聚合物对非离子十二烷基聚氧乙烯聚氧丙烯醚浊点的影响

测定了水溶性高分子聚乙二醇(PEC1000、PEG2000、PEG6000)和聚乙烯吡咯烷酮(PVP-K30、PVP-K90)对三种非离子表面活性剂十二烷基聚氧乙烯聚氧丙烯醚C12H25O(EO)m(PO)nH(LS36,m=3,n=6;LS5,m=4,n=5;LS54,m=5,n=4)浊点的影响.结果表明,聚乙二醇(PEG)可使三种表面活性剂水溶液浊点降低;而聚乙烯吡咯烷酮(PVP)随其浓度增加,表面活性剂溶液浊点先升高然后又下降;浊点下降程度与聚合物浓度和分子量有关.     

水溶性非离子大分子与烷基硫酸钠同系物团簇化的比饱和簇集量

研究了烷基硫酸钠同系物(ROSO₃Na)与聚乙二醇(PEG)及聚乙烯吡咯烷酮(PVP)的γ-lgc曲线的双拐点特征,根据拟双平台现象求得烷基硫酸钠同系物对大分子的饱和簇集量Γ_∞(mmol/L)和比饱和簇集量[Γ_∞].由Γ_∞-cP回归方程的斜率得到ROSO₃Na-PEG及ROSO₃Na-PVP体系的[Γ_∞]_reg分别为0.394和0.415m/n.[Γ_∞]随表面活性剂疏水基链长、大分子分子量及浓度的变化均很小,t检验结果表明回归值[Γ_∞]_reg与实验值[Γ_∞]_exp之间无明显差异,因此超分子相互作用参数[Γ_∞]可以被视为不变量.烷基硫酸钠同系物的类胶束与大分子形成软物质团簇的作用方式为静电超分子自组装.     

利用光化学探针技术研究长链烷烃硫酸钠水溶液中预胶束的生成

罗丹明6G与罗丹明B之间的能量转移和吖啶橙形成聚态的现象用于研究长链烷基硫酸钠(C_nH_(2n+1)OSO_3Na,n=12,14和16)在水溶液中预胶束的生成.结果表明,烷基链的长度影响这些表面活性剂形成预胶束的能力,碳数的增加使预胶束形成浓度降低.     

InnNa和InnNa+(n=2-8)的团簇结构和电子性质

在密度泛函理论B3LYP水平上, 对InnNa和InnNa+(n=2-8)团簇进行了结构优化和振动频率计算. 计算结果表明, InnNa(n=2、3、4、6)最稳定结构中的对称性分别为C2v、C3v、C4v和C2v, 而InnNa(n=5、7、8)的最稳定结构的对称性为C1点群. 从InnNa(n=4-8)的最稳定结构可以看出, Na原子均位于四个In原子形成的四边形面上. 对于InnNa+(n=2-8), 除了In2Na+、In4Na+和In7Na+, 其它结构都与其中性结构相似. 进一步计算InnNa(n=2-8)团簇的平均结合能、能量的二阶差分以及绝热电离能表明, InnNa(n=2-8)团簇能量的二阶差分呈现奇偶交替特征, In4Na和In6Na较其它团簇更为稳定, 而且理论计算得到的绝热电离能和实验结果吻合得很好.     

InnNa和InnNa^＋（n=2—8）的团簇结构和电子性质

在密度泛函理论B3LYP水平上,对Innna和InnNa+(n=2-8)团簇进行了结构优化和振动频率计算.计算结果表明,InnNa(n=2、3、4、6)最稳定结构中的对称性分别为C2v、C3v、C4v和C2v而InnNa(n=5、7、8)的最稳定结构的对称性为C1点群.从InnNa(n=4-8)的最稳定结构可以看出,Na原子均位于四个In原子形成的四边形而上.对于InnNa+(n=2-8),除了In2Na+和In7Na+,其它结构都与其中性结构相似.进一步计算InnNa(n=2-8)团簇的平均结合能、能量的二阶差分以及绝热电离能表明,InnNa(n=2-8)团簇能量的二阶差分呈现奇偶交替特征,In4Na和In6Na较其它团簇更为稳定,而且理论计算得到的绝热电离能和实验结果吻合得很好.     

Sn_mO_n(m=1～3,n=1～2m)系列团簇的结构和电子性质

基于密度泛函理论(DFT)中的广义梯度近似(GGA)系统地研究了Snm On(m=1~3,n=1~2m)团簇的几何结构和电子性质.当m=n时,团簇的基态结构为Sn和O原子彼此相邻的环形结构,当nm时,团簇易于形成链状结构.研究发现:氧化锡团簇的物理和化学特性类似于氧化硅,主要表现为非金属性.对分裂途径、分裂能和能隙(HOMO-LUMO Gap)进行了研究,结果表明类氧化锡(Snm Om)、Sn2O3和Sn3O4团簇具有很好的稳定性,可以作为构建团簇聚合物材料的基本单元.而且,氧化锡团簇的稳定性主要与其组成成分和结构有关,与团簇大小无关.     

十二烷基硫酸钠-水溶性非离子大分子间团簇化作用部位的1H和13C及2D NMR表征

运用 1H NMR, 13C NMR, 2D NOESY-NMR及2D ROESY-NMR等多种波谱技术联合表征典型阴离子表面活性剂十二烷基硫酸钠(SDS)与典型水溶性非离子大分子聚乙烯吡咯烷酮(PVP)或聚乙二醇(PEG)间的团簇化作用部位. NMR综合分析结果表明, SDS分子亲水头基邻近的C1~C2片段与PVP分子中内酰胺氮为中心的主链α-C、 五元环上羰基C1(记为P1)及C4(记为P4)片段给出较强的作用信号, 推断SDS分子亲水头基与PVP分子中内酰胺氮及其两者的相邻区域可能为形成团簇时SDS束缚胶束与PVP间超分子作用的主要部位. 而SDS束缚胶束与PEG形成团簇时, 除极性部位及其相邻区域的相互作用外, 部分PEG链节可能渗入到SDS束缚胶束的C3部位或更深的内部.     

Na2[(VO)12O6B18O39(OH)3]·(11H3O)·4H2O的水热合成和晶体结构

以V2O5, Na2B4O7·0H2O, NaH2PO4·2H2O, 乙二胺和H2O为原料, 按物质的量比0.5∶1∶1∶2.24∶111在180 ℃条件下晶化, 得到棕色晶体Na2[(VO)12O6B18O39(OH)3]·(11H3O)*4H2O. 单晶结构分析结果表明该化合物属单斜晶系, P21/n空间群, 晶胞参数 a=1.389 70(8) nm, b=1.661 59(9) nm, c=1.427 48(8) nm, β=95.691 0(10)°. Z=4, R=0.054 9. 该化合物的结构主要由阴离子簇[(VO)12O6B18O39(OH)3]13-构成. 该阴离子簇由B18O39(OH)3十八元环夹在两个以共边方式交替相连形成的V6O15簇中间, 通过共用氧原子形成三明治式结构新颖的硼-钒-氧阴离子簇, 结构中Na+以离子键方式将阴离子簇相互连接, 形成二维层状结构. 层与层之间通过分子间氢键相互作用. 价态计算结果表明, 结构中n(VⅣ)∶n(VⅤ)=5∶1.     

十二烷基甜菜碱与聚乙烯吡咯烷酮相互作用的研究

通过表面张力测定和13CNMR、ESR波谱研究了十二烷基甜菜碱（C12BE）与聚乙烯吡咯烷酮（PVP）的相互作用．表面张力测定表明,在pH＝6．5及NaCI存在下,C12BE与PVP之间有明显的相互作用,可形成C12BE／PVP复合物,且C12BE－PVP混合溶液的β－lgc曲线出现2个转折点,第一个转折点时C12BE浓度c1（C12BE－PVP开始缔合）低于C12BE的cmc值;而第二个转折点时C12BE浓度c2（C12BE－PVP缔合达饱和）大于cmc值．（c2─c1）与PVP浓度呈线性关系．PVP降低C12BE胶束化标准自由能（△G0）随PVP浓度增加而增大．13CNMR测定表明,PVP骨架上α-CH、β-CH2和吡咯环上与N相连的亚甲基吸附于C12BE胶束表面的碳氢链部位,屏蔽了C12BE胶束表面碳氢链与水的接触．ESR波谱表明,PVP－C12BE聚集体"界面"的粘度高于C12BE胶束"界面"的粘度．     

利用光化学探针技术研究长链烷烃硫酸钠水溶液中预胶束的生成

罗丹明6G与罗丹明B之间的能量转移和吖啶橙形成聚态的现象用于研究长链烷基硫酸钠(C~nH~2~n~+~1OSO~3Na,n=12,14和16)在水溶液中预胶束的生成。结果表明,烷基链的长度影响这些表面活性剂形成预胶束的能力,碳数的增加使预胶束形成浓度降低。     

碱金属硫酸盐-十二烷基硫酸钠-聚乙二醇三元复合体系的束缚胶束特性

采用表面张力、稳态荧光猝灭和荧光分子探针技术研究了部分碱金属(锂、钠、钾)硫酸盐-十二烷基硫酸钠(Sod ium Dodecyl Su lfate SDS)-聚乙二醇(PEG)三元复合体系的聚集特性,发现加入碱金属硫酸盐后SDS仍以束缚胶束(bound m icelle)形式与PEG发生团簇化作用.表面张力实验表明,外加碱金属硫酸盐浓度c_e增加,体系的第一临界浓度c₁渐次降低,而第二临界浓度c₂略有增大,因而形成束缚胶束的浓度区间增宽;比饱和簇集量[Γ_∞]随之增大,如加入50 mmol/L硫酸锂时,[Γ_∞]增大了40%.稳态荧光猝灭实验表明,束缚胶束聚集数N_b随PEG浓度c_p线性减小,却随SDS浓度c线性增大,并呈c_e的单增函数关系;碱金属离子使N_b增大的能力按Li⁺++顺序增加,与碱金属水合离子半径减小的顺序相同.芘分子探针的荧光特性反映了束缚胶束的微环境极性随c和c_e增加而减小,随c_p增加而增大.     

The solution behavior of poly(vinylpyrrolidone): its clouding in salt solution, solvation by water and isopropanol, and interaction with sodium dodecyl sulfate

This article deals with the solution properties of poly(vinylpyrrolidone) (PVP) in salt and surfactant environment. The cloud point (CP) of PVP has been found to be induced by the salts NaCl, KCl, KBr, Na2SO4, MgSO4, and Na3PO4. On the basis of CP values for a salt at different [PVP], the energetics of the clouding process have been estimated. The effect of the surfactant, sodium dodecyl sulfate (SDS), on the salt-induced CP has also been studied, and reduction in CP at low [SDS] and increase in CP at high [SDS] have been observed. The water vapor adsorption of PVP has been determined by isopiestic method. The results display a BET Type III isotherm whose analysis has helped to obtain the monolayer capacity of PVP and formation of multilayer on it. The solvation of PVP in a solution of water and a water-isopropanol mixture has been determined by conductometry from which contribution of the individual components were estimated. The interaction of PVP with SDS in solution led to formation of a complex entity, which has been studied also by conductometry adopting a binding-equilibrium scheme. SDS has been found to undergo two types of binding as monomers in the pre- critical aggregation concentration (CAC) range and as small clusters in the post CAC region. The stoichiometries of binding and binding constant were evaluated.     

Surfactant--polymer aggregates formed by sodium dodecyl sulfate, poly(N-vinyl-2-pyrrolidone), and poly(ethylene glycol)

The interaction of sodium dodecyl sulfate (SDS) in aqueous solution with poly(N-vinyl-2-pyrrolidone) (M(w) = 55,000 g/mol) in the presence of poly(ethylene glycol) (M(w) = 8000 g/mol) is investigated by electrical conductivity, zeta potential measurements, viscosity measurements, fluorescence spectroscopy, and small-angle X-ray scattering (SAXS). The results indicate that SDS-polymer interaction occurs at low surfactant concentration, and its critical aggregation concentration is fairly dependent on polymer composition. The polymer-supported micelles have average aggregation numbers dependent on surfactant concentration, are highly dissociated when compared with aqueous SDS micelles, and have zeta potentials that increase linearly with the fraction of PVP at constant SDS concentration. The analysis of the SAXS measurements indicated that the PVP/PEG/SDS system forms surface-charged aggregates of a cylindrical shape with an anisometry (length to cross-section dimension ratio) of about 3.0.     

Thermodynamics of interaction between sodium bis(2‐ethylhexyl) sulfosuccinae and polymers in aqueous solutions by isothermal titration microcalorimetry

The interactions between sodium bis(2‐ethylhexyl) sulfosuccinae (AOT) and two nonionic water‐soluble polymers, including polyvinyl pyrrolidone (PVP) and polyethylene glycol (PEG) have been investigated by using isothermal titration microcalorimetry in aqueous solutions at 298.15 K. The results show that the critical aggregation concentration, which corresponding to the first turning point in the curve of experimental interaction heat versus concentration of the surfactant, is lower than the critical micellar concentration (cmc), confirming the existence of polymer‐surfactant interactions. The value of cac is not sensitive to the relative amount of polymer in low concentration range of the polymer. The mono‐layer saturated adsorption concentration, which corresponding to the second turning point, rises as the polymer concentration is increased. The interaction between PVP and AOT is stronger than that between PEG and AOT. The results also indicate that the aggregation of AOT in water and polymers solutions is entropically driven. The observed thermal effects have been interpreted in terms of the interactions of the polymer molecules with AOT monomers or the molecular clusters. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 275–283, 2006     

Solvation dynamics in aqueous anionic and cationic micelle solutions: sodium alkyl sulfate and alkyltrimethylammonium bromide

Solvation dynamics of the fluorescence probe, coumarin 102, in anionic surfactant, sodium alkyl sulfate (C(n)H(2n+1)SO(4)Na; n = 8, 10, 12, and 14), and cationic surfactant, alkyltrimethylammonium bromide (C(n)H(2n+1)N(CH(3))(3)Br; n = 10, 12, 14, and 16), micelle solutions have been investigated by a picosecond streak camera system. The solvation dynamics in the time range of 10(-10)-10(-8) s is characterized by a biexponential function. The faster solvation time constants are about 110-160 ps for both anionic and cationic micelle solutions, and the slower solvation time constants for sodium alkyl sulfate and alkyltrimethylammonium bromide micelle solutions are about 1.2-2.6 ns and 450-740 ps, respectively. Both the faster and the slower solvation times become slower with longer alkyl chain surfactant micelles. The alkyl-chain-length dependence of the solvation dynamics in both sodium alkyl sulfate and alkyltrimethylammonium bromide micelles can be attributed to the variation of the micellar surface density of the polar headgroup by the change of the alkyl chain length. The slower solvation time constants of sodium alkyl sulfate micelle solutions are about 3.5 times slower than those of alkyltrimethylammonium bromide micelle solutions for the same alkyl-chain-length surfactants. The interaction energies of the geometry optimized mimic clusters (H(2)O-C(2)H(5)SO(4)(-) and H(2)O-C(2)H(5)N(CH(3))(3)(+)) have been estimated by the density functional theory calculations to understand the interaction strengths between water and alkyl sulfate and alkyltrimethylammonium headgroups. The difference of the slower solvation time constants between sodium alkyl sulfate and alkyltrimethylammonium bromide micelle solutions arises likely from their different specific interactions.     

阴离子表面活性剂与非离子水溶性大分子二元体系的临界类胶束聚集数

将对应于γ～lgc双拐点体系第一拐点c₁的N₁定义为第一临界类胶束聚集数[N₁]₁.实验结果表明,[N₁]₁是依赖于表面活性剂结构以及大分子结构的不变量或结构本征值,不随大分子分子量和大分子浓度变化而改变.     

1-(4-硝基苯基)-3-[4-(苯基偶氮)苯基]-三氮烯-溴化十六烷基三甲铵-阴离子表面活性剂显色反应的研究及应用

在三乙醇胺存在下,１－（４－硝基苯基）－３－［４－（苯基偶氮）苯基］－三氮烯（Ｃａｄｉｏｎ）与溴化十六烷基三甲铵（ＣＴＭＡＢ）和阴离子表面活性剂（ＡＳ）形成红色配合物,其最大吸收位于５５０ｎｍ。改变阴离子表面活性剂十二烷基苯磺酸钠、十二烷基磺酸钠、十二烷基硫酸钠时,有色配合物的表观摩尔吸光系数ε５５０分别为３．０２×１０４、２．１３×１０４、２．９４×１０４（Ｌｍｏｌ－１ｃｍ－１）,阴离子表面活性剂服从比尔定律的范围分别为０～４．１８ｍｇ／Ｌ,０～２．１８ｍｇ／Ｌ,０～３．４６ｍｇ／Ｌ。方法用于测定环境水样中阴离子表面活性剂,结果满意     

Interaction between a partially fluorinated alkyl sulfate and gelatin in aqueous solution

The interaction of a partially fluorinated alkyl sulfate, sodium 1H,1H,2H,2H-perfluorooctyl sulfate (C6F13CH2CH2OSO3Na), with the polyampholyte gelatin has been examined in aqueous solution using surface tension and small-angle neutron scattering (SANS). The 19F chemical shift of each fluorine environment in the surfactant is unaltered by the addition of gelatin, indicating that there is no contact between the gelatin and the fluorocarbon core of the micelle. The chemical shift of the two methylene groups closest to the headgroup is altered when gelatin is present, disclosing the location of the polymer. The critical micelle concentration (cmc) of the surfactant, cmc = 17+/-1 mM, corresponds to an effective alkyl chain (CnH2n+1) length of n = 11. In the presence of gelatin, the cmc is substantially reduced as expected, cmc(1) = 4+/-1 mM, which is also consistent with an effective alkyl chain length of n = 11. In the presence of the fluorosurfactant, the monotonic decay of the SANS from the gelatin-only system is replaced by a substantial peak at an intermediate Q value mirroring the micellar interaction. At low ionic strengths, the gelatin/micelle complex can be described by an ellipsoid. At higher ionic strengths, the electrostatic interaction between the micelles is screened and the peak in the gelatin scattering disappears. The correlation length describing the network structure decreases with increasing SDS concentration as the bound micelles promote a collapse of the network.