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1.
The binding of 1-anilinonaphthalene-8-sulphonate (ANS) to poly(N-vinyl-2-pyrrolidone) (PVP) of molecular weight grades k30
(molecular weight 40,000) and k90 (360,000) was studied by a dialysis technique in 0·05 M phosphate buffer, pH 7·1, at different
temperatures. The intrinsic binding constant,K, was determined. The binding was favoured by negative enthalpy and positive entropy in both the systems indicating respectively
that energetic forces and hydrophobic interactions were contributing to the binding affinity. The effects of addition of urea
and palmitic acid on binding were investigated by dialysis and fluorescence techniques. The results showed that the binding
of ANS to PVP was dependent on the nature and microenvironment of the binding sites and thereby pointed out the importance
of the iceberg structure of water in the binding system. 相似文献
2.
The interaction of 1-anilinonaphthalene-8-sulphonate (ANS) with cross-linked poly(N-vinyl-2-pyrrolidone) (CPVP) was studied
by the adsorption technique at different temperatures and at two different pH values. Analysis by the Scatchard method and
the study made in the presence of urea showed that the iceberg structure of water affects the sorption of ANS to CPVP, leading
to cooperativity. The observed Giles sorption isotherms at both the pH values were of theL-type which indicated the interaction of ANS in flat configuration with the binding site in CPVP. The sorption of ANS to CPVP
was enhanced considerably at acidic pH due to some structural factors which also resulted in multilayer sorption at this pH.
Comparison of binding of ANS to CPVP and to linear poly(N-vinyl-2-pyrrolidone) demonstrated the greater contribution of hydrophobic
interaction in CPVP than in the linear polymer. 相似文献
3.
用差示量热扫描热分析仪(DSC)测试了不同降温速率下聚2-吡咯烷酮(PPD)样品的温度-热焓曲线,样品黏均分子量为2.2×10~4,熔点为272℃。采用Jeziorny法、Ozawa法和莫志深法分析了PPD的非等温结晶动力学。结果表明,在给定降温速率范围内,Ozawa法不适用于描述PPD的非等温结晶动力学过程,Jeziorny法只适用于描述PPD的主结晶阶段,而莫志深法能很好地描述整个结晶过程。Jeziorny法处理结果表明,PPD主结晶阶段的Avrami指数(n)为1.68~1.78,晶体生长为准二维生长。莫志深法处理结果表明,在单位结晶时间里达到某一相对结晶度所需的降温速率随相对结晶度的增加而增大。用Kissinger方程求得PPD的非等温结晶活化能为-31.9kJ/mol。 相似文献
4.
A headspace solid-phase microextraction and gas chromatography-nitrogen-phosphorous detection (HS-SPME-GC-NPD) method using polypyrrole (PPy) fibers has been introduced to determine two derivatives of pyrrolidone; N-vinyl-2-pyrrolidone (NVP) and N-methyl-2-pyrrolidone (NMP). Two types of PPy fibers, prepared using organic and aqueous media, were compared in terms of extraction efficiency and thermal stability. It was found that PPy film prepared using organic medium (i.e. acetonitrile) had higher extraction efficiency and more thermal stability compared to the film prepared in aqueous medium. To enhance the sensitivity of HS-SPME, the effects of pH, ionic strength, extraction time, extraction temperature and the headspace volume on the extraction efficiency were optimized. Using the results of this research, high sensitivity and selectivity had been achieved due to the combination of the high extraction efficiency of PPy film prepared in organic medium and the high sensitivity and selectivity of nitrogen-phosphorous detection. Linear range of the analytes was found to be between 1.0 and 1000 μg L−1 with regression coefficients (R2) of 0.998 and 0.997 for NVP and NMP, consequently. Limits of detection (LODs) were 0.074 and 0.081 μg L−1 for NVP and NMP, respectively. Relative standard deviation (R.S.D.) for five replications of analyses was found to be less than 6.0%. In real samples the mean recoveries were 94.81% and 94.15% for NVP and NMP, respectively. The results demonstrated the suitability of the HS-SPME technique for analyzing NVP and NMP in two different pharmaceutical matrices. In addition, the method was used for simultaneous detection of NVP, 2-pyrrolidone (2-Pyr), γ-butyrolactone (GBL) and ethanolamine (EA) compounds. 相似文献
5.
A novel thermo-responsive diblock copolymer of poly(N-vinyl-2-pyrrolidinone)-block-poly(N-isopropylacrylamide) (PNVP-b-PNIPAM) was synthesized. FT-IR, 1H-NMR and SEC results confirmed the successful synthesis of PNVP-b-PNIPAM diblock copolymer via anionic polymerization. The polymeric micelles formed from PNVP-b-PNIPAM copolymer in aqueous solution were developed and characterized as a potential thermo-responsive and biocompatible drug delivery system. Micellization of the diblock copolymer in aqueous solution was characterized by dynamic laser scattering (DLS), turbidity measurement, tension measurement and transmission electron microscopy (TEM). The thermo-responsive polymeric micelles with the size ranges of 200 to 260 nm and thickness of 30 nm are localized, selected and targeted for drug release, having a great potential in response to external-stimulus such as temperatures from 35 to 39°C. The critical micellization concentration (cmc) of PNVP-b-PNIPAM in aqueous solution is 0.0026 wt% determined by turbidity measurement. The size of micelles determined by DLS increased from 163 to 329 nm with increasing concentration of PNVP-b-PNIPAM from 0.25 to 0.5 wt% in aqueous solution at 40°C, which is determined by DLS. 相似文献
6.
A physico-chemical investigation on the binding of some nonsteroidal anti-inflammatory drugs, Naproxen (NP) and Ketoprofen
(KP) and a drug model compound, salicylic acid (SA) to poly(N-vinyl-2-pyrrolidone) (PVP, molecular weight = 360,000), was
performed at pH 7.1 by the fluorescence competition method employing 1-anilinonaphthalene-8-sulphonate (ANS) as the fluorescent
probe. The binding affinities of these substrates to PVP are in the order KP < SA < NP which has been explained on the basis
of their structural features and the consequent effect on the interacting forces. Theπ-π interaction between the carbonyl group of PVP and theπ-ring system of the substrate molecule seems to be crucial in deciding the binding affinities of the substrates 相似文献
7.
Deswelling kinetics of water and terbinafine hydrochloride adsorbed poly(N-vinyl-2-pyrrolidone/itaconic acid) P(VP/IA) hydrogels were investigated. Hydrogels were prepared by irradiating the ternary mixture of VP/IA and cross-linking agent ethylene glycol dimethacrylate (EGDMA) in water by γ-rays at ambient temperature. Hydrogels swelled in pure water and terbinafine hydrochloride (TER-HCl) solutions at room temperature and deswelling or water loss were investigated between 4 and 45 °C temperature range and on human skin. The influence of IA content, % swelling, temperature and TER-HCl content on the water loss from gel matrix were investigated. Induction time for 80% water loss from hydrogel systems are found to increase from 9.6 to 21.2 h by increasing IA content in the gel system at 25 °C and decreased by 11 h with addition of TER-HCl in the gel system. Kinetic analyses had shown that the basic properties affecting the water loss behavior of these hydrogels are the IA and TER-HCl content and temperature of the medium. 相似文献
8.
A copolymer containing vinylcyclohexane (VCH) and N-vinyl-2-pyrrolidone (VP) at different compositions was synthesized and characterized. The monomer reactivity ratios (MRR) were estimated by using the classical Fineman-Ross and Kelen-Tüdõs linear fitting methods. These parameters were also estimated using a nonlinear computational fitting procedure, known as reactivity ratios error in variable model (RREVM). In this case, the values of MRR are rVP=2.2 and rVCH=0.0. Composition shifts and MRR values for (vinylcyclohexane-co-N-vinyl-2-pyrrolidone) copolymer (VCH-co-VP) are interpreted in terms of the relative comonomeric structures. A copolymer with zones containing VP blocks with isolated units of VCH between them is obtained. The presence or absence of the resonance stabilization effect is taken into account. The results are compared with those of similar related copolymeric systems. 相似文献
9.
The interactions between PEO and sodium alkylcarboxylates (octyl, decyl, and dodecyl) have been investigated by conductivity measurements and gel permeation chromatography (GPC). Also included in the study was sodium dodecyl sulfate. From the conductivity measurements the critical aggregation concentration, ionization degree, and binding ratios were determined; the binding ratio was also determined from GPC. PEO–surfactant interactions were observed for all the studied surfactants, except sodium octanoate. For the polymer–surfactant complexes the ionization degree was in all cases observed to be about 0.2 higher than the ionization degree for the corresponding aqueous micelles. Further, the binding ratio decreased somewhat with decreasing chain length of the alkylcarboxylate. The Gibbs free energy showed that the polymer–surfactant interaction decreases with decreasing chain length of the alkylcarboxylates and is weaker for alkylcarboxylate compared to alkylsulfate of similar chain length. 相似文献
10.
Yeast alcohol dehydrogenase (YADH) solubilized in reverse micelles of aerosol OT (i.e., AOT or sodium bis (2-ethyl hexyl) sulfosuccinate) in isooctane has been shown to be catalytically more active than that in aqueous buffer under optimum conditions of pH, temperature, and water content in reverse micelles. Studies of the secondary structure conformational changes of the enzyme in reverse micelles have been made from circular dichroism spectroscopy. It has been seen that the conformation of YADH in reverse micelles is extremely sensitive to pH, temperature, and water content. A comparison has been made between the catalytic activity of the enzyme and the α-helix content in the conformation and it has been observed that the enzyme is most active at the maximum α-helix content. While the β-sheet content in the conformation of the entrapped enzyme was found to be dependent on the enzyme–micelle interface interaction, the α-helix and random coil conformations are governed by the degree of entrapment and the extent of rigidity provided by the micelle core to the enzyme structure. 相似文献
11.
Gun'ko VM Zarko VI Leboda R Marciniak M Janusz W Chibowski S 《Journal of colloid and interface science》2000,230(2):396-409
Fumed oxides, such as silica, alumina, titania, and mixed X/silicas (X=Al2O3 (AS), TiO2 (TS), CVD-TiO2, Al2O3/TiO2 (AST)), pristine or covered by carbon deposits formed due to pyrolysis of cyclohexene, were studied using nitrogen adsorption–desorption, photon correlation spectroscopy particle sizing, and electrophoresis. A significant influence of the nature of surface-active sites and structural features of oxides (individual silica, mixed fumed, or prepared using chemical vapor deposition (CVD)) on the pyrolysis of cyclohexene is observed with respect to the pore size distributions due to differences between primary particles in aggregates and on their outer surfaces in the filling of channels by pyrocarbon, resulting also in a decrease in fractal dimension. Structural characteristics and dependences of the particle size distribution and electrokinetic potential of X/SiO2 and C/X/SiO2 on the pH of aqueous suspensions suggest that the carbon deposit covers mainly acidic sites at the X/SiO2 interfaces and X phase patches possessing catalytic activity in pyrolysis, as the negative charge of particles is reduced by pyrocarbon grafting. 相似文献
12.
Chojnacka A Ghaffar A Feilden A Treacher K Janssen HG Schoenmakers P 《Analytica chimica acta》2011,(2):305-311
Knowledge on the solubility behaviour and dissolution rate of speciality and commodity polymers is very important for the use of such materials in high-tech applications. We have developed methods for the quantification and characterization of dissolved copolymers of N-vinyl-2-pyrrolidone (VP) and vinyl acetate (VA) during dissolution in water. The methods are based on pyrolysis (Py) performed in a programmed-temperature vaporization injector with subsequent identification and quantification of the components in the pyrolysate using capillary gas chromatography–mass spectrometry (GC–MS). By injecting large volumes and applying cryo-focussing at the top of the column, low detection limits could be achieved.The monomer ratio was found to have the greatest effect on the dissolution rate of the PVP-co-VA copolymers. The material with the highest amount of VA (50%) dissolves significantly slower than the other grades. Size-exclusion chromatography (SEC) and Py–GC–MS were used to measure molecular weights and average chemical compositions, respectively. Combined off-line SEC//Py–GC–MS was used to determine the copolymer composition (VP/VA ratio), as a function of the molecular weight for the pure polymers. In the dissolution experiments, a constant VP/VA ratio across the dissolution curve was observed for all copolymers analysed. This suggests a random distribution of the two monomers over the molecules. 相似文献
13.
Temperature-programmed desorption was performed at temperatures up to 850 K on as-received fumed and precipitated silica particles. Physisorbed water molecules on both types of silica had activation energies in the range of 38–61 kJ/mol. However, the activation energies of desorption for chemisorbed water varied from 80 to >247 kJ/mol for fumed silica, Cab-O-Sil-M-7D, and 96 to 155 kJ/mol for precipitated silica, Hi-Sil-233. Our results suggest that physisorbed water can be effectively pumped away at room temperature (or preferably at 320 K) in a matter of hours. Chemisorbed water with high activation energies of desorption (>126 kJ/mol) will not escape silica surfaces in 100 years even at 320 K, while a significant amount of the chemisorbed water with medium activation energies (80–109 kJ/mol) will leave the silica surfaces in that time span. Most of the chemisorbed water with activation energies <126 kJ/mol can be pumped away in a matter of days in a good vacuum environment at 500 K. We had previously measured about 0.1–0.4 wt% of water in silica-reinforced polysiloxane formulations containing 21% Cab-O-Sil-M-7D and 4% Hi-Sil-233. Comparing present results with these formulations, we conclude that the adsorbed H2O and the Si–OH bonds on the silica surfaces are the major contributors to water outgassing from these types of silica-filled polymers. 相似文献
14.
Junlin Yang Junfeng Xiang Ciping Chen Daohui Lu Guangzhi Xu 《Journal of colloid and interface science》2001,240(2):425
The S-center radical (ANS·) of sodium 1-anilino-8-naphthalene sulfate (ANS) generated by photoinduced charge transfer in ANS/CdS and ANS/CdS/β-cyclodextrin(β-CD) systems has been studied by using spin trapping electron spin resonance techniques, UV-visible spectroscopic methods, and fluorescence spectroscopic methods. It was found that the S-centered radical (ANS·) was produced by the charge transfer reaction between the ground state ANS and the positive hole h+(CdS) from the valence band of CdS colloids, by the charge transfer from the excited singlet state 1ANS* to the conduction band of CdS colloids, or by both in the ANS/CdS and ANS/CdS/β-CD systems. The ESR signal intensity of the spin adduct (5,5′-dimethyl-1-pyrroline-N-oxide (DMPO)–ANS)·, which is formed from ANS· trapped by DMPO, in the latter system is 15 times stronger than that in the former system. The apparent association constants between ANS and CdS colloids in the absence and presence of β-CD determined from fluorescence quenching experiments are 1097 and 1606 M−1, respectively. From ESR and fluorescence results, it is estimated that the efficiency of photoinduced charge transfer from ANS to CdS colloids in the ANS/CdS/β-CD system is 12.5 times that in the ANS/CdS system. 相似文献
15.
In this study, radiation synthesis and characterization of swelling behavior and network structure of poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA), and poly(N,N-dimethylaminoethyl methacrylate-co-N-vinyl 2-pyrrolidone) (P(DMAEMA-co-VP)), hydrogels were investigated. PDMAEMA and P(DMAEMA-co-VP) hydrogels in the rod forms were prepared by irradiating the ternary mixtures of DMAEMA/VP/cross-linking agent, ethyleneglycol dimethacrylate (EGDMA), by gamma rays at ambient temperature. In composition ranges where the three components were completely miscible, water was also added to the ternary mixture to provide the formation of homogeneous polymerization and gelation. The influence of irradiation dose, comonomer, VP, and cross-linking agent, EGDMA, content on the total percentage gelation and monomer conversion were investigated. The effect of pH and temperature on the swelling behavior of hydrogels have also been examined. Hydrogels showed typical pH response and temperature responses, such as low-pH and low temperature swelling and high-pH and high temperature deswelling. Polymer-solvent interaction parameter (χ) and enthalpy and entropy changes appearing in the χ parameter for the P(DMAEMA-co-VP)-water system were determined by using Flory-Rehner theory of swelling equilibrium. The negative values for ΔH and ΔS indicate that prepared pure PDMAEMA and P(DMAEMA-co-VP) hydrogels have lower critical solution temperature (LCST) and Flory-Rehner theory of swelling equilibrium provides a satisfactory agreement to the experimental swelling data of the hydrogels. 相似文献
16.
N-(3-Azido-2-nitroxypropyl)-N-alkylnitramines andN-(2,3-diazidopropyl)-N-alkylnitramines were prepared by nitration and azidation ofN-alkyl-N-(2-hydroxy-3-chloropropyl)sulfamates andN-(3-azido-2-hydroxypropyl)-N-alkylsulfamates.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 206–208, January, 1999. 相似文献
17.
Shufeng Pang Zhifeng Ye Chun Li Yingqiu Liang 《Journal of colloid and interface science》2001,240(2):480
Mixed monolayers of Schiff-base complex Cu(SBC18)2 with an octadecyl hydrocarbon chain and Calix[4]arene without a long alkyl chain at an air/water interface were studied in ultrapure water at different temperatures. Interface behavior and thermodynamic estimation of the mixed monolayer indicate that a strong intermolecular interaction exists between the mixed components (Cu(SBC18)2 and calix[4]arene) and the two-dimensional miscibility decreases with the molar fraction of Cu(SBC18)2. It is noticeable that the calix[4]arene monolayer can be transferred successfully onto solid substrates due to the introduction of Cu(SBC18)2. FTIR transmission and UV-Vis absorption spectra of mixed LB films provide further evidence of molecular interaction between the headgroups. 相似文献
18.
Soyoung Kwon Kyoungwon Lee Hwayong Kim Youn-Woo Lee Won Bae 《Colloid and polymer science》2008,286(10):1181-1191
The free radical copolymerization of N-vinyl-2-pyrrolidone and 2-methylene-1,3-dioxepane was carried out in supercritical carbon dioxide (scCO2) using three kinds of dispersants and 2,2′-azobisisobutyronitrile as the initiator. Polymerization was performed with fluorinated
polymeric dispersants synthesized in scCO2 using the solution polymerization method and commercially available siloxane-based surfactant. Spherical biocompatible and
biodegradable polymeric particles were prepared within the sub-micron size range. The effect of various ratios of the comonomer,
reaction temperature, and concentration of initiator, in addition to the types and concentrations of the dispersants, on the
particle size and morphology was investigated. The particle size and particle size distribution of copolymer particles were
controlled using the above mentioned experimental parameters. Glass transition temperatures of copolymers were varied according
to the comonomer ratios used. 相似文献
19.
M. Madesclaire P. Coudert V. P. Zaitsev J. V. Zaitseva 《Chemistry of Heterocyclic Compounds》2006,42(4):506-511
A series of isomeric 2-oxazolidinones has been synthesized from (1S, 2S)-2-amino-1-(4-nitrophenyl)-1,3-propanediol.
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Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 579–584, April, 2006. 相似文献
20.
The binding mechanism of benzopurpurin 4B to poly(N-vinyl-2-pyrrolidone) was studied by a spectrophotometric absorbance change method at pH 7.1 in 0.05 mol dm–3 phosphate buffer. The results were analyzed by Scatchard, Hill, and Schwarz methods. The different shapes of the Scatchard plots indicated the varying degrees of cooperativity which depended on the percent saturation of binding sites. The Hill method elucidated the pairwise binding of the dye to polymer at the intermediate saturation and multimolecular binding both at the low and high saturations. The Schwarz method confirmed the interaction between bound dye molecules which led to cooperativity. The difference spectra of the polymer-dye complex evidenced the elucidated binding mechanism. 相似文献