV， MS， XPS and elemental analysis. No stable complexes were formed with bidentate bis(oxazoline)(2) ins- tead of bis(oxazolinylpyridine).     

新型温度敏感性自组装胶束P(NiPAAm-co-DMAA)-co-P(L-Ala)的合成和性能

通过原子转移自由基聚合(ATRP)合成了一种带有活性—NH2基团的温度敏感性亲水型共聚物P(NiPAAm-co-DMAA), 并将其作为引发剂, 合成了P(NiPAAm-co-DMAA)-co-P(L-Ala), 其分子量分布(PDI)在1.3左右. 聚合物通过自组装形成纳米胶束. 透射电镜(TEM)结果表明, 胶束大小200~300 nm, 具有明显的核壳结构. 共聚物的最低临界溶解温度(LCST)为45.5 ℃. 温度低于LCST时, 聚合物溶解形成胶束; 高于LCST时, 胶束解离, 聚合物不溶. 聚合物对温度的响应是快速而可逆的.     

SYNTHESES AND MASS SPECTRAL REARRANGEMENTS OF UNSATURATED BIS-SULPHIDES AND BIS-SULPHONES

Abstract

The synthesis of (E)- and (Z)-1.2-bis(p-fluorophenylsulphenyl)stilbenes (2a and 2b) and 1,2-bis(p-fluorophenylsulphonyl)stilbenes (3a and 3b) was carried out and their configurations were consistent with their stereospecific synthesis. The isomeric 1,1-bis(p-fluorophenylsulphenyl)- and 1,1-bis(p-fluorophenylsulphonyl)-2,2-bis(phenyl)ethylenes (8 and 9) were also synthesised and configurations were established by degradative oxidation. Mass spectral rearrangements of all these compounds were examined. Mass spectra of 1,1-bis-sulphide and 1,1-bis-sulphone bears close relationship with those of (E)- and (Z)-isomeric counterparts. Smiles-type rearrangement observed in 1,2-bis-sulphides was absent in 1,2-bis-sulphones. McLafferty-type rearrangement involving hydrogen migration, from aryl group was noticed in both bis-sulphides and bis-sulphones. Vinyl migration to the sulphone oxygen predominates over aryl migration in three isomeric bis-sulphones.     

界面缩聚法合成双(烯基环戊二烯基)钛(锆)聚醚的研究

本文通过界面缩聚法利用双(烯基环戊二烯基)钛(锆)二氯化物与二酚反应,制成了16个新的高分子化合物,对它们进行了IR、TGA和分子量的测定。文中还对反应条件与分子量的关系进行了讨论。     

Asymmetric Synthesis of (R)-and (S)-Moprolol

A simple and effective procedure for the enantioselective synthesis of (R)-and (S)-moprolol was described.The key step was the asymmetric synthesis of enantiopure (R)-and (S)-guaifenesin,which were synthesized from enantioenriched (R)-3-chloro-1,2-propanediol and (S)-epichlorohydrin via kinetics of hydrolysis resolution of racemic epichlorohydrin by chiral Salen-CoIIII complex.The e.e.values of both the optical compounds were above 98%,and the chemical structures of the target compounds were confirmed by 1H NMR,13C NMR,IR,and MS.     

Fluorinated phosphorus compounds: Part 6. The synthesis of bis(fluoroalkyl) phosphites and bis(fluoroalkyl) phosphorohalidates

Reaction of phosphorus trichloride with tert-butanol and fluoroalcohols gave bis(fluoroalkyl) phosphites (R_FO)₂P(O)H in 42-89% yield, where R_F=HCF₂CH₂, H(CF₂)₂CH₂, H(CF₂)₄CH₂, CF₃CH₂, C₂F₅CH₂, C₃F₇CH₂, (CF₃)₂CH, (FCH₂)₂CH, CF₃(CH₃)₂C, (CF₃)₂CH₃C, CF₃CH₂CH₂, C₄F₉CH₂CH₂ and C₆F₁₃CH₂CH₂. Treatment of these with chlorine in dichloromethane gave the bis(fluoroalkyl) phosphorochloridates (R_FO)₂P(O)Cl in 49-96% yield. The chloridate (CF₃CH₂O)₂P(O)Cl was isolated in much lower yield from the interaction of thionyl chloride with bis(trifluoroethyl) phosphite. Heating the latter in dichloromethane with potassium fluoride and a catalytic amount of trifluoroacetic acid gave the corresponding fluoridate (CF₃CH₂O)₂P(O)F in 84% yield. Treatment of bis(trifluoroethyl) phosphite with bromine or iodine gave the bromidate (CF₃CH₂O)₂P(O)Br and iodidate (CF₃CH₂O)₂P(O)I in 51 and 46% yield, respectively. The iodidate is the first dialkyl phosphoroiodidate to have been isolated and characterised properly—its discovery lags behind the first isolation of a dialkyl phosphorochloridate by over 130 years. The fluoroalkyl phosphoryl compounds are generally more stable than known unfluorinated counterparts.     

以氯醌酸二价阴离子为桥联配体的Fe(Ⅲ)-Fe(Ⅲ)和Mn(Ⅱ)-Mn(Ⅱ)双核配合物的合成与磁性

基于铁和锰的双核配合物在生物氧化还原过程中的重要作用及在化学的氧化还原过程中可能做为催化剂的应用前景,本文合成了两个新的以氯醌酸二价阴离子为桥联配体的Fe(Ⅲ)双核和Mn(Ⅱ)双核配合物:[Fe_2(phen)_4(μ-CA)](ClO_4)_4·2H_2O(1)和[Mn_2(phen)_4(μ-CA)](ClO_4)_2·3H_2O(2)(phen=1,10菲咯啉;CA=氯醌酸二价阴离子)。经元素分析、IR、电子光谱及磁性等测定,对两配合物进行了表征。