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2.
The chain conformation of sodium poly(styrenesulfonate) (NaPSS) in the semidilute aqueous solution, estimated from the plots of reduced viscosity versus segmental concentration, was found to be dependent on the degree of sulfonation and dissociation extent of counterions. The latter, altered by the content of sodium chloride external salt, was estimated from the ionic conductivity measurements on the basis of the modified Manning's conductivity theories with consideration of the influence of chain overlapping in the semidilute regime. The results indicate that the increase of chain extension of NaPSS with counterion dissociation was further enhanced by increasing the degree of sulfonation. 相似文献
3.
The behavior of lithium ions in a comb-like polymer electrolyte with a chelating functional group have been characterized by differential scanning calorimeter (DSC), dynamic mechanical analysis (DMA), Fourier transform infrared (FTIR) spectroscopy, ac impedance and 7Li solid-state NMR measurements. The comb-like copolymer is synthesized by poly(ethylene glycol-methyl ether methacrylate) (PEGMEM) and (2-methylacrylic acid 3-(bis-carboxymethylamino) -2-hydroxy-propyl ester) (GMA-IDA). FTIR and 7Li solid-state NMR spectra demonstrate the interactions of Li+ ions with both the ether oxygen of the PEGMEM and the nitrogen atom of the GMA-IDA segments. Moreover, 7Li solid-state NMR shows that the lithium ions are preferentially coordinated to the GMA-IDA segment. The Tg increases for the copolymers doped with LiClO4. These results indicate the interactions of Li+ with both PEGMEM and GMA-IDA segments form transient cross-links. The Vogel-Tamman-Fulcher (VTF)-like behavior of conductivity implies the coupling of the charge carriers with the segmental motion of the polymer chains. The dependence of the maximum conductivity on the composition of the copolymers and the doping lithium ion concentration was determined. The GMA-IDA unit in the copolymer improves the dissociation of the lithium salt, the mechanical strength and the conductivity. 相似文献
4.
Xuping Sun 《Polymer》2004,45(7):2181-2184
Polyelectrolyte-protected gold nanoparticles have been facilely obtained by heating an amine-containing polyelectrolyte/HAuCl4 aqueous solution without the additional step of introducing other reducing agents. All experimental data indicate that different initial molar ratio of polyelectrolyte to gold can lead to the formation of dispersed nanoparticles, quasi one-dimensional aggregates of nanoparticles or bulk metal deposits. More importantly, the growth kinetics of gold particles thus formed can be tuned by changing the initial molar ratio of polyelectrolyte to gold. 相似文献
5.
Zwitterionic compounds such as those based on 1-butylimidazolium-3-(n-butanesulfonate) have previously been shown to have positive effects on the transport properties of polyelectrolytes. The addition of the zwitterion has been found to, in some cases, increase the dissociation of the lithium ion and enhance the conductivity by almost an order of magnitude. In this work, we report the effects of adding the above-mentioned zwitterion into the polyelectrolyte gel system poly(lithium methacrylate-co-N,N-dimethyl acrylamide); the anionic group being a stronger base leads to different behaviour for this copolymer compared to previous work. Polyelectrolyte gels based on dimethyl sulfoxide and polyether solvents were investigated to determine the breadth of applicability of the zwitterion in improving lithium ion transport. Impedance spectroscopy and pulse field gradient-NMR diffusion indicate an increase in the number of available charge carriers with zwitterion addition in some gel systems, however, the effect is not universal. 相似文献
6.
Self-association (i.e. interchain aggregation) behavior of atactic poly(ethacrylic acid) PEA in dilute aqueous solution as function of degree-of-neutralization by Na+ counter-ions (i.e. charge fraction f) was investigated by molecular dynamics simulations. Aggregation is found to occur in the range 0 ≤ f ≤0.7 in agreement with experimental results compared at specified polymer concentration Cp = 0.36 mol/l in dilute solution. The macromolecular solution was characterized and analysed for radius-of-gyration, torsion angle distribution, inter and intra-molecular hydrogen bonds, radial distribution functions of intermolecular and inter-atomic pairs, inter-chain contacts and solvation enthalpy. The PEA chains form aggregate through attractive inter-chain interaction via hydrogen bonding, in the range f < 0.7, in agreement with experimental observation. The numbers of inter-chain contacts decreases with f. A critical structural transition occurs at f = 0.7, observed via simulations for the first time, in Rg as well as inter-chain H-bonds. The inter-chain distance increases with f due to repulsive interactions between COO− groups on the chains. PEA-PEA electrostatic interactions dominant solvation enthalpy. The PEA solvation enthalpy becomes increasingly favorable with increase in f. The transition enthalpy change, in going from uncharged (acid) state to fully charged state (f = 1) is unfavorable towards aggregate formation. 相似文献
7.
A single chip, multi-channel surface plasmon resonance (SPR) imaging system has been developed. The equipment has no moving parts and uses a single sensor chip on which multiple channels can be incorporated. A light emitting diode is used as a photon source while a CCD camera forms the detector. The optical configuration has been designed to achieve a uniform illumination of the sample over a fixed area with a range of incident angles. A calibration test using sucrose solutions shows that the sensitivity of the equipment is 4.3×10−4 refractive index units per pixel line-pair. The use of the system for simultaneous interrogation of different polyelectrolyte thin films, formed by the electrostatic layer-by-layer deposition method, is demonstrated. A reversible pH-dependent response for these organic layers is also reported. 相似文献
8.
Uric acid (UA) was detected in the presence of ascorbic acid (AA) at GC electrode by cyclic voltametry (CV) and differential pulse voltametry (DPV) in aqueous media of cationic polyelectrolyte (poly(diallyldimethylammonium chloride) (PDDA)). Both, UA and AA are anionic nature and electro-static attraction with cationic solution. This lowered their oxidation potentials and increased anodic current. In CV studies, the UA oxidation potential was decreased by 400 mV in the presence of PDDA along with increase in peak current. Effect of PDDA and pH on Epa and Ipa were also studied. About 360 mV difference in oxidation peak potentials was observed for AA and UA in PDDA media, which established a quick method for their simultaneous determination. The detection limit of UA in the presence of 200 folds AA was found as 1 μM with correlation coefficient of 0.994 and sensitivity of 0.05 μA μM−1. The proposed method has been also applied for determining the UA in human urine without any pretreatment, and found to be satisfactory. 相似文献
9.
Polysaccharides from okra pods (Abelmoschus esculentus) were extracted using a sequential extraction protocol and compared with a simple extraction at pH 6. Rheological properties of three okra extracts were then investigated by means of molecular weight determination, dilute solution rheology, steady shear and oscillatory rheological measurements. The extraction protocols resulted in extracts of relatively high purity and multimodal molecular weight distribution. Furthermore, molecular parameters of the isolated biopolymers such as intrinsic viscosity, Huggins constant, critical concentration and coil overlap parameter were calculated from dilute solution viscometry. Investigation of the generalized flow behaviour using a modified Cross equation and Cox–Merz plots showed evidence that as concentration increases specific interactions start taking place among the polymeric chains that modify the rheological behaviour of the extracts. The change in the rheological behaviour could not only be explained by differences in the molecular weight of the samples but also should be attributed to the fine structure of the chains that are obtained under the different extraction protocols. Present investigation shows that further optimization of such protocols may result in polysaccharide fractions with specific rheological properties. 相似文献
10.
Polyelectrolyte bilayers, which consist of poly-l-lysine (PLL) and hyaluronic acid (HA) were simulated with lipid membranes at different temperatures and ion concentrations. Starting with the sequential deposition of PLL and HA above the membrane surface, PLL and HA become completely mixed, leading to the formation of stable bilayers. PLL/HA bilayers are thicker at higher salt concentration because of weakened electrostatic interactions between PLLs and membrane lipids, in agreement with experiments. This salt effect decreases as PLL size increases. Also, bilayers become thinner at higher temperature because of the increased surface area of membrane. In particular, regardless of temperature and salt concentration, larger PLLs induce thicker bilayers, although larger PLLs have lower diffusivities than do smaller ones. Bilayers with larger PLLs show larger vacancy (more water) inside the bilayer, indicating that larger PLLs are less densely stacked on membrane surface than do smaller ones and thus form the thicker bilayer. These findings show the lower diffusivity of larger polyelectrolytes, which supports the experimental observation regarding the restricted diffusion of large polymers, and also imply the dependence of bilayer thickness on the polymer size. 相似文献