NMR investigations of self-aggregation characteristics of SDS in a model assembled tri-block copolymer solution

The present work was undertaken with a view to understand the influence of a model non-ionic tri-block copolymer PEO-PPO-PEO (poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide)) with molecular weight 5800 i.e., P123 [(EO)(20)-(PO)(70)-(EO)(20)] on the self-aggregation characteristics of the anionic surfactant sodium dodecylsulfate (SDS) in aqueous solution (D(2)O) using NMR chemical shift, self-diffusion and nuclear spin-relaxation as suitable experimental probes. In addition, polymer diffusion has been monitored as a function of SDS concentration. The concentration-dependent chemical shift, diffusion data and relaxation data indicated the significant interaction of polymeric micelles with SDS monomers and micelles at lower and intermediate concentrations of SDS, whereas the weak interaction of the polymer with SDS micelles at higher concentrations of SDS. It has been observed that SDS starts aggregating on the polymer at a lower concentration i.e., critical aggregation concentration (cac=1.94 mM) compared to polymer-free situation, and the onset of secondary micelle concentration (C(2)=27.16 mM) points out the saturation of the 0.2 wt% polymer or free SDS monomers/micelles at higher concentrations of SDS. It has also been observed that the parameter cac is almost independent in the polymer concentrations of study. The TMS (tetramethylsilane) has been used as a solubilizate to measure the bound diffusion coefficient of SDS-polymer mixed system. The self-diffusion data were analyzed using two-site exchange model and the obtained information on aggregation dynamics was commensurate with that inferred from chemical shift and relaxation data. The information on slow motions of polymer-SDS system was also extracted using spin-spin and spin-lattice relaxation rate measurements. The relaxation data points out the disintegration of polymer network at higher concentrations of SDS. The present NMR investigations have been well corroborated by surface tension and conductivity measurements.     

The phases of polymers as determined by NMR

Nuclear magnetic resonance (NMR) spectroscopy has been used to study the morphology and dynamics in semicrystalline polymers. Dynamics may be observed through NMR relaxation rates that are sensitive to motions in the 1–10⁸ Hz range, or through modulation of anisotropic magnetic interactions, such as the chemical shift and dipole-dipole interactions. Morphological structure may be inferred through NMR measurements of polymer dynamics or investigated directly through studies of the magnetic interactions. Here, we discuss the study of morphological structure in semicrystalline polymers using NMR, and review results on poly(ethylene terephthalate) that address the question of the number of phases in this semicrystalline polymer.This work was funded by the Office of Naval Research.     

Characterization of sodium dodecylsulphate and dodecylphosphocholine mixed micelles through NMR and dynamic light scattering

The complexity of biological membranes leads to the use of extremely simplified models in biophysical investigations of membrane‐bound proteins and peptides. Liposomes are probably the most widely used membrane models due, especially, to their versatility in terms of electric charge and size. However, liquid‐state NMR suffers the lack of such a model, because even the smallest liposomes slowly tumble in solution, resulting in a dramatic signals broadening. Micelles are typically used as good substitutes, with sodium dodecylsulphate (SDS) and dodecylphosphocholine (DPC) being the most widely employed surfactants. However, they are always used separately to mimic prokaryotic and eukaryotic membranes, respectively, and accurate investigations as a function of surface charge cannot be performed. In this work, the critical micelle concentration (CMC) of binary mixtures with different SDS/DPC ratios has been determined by following the chemical shift variation of selected ¹H and ³¹P NMR signals as a function of total surfactant concentration. The regular solution theory and the Motomura's formalism have been applied to characterize the micellization both in water and in phosphate buffer saline, and results were compared with those obtained directly from the experimental NMR chemical shift. The ζ‐potential and size distribution of the mixed micelles have been estimated with dynamic light scattering measurements. Results showed that SDS and DPC are synergic and can be used together to prepare mixed micelles with different negative/zwitterionic surfactants molar ratio. Copyright © 2013 John Wiley & Sons, Ltd.     

二元钠硅酸盐的精细结构和 29Si化学位移的从头计算研究

本文应用量子化学从头计算方法研究二元钠硅酸盐的精细结构，对典型的系列二元钠硅酸盐团簇模型采用闭壳层Hartree-Fock(RHF)方法和基组6-31G(d)优化构型，并计算了硅酸盐团簇中 ²⁹Si核磁共振化学位移δ_iso^Si，用硅氧四面体应力指数这一精细结构参数分析了计算得到的δ_iso^Si数值。同时对 ²⁹Si核磁共振化学位移δ_iso^Si的计算值和实验值进行比较，并讨论了两者间在数值上存在的差异。研究表明， ²⁹Si核磁共振化学位移与硅酸盐的精细结构密切相关，这说明硅酸盐的宏观物理和化学性质可能主要依赖于其精细结构而非初级结构单元-硅氧四面体。     

Fluorescence Probe Study of the Interaction Between Acrylic Acid-co-Ethyl Methacrylate Copolymers and Sodium Dodecylsulfate

The interaction between sodium dodecylsulfate (SDS) and acrylic acid (AA)–ethyl methacrylate (EMA) copolymers has been investigated using steady state fluorescence and conductimetric measurements to assess the effect of the polymer composition on the aggregation process. Micropolarity studies using the ratio between the emission intensities of the vibronic bands of pyrene (I₁/I₃) and the shift of the fluorescence emission of pyrene-3-carboxaldehyde show that the interaction of SDS with AA-EMA copolymers occurs at surfactant concentrations smaller than that observed for the pure surfactant in water and depends on the copolymer composition. The increase of ethyl methacrylate in the copolymers lowers the critical aggregation concentration (CAC) due to the larger hydrophobic character of the polymer backbone. The formation of aggregates on the macromolecule is induced mainly by hydrophobic interactions, but the process is also influenced by the ionic strength due to the counter-ions of the polyelectrolyte.     

Aggregation behavior of acrylamide/2-phenoxyethyl acrylate and its interaction with sodium dodecyl sulfate in aqueous solution studied by proton 1D and 2D NMR

¹H NMR self-diffusion coefficient, spin-lattice relaxation time, spin-spin relaxation time, and two-dimensional nuclear Overhauser enhancement (2D NOESY) measurements have been used to study the association behavior of a novel hydrophobically associating copolymer composed of acrylamide (AM) and a small amount of 2-phenoxyethyl acrylate (POEA), and its interaction with the anionic surfactant sodium dodecyl sulfate (SDS). Three sets of copolymers with approximately the same composition but with different hydrophobic POEA contents were investigated. The POEA contents for these copolymers were about 1.41, 1.03, and 0.56 mol% respectively, as validated by ¹H NMR spectra. Self-diffusion coefficient measurements show that the aggregation process occurs in a relative narrow concentration range and the critical association concentrations (cacs), of these copolymers are within this narrow concentration range, which are in agreement with those measured by viscosity measurements (6 g L^–1). Above this concentration, the hydrophobic POEA moieties are found to associate and possibly build a transitory three-dimensional network along the polyacrylamide (PAM) backbones, which induces a strong decrease in NMR parameters including self-diffusion coefficients and relaxation times. The surfactant SDS showed a significant interaction with the copolymer in the dilute solution. Addition of SDS resulted in the binding of SDS on copolymer POEA-PAM segments and reinforced the interchain transient network formation of copolymer at a concentration below its cac. In the SDS/POEA-PAM mixed systems, the hydrophobic methylene groups of the SDS molecules were preferentially located in the vicinity of the phenoxy groups of the POEA hydrophobes.     

Study of ion exchange selectivity of organic ions by using (31)P NMR spectroscopy

Ion exchange distribution of the phenylphosphoric acid has been studied on various types of chloride form strong base resins as a function of pH at 25 °C, at 0.1 M ionic strength. Equilibrium measurements were supplemented by the study of pH dependence of the ³¹P NMR spectra of the resin-phase phenylphosphate species. Equations were derived to describe the pH dependence of the overall distribution coefficient and the chemical shift of the resin-phase solute species. Experimental data were evaluated by using these model equations and the values of the individual distribution coefficients, ion exchange selectivity coefficients and the resin-phase ³¹P chemical shifts of the mono- and divalent ions have been calculated. Comparison of distribution data of the individual species corroborated the significance of the role of hydrophobic interaction in the selectivity of organic ion exchange processes. A well-defined correlation between the ion exchange selectivity and the resin-phase ³¹P NMR chemical shift data has been pointed out.     

Molecular interactions in polystyrene cosolvent systems

Studied here are miscible binary cosolvents for polystyrene, for which polystyrene is insoluble in either of the individual solvents. Polymer-solvent interactions in solutions of atactic polystyrene in acetone/diethyl ether and in methylcyclopentane (MCP)/acetone binary cosolvents have been investigated using nuclear magnetic resonance (NMR) spectroscopy. Polystyrene ¹³C chemical shifts were measured as a function of miscible binary solvent compositions and temperature. The NMR data were used to calculate “association constants” as a measure of specific interactions of the solvent components with all sites on the polymer. In mixtures of acetone and diethyl ether, ¹³C-NMR indicates a weak interaction between the polystyrene phenyl ring and the diethylether solvent component. In the polystyrene/MCP/acetone system, present NMR data reveal no preferential interactions. Additional NMR measurements were performed on polystyrene in mixtures of CCl₄/acetone. From these results, it is concluded that although preferential polymer-solvent interactions are present in some cosolvent systems, they are not a prerequisite for such behavior.     

DFT和热力学研究氢键协同效应及对关联1H NMR的影响

用DFT方法在B3LYP/6-311＋＋G (d,p)水平下研究了甲醇线性和环状分子簇. 对于不同大小的分子簇之间定义了协同因子. 计算得到的协同因子可以验证氢键的强协同效应, 环状分子簇之间的协同效应远远大于线性分子簇. 做为理论验证和比较, 热力学模型分别采用含氢键缔合的格子流体状态方程(LFHB), 以及含氢键协同效应的LFHB, 关联醇-惰性体系的¹H核磁共振化学位移. 考虑协同效应的关联结果优于原始的LFHB. 比较量子化学计算的和热力学模型中采用的协同因子, 认为甲醇和乙醇在溶液中更可能大部分以线性缔合形式存在.     

Image analysis of the spatial distribution of paramagnetic Pr3+ ions in a polymer gel by a 1H-chemical shift NMR imaging method

¹H-chemical shift NMR imaging patterns of a poly(methacrylic acid) gel containing water with paramagnetic praseodymium ions(Pr³⁺) were successfully observed, in order to elucidate spatial distribution of Pr³⁺ ions in the gel. The ¹H chemical shift of water associated with Pr³⁺ ions in the gel moves largely downfield. By analyzing these experimental results, the immersion process of Pr³⁺ ions into the network of the polymer gel was spatially clarified. Further, it is shown that the chemical shift NMR imaging method is a useful means for determining the spatial distribution of paramagnetic metal ions in polymer gels.     

Phase conditions,hydrodynamic features and salt influence in the polymer-amphiphile interaction for the EHEC/SDS/water system

Two fractions of ethyl(hydroxy)ethyl cellulose, EHEC, and their interactions with sodium dodecyl sulphate, SDS, have been investigated. The effect of salt on these interactions was explored. The more hydrophobic fraction exhibits a cloud point (CP) of 30°C, and the more hydrophilic fraction has a CP around 65°C. The properties of the systems were studied by means of hydrodynamic (viscosity), equilibrium dialysis and cloud point measurements. Dye solubilization was used to obtain indications of cluster formation on the polymer backbone. The equilibrium dialysis shows a steep binding beginning at a critical surfactant concentration indicating a cooperative effect in the EHEC/SDS/water system. It is found that when the degree of binding is moderate and only 10–20% of the value at saturation, the specific viscosity effects occur and solutions containing high polymer concentrations pass a marked maximum in viscosity. It is shown that the maximum in viscosity and the collcoil interaction, expressed as Huggins constant,k _H, appear a composition with the same fractional amount of SDS adsorbed to both EHEC fractions. It was found that the onset of redistribution and increase in viscosity were shifted to higher SDS concentrations, although still below the normal CMC, for the EHEC fraction with a high CP. When small amounts of salt are present in the EHEC/SDS/water solutions, the CP curves develop a pronounced minimum at low SDS concentrations. The redistribution of SDS to the polymers starts immediately in the presence of salt, but the viscosity of the solutions is affected only in a very narrow composition interval.     

Inclusion Compounds Formation of Poly(azomethine ether)s and β‐Cyclodextrin

In this study, two poly(azomethine ether)s were synthesized and they can form inclusion compounds (ICs) with β‐cyclodextrin (β‐CD). Fourier transform infrared (FTIR) spectroscopy, ¹H nuclear magnetic resonance spectroscopy (¹H‐NMR), thermogravimetric analysis (TGA), X‐ray diffraction (XRD) have been utilized to observe the formation of polymer‐CD‐ICs. The differentiation in their FTIR spectra may indicate the formation of the inclusion compounds between poly(azomethine ether)s and β‐CD. Compared the ¹H‐NMR of polymer‐CD‐ICs with β‐CD, proton signals belonging to both β‐CD and poly(azomethine ether)s can be found in the spectrum. The chemical shift of the protons H‐3, H‐5 has changed after the formation of inclusion compounds, which is perhaps due to the interaction of these protons with polymers. TGA scans showed the much higher decomposition temperatures observed for two polymer‐CD‐ICs may imply that polymer chains included inside the β‐CD's cavity can greatly improve β‐CD's stabilities. The X‐ray diffraction patterns were confirmed to be the new crystal structures.     

Fluorine chemical shift anisotropy in 1,1-difluoroethene

Chemical shift anisotropies can be determined from NMR in liquid crystalline solutions. In interpreting the experimental data it is customary to assume that the chemical shift is axially symmetric around the bond axis.NMR experiments on 1,1-difluoroethene are reported from which this assumption can be tested. The results confirm axial symmetry of the ¹⁹F chemical shift tensor around the CF bond.     

Poly(N-vinyl-2-pyrrolidone) and 1-Octyl-2-pyrrolidinone Modified Ionic Microemulsions

The influence of the nonionic polymer poly(N-vinyl-2-pyrrolidone) (PVP) in comparison to the surfactant 1-octyl-2-pyrrolidinone (OP) on the phase behavior of the system SDS/pentanol/xylene/water was studied. In both modified systems a strong increase in the water solubilization capacity was found, accompanied by a change in the spontaneous curvature toward zero. In the polymer-modified system an isotropic phase channel is formed with increasing polymer content that connects the L1 and the L2 phase. The lamellar liquid crystalline phase is destabilized in both cases. In the L1 phase the adsorption of PVP at the surface of the microemulsion droplets and the formation of a cluster-like structure is proven by several methods like ¹³C NMR T₁ relaxation time measurments, zeta potential measurements, and rheology. In the L2 phase a modification of the interface of the inverse droplets is detected by a shift in the percolation boundary (conductivity) and ¹³C NMR T₁ relaxation measurements. The formation of a cluster-like structure can be assumed on the basis of our rheological measurements.     

H/P NMR pH indicator series to eliminate the glass electrode in NMR spectroscopic pKa determinations

NMR titration is an efficient method to determine pK_a values of multiprotic acids in aqueous solution. While modern 1D/2D NMR techniques yield chemical shifts with increasing precision, the glass electrode-based pH measurement becomes the limiting factor to affect the precision of the resulting dissociation constants. The pH in the NMR tube can also be deduced from the actual chemical shift of an appropriate monoprotic indicator molecule. In the present work, the in situ NMR pH measurement has been extended for the entire pH range 0-12 using indicators with overlapping ranges of dissociation. In the first, calibrating ¹H/³¹P NMR titration, limiting chemical shifts and pK were determined for each indicator. An analysis of error propagation showed that the accuracy and precision of glass electrodes can be achieved at 1.8 < pH < 12 and even exceeded at pH extremes by NMR indicators, respectively. The assembled set of indicators was applied for in situ pH monitoring in the following “electrodeless” ¹H/³¹P NMR titration of a newly synthesized aminophosphinophosphonic acid. Multivariate nonlinear parameter estimation was used to calculate the pK values that were confirmed by potentiometric titrations.     

High Temperature Interaction Chromatography of Olefin Copolymers

Summary: The synthesis and characterization of polyolefins continues to be one of the most important areas for academic and industrial polymer research. One consequence of the development of new “tailor-made” polyolefins is the need for new and improved analytical techniques for the analysis of polyolefins with respect to molar mass and chemical composition distribution. The present article briefly reviews different new and relevant chromatographic techniques for polyolefin analysis. For the fast analysis of the chemical composition distribution of polyolefins a new high-temperature gradient high-performance liquid chromatography (HPLC) system has been introduced. The efficiency of this system for the separation of various olefin copolymers is demonstrated. The correlation between elution volume and chemical composition can be accessed by on-line coupling of high temperature HPLC with FTIR spectroscopy. For the elucidation of the chemical composition as a function of molar mass high-temperature size exclusion chromatography and ¹H-NMR spectroscopy can be coupled. It is shown that the on-line NMR analysis of chromatographic fractions yields information on microstructure and chemical composition in addition to molar mass distribution.     

Selenate—An internal chemical shift standard for aqueous 77Se NMR spectroscopy

The ⁷⁷Se NMR spectra of selenate were studied under various circumstances, such as concentration, pH, temperature, ionic strength, and D₂O:H₂O ratio, in order to examine its potential as a water-soluble internal chemical shift standard. The performance of selenate as a chemical shift reference and that of other attempted ones from the literature (dimethyl selenide, tetramethylsilane/TMS, and 3-(trimethylsilyl)propane-1-sulfonate/DSS) was also explored. The uncertainty in the resulting chemical shift relative to the effective spectral width is comparable to that of DSS. Compared to the currently prevalent water-soluble external chemical shift reference, selenic acid solution, the properties of internal selenate are much more favorable in terms of ease of use. We have also demonstrated that selenate can be used in reducing media, which is inevitable for the analysis of selenol compounds. Thus, it can be stated that sodium selenate is a robust internal chemical shift reference in aqueous media for ⁷⁷Se NMR measurements; the chemical shift of this reference in a solution containing 5 V/V% D₂O at 25°C and 0.15 mol·dm⁻³ ionic strength is 1048.65 ppm relative to 60 V/V% dimethyl selenide in CDCl₃ and 1046.40 ppm relative to the ¹H signal of 0.03 V/V% TMS in CDCl₃. In summary, a water-soluble, selenium-containing internal chemical shift reference compound was introduced for ⁷⁷Se NMR measurements for the first time in the literature, and with the aforementioned results all previous ⁷⁷Se measurements can be converted to a unified scale defined by the International Union of Pure and Applied Chemistry.     

Binding of sodium dodecyl sulfate and hexaethylene glycol mono-n-dodecyl ether to the block copolymer L64: electromotive force, microcalorimetry, surface tension, and small angle neutron scattering investigations of mixed micelles and polymer/micellar surfactant complexes

The interactions of sodium dodecyl sulfate (SDS) with the triblock copolymer L64 (EO13-PO30-EO13) and hexaethylene glycol mono-n-dodecyl ether (C12EO6) were studied using electromotive force, isothermal titration microcalorimetry, differential scanning microcalorimetry, and surface tension measurements. In certain regions of binding, mixed micelles are formed, and here we could evaluate an interaction parameter using regular solution theory. The mixed micelles of L64 with both SDS and C12EO6 exhibit synergy. When L64 is present in its nonassociated state, it forms polymer/micellar SDS complexes at SDS concentrations above the critical aggregation concentration (cac). The cac is well below the critical micellar concentration (cmc) of pure SDS, and a model suggesting how bound micelles are formed at the cac in the presence of a polymer is described. The interaction of nonassociated L64 with C12EO6 is a very rare example of strong binding between a nonionic surfactant and a nonionic polymer, and C12EO6/L64 mixed micelles are formed. We also carried out small angle neutron scattering measurement to determine the structure of the monomeric polymer/micellar SDS complex, as well as the mixed L64/C12EO6 aggregates. In these experiments, contrast matching was achieved by using the h and d forms of SDS, as well as C12EO6. During the early stages of the formation of polymer-bound SDS micelles, SDS aggregates with aggregation numbers of approximately 20 were found and such complexes contain 4-6 bound L64 monomers. The L64/C12EO6 data confirmed the existence of mixed micelles, and structural information involving the composition of the mixed micelle and the aggregation numbers were evaluated.     

Investigation of the Interactions of Polyvinylpyrrolidone with Mixtures of Anionic and Nonionic Surfactants or Anionic and Zwitterionic Surfactants by Pulsed Field Gradient NMR

The interaction of polyvinylpyrrolidone (PVP) with an anionic surfactant (sodium dodecyl sulfate, SDS), a nonionic surfactant (pentaethylene glycol monodecyl ether, C(10)E(5)), and a zwitterionic surfactant (lauryl amido propyl betaine, LAPB) has been investigated by means of pulsed gradient spin-echo NMR (FT-PGSE NMR), allowing self-diffusion coefficients to be determined. The results confirm the strong interaction prevailing in the PVP/SDS system, whereas no association has been observed in the PVP/C(10)E(5) and PVP/LAPB systems. Mixing PVP with two surfactants, namely SDS and C(10)E(5) or SDS and LAPB, results in the formation of ternary aggregates between the polymer and the mixed micelles. Copyright 2001 Academic Press.