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1.
Cyclic alcohols (n = 5‐7) are compounds of distinctive nonplanar structure. Effect of the alcohols on micellization of sodium dodecyl sulfate (SDS) in aqueous solution are examined by determining the critical micelle concentration (CMC) by conductometry and the micelle aggregation numbers (Nagg) by fluorometry, respectively. In general, the CMC of SDS decreases with increase in volume of a cyclic alcohol in water and increases further after attaining a minimum value. The Nagg of SDS varies little with small addition of a cyclic alcohol, but decreases when added in sufficient volume. Both the changes of the CMC and Nagg with carbon number in the ring of the alcohols occur irregularly due to their steric reasons and nonplanar nature. The irregularity makes a difference between the cyclic alcohols and their chain counterparts. Based on 1H NMR chemical shift measurements, the cyclic alcohols are found to be solubilized in the palisade layer in SDS micelles.  相似文献   

2.
CeO2 nanocrystals (NCs) have attracted increasing interest over the past few years, in particular for their use in catalytic reactions. Syntheses mediated by near‐ and supercritical alcohols have proven to be innovative ways to obtain CeO2 NCs with controlled crystallite sizes (from 3 to 8 nm depending on the alcohol) and surface functionalities, with alcohol moieties. When submitted to a thermal treatment at 500 °C, required to desorb/degrade surface organic species, these powders displayed different behaviors depending on the alcohol used during the synthesis. Cerium oxide powders synthesized in sc‐MeOH, sc‐EtOH and sc‐iPrOH undergo sintering during treatment at 500 °C, with a decrease of their specific surface area. Conversely, those synthesized in sc‐BuOH, nc‐PentOH and nc‐HexOH keep their initial crystallite sizes and morphology, but show a great enhancement of their specific surface area (up to 200 m2 g?1), which is unprecedented after such a thermal treatment.  相似文献   

3.
The critical micelle concentration (CMC) and the thermodynamic function of the anionic surfactant, sodium laurate (SLA) and sodium dodecyl sulfate (SDS) in the N,N-dimethyl acetamide (DMA)/long-chain alcohol systems were studied using titration microcalorimetric method. The power-time curves of SLA and SDS in the presence of a long-chain alcohol (n-heptanol, n-octanol, n-nonanol, n-decanol) in the DMA medium were determined. Then, from the curves, the critical micelle concentration (CMC) and the thermodynamic standard formation functions (ΔH ϑ m, ΔG ϑ m and ΔS ϑ m) were obtained through thermodynamic theories. The relationships between temperature, alcohol’s carbon number, concentration and thermodynamic properties were discussed. For SLA or SDS in a DMA solution, under the same concentration of alcohol, the values of CMC, ΔH ϑ m and ΔS ϑ m increase, while the value of ΔG ϑ m decrease with the increase of temperature. Under the same condition of identical temperature and alcohol concentration, the values of CMC, ΔH ϑ m, ΔG ϑ m and ΔS ϑ m decrease with the increase of the alcohol’s carbon number. In the presence of the same kind of alcohol, the values of CMC and ΔG ϑ m increase, but the values of ΔH ϑ m and ΔS ϑ m decrease with the concentration increases in alcohol series at the same temperature. __________ Translated from Acta Chimica Sinica, 2007, 65(10): 906–912 [译自: 化学学报]  相似文献   

4.
 The effect of small amounts of salt on the interaction between two fractions of ethyl(hydroxy)ethyl cellulose, EHEC, and sodium dodecyl sulfate, SDS, has been investigated by means of steady-state fluorescence measurements. The two polymer fractions display different properties in hydrophobicity expressed as different cloud points. The results are discussed in relation to hydrodynamic (viscosity) and thermodynamic (equilibrium dialysis) properties. The micropolarity as sensed by the probe pyrene shows that the polymers begin to interact with SDS at a lower concentration in the presence of salt. The average aggregation numbers of polymer-bound clusters, N p, were obtained by fluorescence-quenching data in combination with equilibrium dialysis experiments. N p was found to increase in the presence of salt for the EHEC fraction with a high cloud point (CP). The polymer with a low CP displays higher N p in the presence of salt at low SDS concentrations, but exhibit lower N p at higher SDS concentrations than in the salt-free system. The microviscosity index as determined by intramolecular excimer formation of 1, 3-di(1-pyrenyl)propane (P3P) is highest for the lowest N p and there is a corre-lation with N p in the presence as well as absence of salt for both EHEC fractions. It is found that when the same fractional amount of SDS is bound to the polymers, 10–20% of the value of saturation, the increase in macroviscosity occurs and the microviscosity shows high rigidity. Received: 3 March 1997 Accepted: 23 May 1997  相似文献   

5.
The dynamics of the changing microenvironment of the fluorescent probe pyrene in slightly cross-linked networks of poly(diallyldimethylmmonium bromide) during diffusion of sodium dodecyl sulfate (SDS) in the gel phase has been investigated by fluorescence spectroscopy. Values of the spectral ratio I3/I1 for pyrene monomer included in SDS micelles in the swollen networks fall between the corresponding values for pyrene in water and for pyrene dissolved in SDS micelles in aqueous solution. In the narrow interval of the surfactant concentrations in the gel phase, the formation of pyrene excimers is observed. The values of the critical micelle concentration in the gel phase (ca. 5 × 10?4 to 8 × 10?4 mol/L) are tenfold lower than in aqueous solutions of the surfactant. The effective micellar diffusion coeffecient D in the gel phase increases with increasing swelling of the network. © 1993 John Wiley & Sons, Inc.  相似文献   

6.
The synergistic behavior of sodiumdodecylsulfate (SDS) and 1,2-diheptanoyl-sn-glycero-3-phosphocholine (DHPC) binary mixtures has been studied with interfacial and pyrene fluorescence(I 1/ I 3) intensity measurements. From the interfacial data, the interfacial parameters; the maximum surface excess (Γmax), or the minimum area per molecule (A min), and the surface pressure at the critical micellar concentration (πcmc) have been evaluated. The cmc value has been used for evaluating the free energies of micellization (ΔG o m). The mixed micelle formation was evaluated with the help of the Clint equation. The SDS plus DHPC mixed micelles showed negative departure from ideality indicating synergistic interactions between the unlike components. The quantitative analysis of mixed micelle, mixed monolayer and the composition of the mixed micelle was carried out with the help of regular solution approximation. The interaction parameters, β and βσ, in the mixed micelle as well as in the mixed monolayer, respectively showed negative values indicating synergistic behavior of SDS and DHPC molecules.  相似文献   

7.
Suwa  K.  Yamamoto  K.  Akashi  M.  Takano  K.  Tanaka  N.  Kunugi  S. 《Colloid and polymer science》1998,276(6):529-533
 We examined the effects of salt on the lower critical solution temperature (LCST) and lower critical solution pressure (LCSP) of aqueous solutions of poly (N-vinylisobutyramide), polyNVIBA, and compared them with those on poly(N-isopropylacrylamide), polyNIPAAm. We found that the addition of salt (such as Na2SO4, NaCl, or KCl) decreased the LCST of aqueous polyNVIBA from 45 °C to below 20 °C, almost linearly with the salt concentrations and dependent on the type of salt. We observed a similar concentration-dependent decrease in LCST for polyNIPAAm. When KI or NaSCN was added to each aqueous polymer solution, some smaller increases in LCST were observed at relatively low salt concentrations; higher concentrations of salt gave an almost linear decrease in LCST. As for LCSP, the addition of most types of salt lowered the transition pressure, but the effects were much more dependent on the type and the valence of the salt (especially of anion) in both polymers. Salt with divalent anion showed a larger decrease in LCSP, but those with mono valent anion showed a relatively small decrease, even showed a slight increase at lower salt concentrations in the case of polyNVIBA. Salt with I- or SCN- showed evident increases in LCSP up to 1 M and was maintained higher than the control even at 2 M. We discuss the interactions of the amide group in the side chains of polymers and water and their perturbation by ions. Received: 13 November 1997 Accepted: 22 January 1998  相似文献   

8.
 The effects of adding 0.1 molal 1-butanol to the aqueous SDS system at 298.1 K and the aqueous PEO–SDS system at 298.1 and 283.1 K have been studied. NMR NOESY experiments on the PEO– SDS–1-butanol system in D2O were obtained. NMR self-diffusion experiments and measurements of NMR chemical shifts and specific conductivity were carried out on the samples, i.e. on samples with PEO and without PEO. The addition of 1-butanol to an aqueous SDS–PEO system decreases the critical aggregation concentration (c.a.c). Determination of the second critical concentration (c 2) depends on the method of measurements, i.e. the molecular species monitored. Conductivity measurements will give c 2 as the SDS concentration where free micelles (micelles not bound to the polymer) are formed. PEO self-diffusion measurements, on the other hand, determine c 2 as the SDS concentration where the polymer is saturated with SDS. Both the c.a.c and the c 2 decrease upon 1-butanol addition. However, the c 2 value exhibits a larger decrease than the c.a.c value. Thus, the amount of polymer bound surfactant molecules decreases upon addition of 1-butanol. Micellar solubilization of 1-butanol starts at c.a.c., but the solubilization capacity is low until the surfactant concentration reaches c 2, where the increase in solubilization is significant. Thus, solubilization data can be used to detect c 2, the concentration where free micelles form. Received: 21 July 1997 Accepted: 9 February 1998  相似文献   

9.
Thermoresponsive colloidal microgels were prepared by polymerisation of N-isopropylacrylamide (NIPAM) with varying concentration of a cross-linking monomer, N,N-methylenebisacrylamide (MBA), in water with either 0.4 or 6.7 mM concentration of an anionic surfactant, sodium dodecylsulphate (SDS). Volume phase transitions of the prepared microgels were studied in D2O by 1H-NMR spectroscopy including the measurements of spin–lattice (T1) and spin–spin (T2) relaxation times for the protons of poly(N-isopropylacrylamide) (PNIPAM) at temperature range 22–50 °C. In addition, microcalorimetry, turbidometry, dynamic light scattering and electrophoretic mobility measurements were used to characterise the aqueous microgels. The results from the different characterisation methods indicated that PNIPAM microgels prepared in 6.7 mM SDS concentration are structurally different compared to their correspondences prepared in 0.4 mM concentration. Increasing MBA concentration in the microgel synthesis appears to increase the structural heterogeneity in both cases of SDS concentration. PNIPAM structures with significantly higher molecular mobilities at temperatures above 35 °C were observed in the microgels prepared in 0.4 mM SDS concentration, as indicated by the 1H NMR relaxation times of different PNIPAM protons. We conclude that the high mobilities measured with NMR at elevated temperatures and also the clearly negative values of zeta potential are in connection to a fairly mobile surface layer with polyelectrolyte nature and a consequent high local lower critical solution temperature.  相似文献   

10.
Density measurements of water-dodecyltrimethylammonium bromide (DTAB)-alcohol ternary systems as a function of alcohol and surfactant concentrations were carried out at 25°C. The alcohols were propanol (PrOH), 2-propanol (2-PrOH) and hexanol (HexOH). The apparent molar volume V,R of alcohols have been calculated and the standard (infinite dilution) partial molar volumes of alcohols V R at each surfactant concentration were obtained by means of a least squares fit of V,R vs. the alcohol concentration. The V R vs. surfactant concentration curves have been rationalized in terms of the partial molar volume of alcohol in the aqueous V f and the micellar V b phases and the distribution constant of alcohol between the aqueous and the micellar phases K. The V b values for PrOH and HexOH together with those of butanol and pentanol previously reported satisfy the additivity rule giving a methylene group contribution of 16.7 cm3-mol–1 which is identical to that reported in the literature from the study of pure liquid alcohols. No difference between V b for PrOH and 2-PrOH has been found. From density data of water-alcohol and water-surfactant binary systems and of water-surfactant-alcohol ternary system, the apparent molar volume of the surfactant in the water-alcohol mixed solvent V,S have been calculated as a function of the surfactant concentration and of the mixed solvent composition. The effect of the alkyl chain length of the alcohols and the effect of isomerization of the alcohols on the V,S vs. surfactant concentration trends have been analyzed.  相似文献   

11.
Fluorescence decay and quenching of pyrene labels on copolymers of 2-acrylamido-2-methylpropanesulphonic acid (AMPS) and N,N-dimethylacryl-amide (DMAA) were observed in dilute salt-free aqueous solutions as a function of the mole fraction FAMPS of AMPS from 0 to 0.896. Monoexponential and biexponential decays were found for the samples of FAMPS < 0.35 and samples of FAMPS > 0.35, respectively. The fast decay component is 80% and the averaged lifetime <τ> and lifetime τ1 of the fast decay decreased with increasing FAMPS. Quenching efficiency of Cu2+, CH3NO2, and dinitrobenzene to the pyrene label was investigated in the framework of Stern-Volmer plot. The quenching effects of Cu2+ included both of dynamic and static ones, the latter was due to the condensed Cu2+. For the neutral quenchers, the quenching rate constant kq increased when FAMPS < 0.449 then decreased, showing a decline of accessibility to the pyrene label. I1/I3 value in salt-free dilute aqueous solution and in DMSO solution decreased obviously with an increase in FAMPS, indicating that the labeled fluorophore experienced a decrease in polarity of its microenvironment with increasing charge density of the polymer. This I1/I3 decrease was enhanced with increasing the polymer concentration and adding salt NaCl up to 0.75 mol/L showed no effect on the appearance of this decrease. These results were interpreted consistently with the counterion condensation concept, where condensed counterions induced the “temporal” aggregation of less-polar in the polyelectrolyte solutions surrounding the pyrene labels.  相似文献   

12.
Sodium dodecyl sulfate (SDS) has been well known as a promoter for the formation of hydrates. However, the use of SDS to enhance the formation of CO2 hydrates has not been effective. This work will present an idea of competitive adsorption that will provide insights into the nonpromoting effect of SDS under high carbonate concentrations. The competitive adsorption is studied between DS? monomers and carbonate ions on tetrahydrofuran (THF) hydrates. The adsorption is qualitatively investigated by using pyrene fluorescence measurements. The SDS concentration at which hydrophobic domains occur on the hydrate surface increases with the increased carbonate concentration and this trend is less dependent on the order of addition of these two species. This concentration is 0.17 mM at carbonate concentrations less than 2 μM and it shifts to 3.47 mM at carbonate concentrations higher than 2.5 μM. Thus, using carbonate with its concentration higher than 2.5 μM would be enough to displace the hydrophobic domains formed by SDS up to the solubility limit.  相似文献   

13.
The pH dependence of an anionic surfactant, sodium N-dodecanoylsarcosinate (SLAS), has been studied by measuring interfacial tension, fluorescence, dynamic light scattering, etc., in aqueous solutions with phosphate and borate buffers. The interfacial tension (γ) of SLAS decreases remarkably with a pH decrease and is constant at pH > 7.3. The observed values for the critical micelle concentration (cmc) and the surfactant concentration at which its γ value is reduced by 20 mN/m from that of pure water (C 20) decrease with a pH decrease, while those also become constant at pH > 6.5 and >7.3, respectively. On the other hand, the interfacial excess of SLAS increases at pH < 7.3. These interfacial behaviors have been further investigated by the addition of Tl+ which replaces Na+ of SLAS. The observed γ values of LAS with the different counter cations are in the order of H+ < Tl+ < Na+. In order to reveal aggregation properties of SLAS, the aggregation number (N agg), the micropolarity, the hydrodynamic radius (R h) of micelle, and the fluorescence anisotropy of Rhodamine B (r) have been evaluated at various pHs. The N agg value shows a decreasing tendency with a pH increase. The I 1/I 3 ratio and the R h values do not strongly depend on pH. The r value decreases until pH 7 and remains constant at pH > 7.0. These interfacial and micelle properties have been discussed in detail considering the electrostatic interaction and the molecular structures of the hydrophilic headgroup.  相似文献   

14.
张洪林  孔哲  闫咏梅  李干佐  于丽  李真 《化学学报》2007,65(10):906-912
N,N-二甲基乙酰胺(DMA)/长链醇非水溶液体系中, 利用微量量热仪, 研究阴离子表面活性剂十二烷基羧酸钠(SLA)、十二烷基硫酸钠(SDS)的临界胶束浓度(CMC)和热力学函数. 本文在十二烷基羧酸钠, 十二烷基硫酸钠的N,N-二甲基乙酰胺溶液中, 分别加入长链醇(庚醇、辛醇、壬醇、癸醇), 测定体系的热功率-时间曲线. 借助热力学理论, 由测得曲线, 进一步得到临界胶束浓度和热力学函数(ΔHm0, ΔGm0和ΔSm0). 讨论了温度、醇的碳原子数目、醇的浓度与热力学参数之间的关系. 结果表明, 对十二烷基羧酸钠或十二烷基硫酸钠的DMA溶液, 在含有相同浓度的各种醇的体系中, CMC, ΔHm0和ΔSm0的值随着温度的升高而增加, 而ΔGm0的值随着温度的升高而降低. 在相同温度及相同浓度的醇体系中, CMC, ΔHm0Gm0和ΔSm0的值都随着醇中碳原子数目的增加而降低. 在相同温度及相同醇的体系中, CMC, ΔGm0的值随着醇的浓度的增加而增大, 而ΔHm0, ΔSm0的值随着醇的浓度的增加而减少.  相似文献   

15.
 The performance of two liquid chromatography-mass spectrometry (LC/MS) interfacing techniques, thermospray (TSP) and atmospheric pressure chemical ionization (APCI), for the analysis of benzo[a]pyrene (BaP) metabolites (hydroxy, epoxy and quinone derivatives) was compared. Interface and detection parameters such as source temperature, eluent composition or flow rate were optimized using negative ion mode. In TSP, the main ions are mostly [M]-, [M−H2O]- or [M+CH3COO]-, whereas APCI gives mainly the [M]- and [M−H]- ions. Quantification was carried out by flow injection. Calibration graphs were linear in the range of 10 ng to 1000 ng in TSP and 0.1 ng to 10 ng in APCI. Detection limits were in the range of 1 ng to 20 ng in TSP and 0.002 ng to 0.2 ng in APCI. The presence of BaP-1,6-dione, BaP-3,6-dione, and BaP-6,12-dione was confirmed in environmental samples of air particulate matter. Received: 6 January 1997/Accepted: 18 April 1997  相似文献   

16.
 The performance of two liquid chromatography-mass spectrometry (LC/MS) interfacing techniques, thermospray (TSP) and atmospheric pressure chemical ionization (APCI), for the analysis of benzo[a]pyrene (BaP) metabolites (hydroxy, epoxy and quinone derivatives) was compared. Interface and detection parameters such as source temperature, eluent composition or flow rate were optimized using negative ion mode. In TSP, the main ions are mostly [M]-, [M−H2O]- or [M+CH3COO]-, whereas APCI gives mainly the [M]- and [M−H]- ions. Quantification was carried out by flow injection. Calibration graphs were linear in the range of 10 ng to 1000 ng in TSP and 0.1 ng to 10 ng in APCI. Detection limits were in the range of 1 ng to 20 ng in TSP and 0.002 ng to 0.2 ng in APCI. The presence of BaP-1,6-dione, BaP-3,6-dione, and BaP-6,12-dione was confirmed in environmental samples of air particulate matter. Received: 6 January 1997/Accepted: 18 April 1997  相似文献   

17.
The power-time curves for the micelle formation process were determined for two anionic surfactants, sodium laurate (SLA) and sodium dodecyl sulfate (SDS), in mixed alcohol + N,N-dimethylacetamide (DMA) solvent using titration microcalorimetry. From the data of the lowest point and the area of the power-time curves, their critical micelle concentration (CMC) and ΔH mo were obtained. The other thermodynamic functions of the micellization process (ΔG mo and ΔS mo) were also calculated with thermodynamic equations. For both surfactants, the effects of the carbon number (chain length) of the alcohol, the concentration of alcohol, and the temperature on the CMC and thermodynamic functions are discussed. For systems containing identical concentrations of a different alcohol, values of the CMC, ΔH mo and ΔS mo increased whereas ΔG mo decreased with increasing temperature. For systems containing an identical alcohol concentration at the same temperature, values of the CMC, ΔH moG mo and ΔS mo decrease with increasing carbon number of alcohol. For systems containing the same alcohol at the same temperature, the CMC and ΔG mo values increase whereas ΔH mo and ΔS mo decrease with increasing alcohol concentration.  相似文献   

18.
Novel cellobiose and cellulose (DP n =ca. 30) derivatives, N-(1-pyrenebutyloyl)-4-O-(β-d-glucopyranosyl)-β-d-glucopyranosylamine (6), N-(15-(1-pyrenebutyloylamino)-pentadecanoyl)-4-O-(β-d-glucopyranosyl)-β-d-glucopyranosylamine (7), N-(1-pyrenebutyloyl)-β-cellulosylamine (13), N-(15-(1-pyrenebutyloylamino)-pentadecanoyl)-β-cellulosylamine (14) carrying a pyrene group as a single fluorescent probe at the reducing end, were prepared in order to investigate their self-assembly systems in solutions. The relative intensity of the excimer emission at ca. 480 nm due to dimerized pyrenes (intensity I E) to the monomer emission at ca. 380 nm due to isolated pyrene (intensity I M), i.e., I E/I M, was monitored in various solutions. In water/dimethyl sulfoxide (DMSO) mixed solvent (0–98%, v/v), the ratio I E/I M remained low (0.04) for compound 6 over the range of water concentrations, indicating that pyrenes at C-1 position of compound 6 were diffused. On the other hand, the ratio I E/I M increased (0.04–4.96) for compound 7 with the increase in water concentration, indicating that pyrenes at C-1 position were associated. In aqueous NaOH solutions (4.4–17.5%, w/w), compound 14 showed a large increase in the ratio I E/I M (0.84–8.14) with the increase in NaOH concentration, compared to compound 13 (0.06–0.41). It was found that the association of hydrophobic groups at the reducing-end of cellulose could be controlled by the hydrophilic–hydrophobic balance of compounds and the solvent polarity.  相似文献   

19.
The interactions of non-ionic amphiphilic diblock copolymer poly(oxyethylene/oxybutylene)(E39B18) with anionic surfactant sodium dodecyl sulphate(SDS) and cationic surfactant hexadecyltrimethylammonium bromide(CTAB) were studied by using various techniques such as surface tension,conductivity,steady-state fluorescence and dynamic light scattering.Surface tension measurements were used to determine the critical micelle concentration(CMC) and thereby the free energy of micellization(△Gmic),free energy of adsorption(△Gads),surface excess concentration(Γ) and minimum area per molecule(A).Conductivity measurements were used to determine the critical micelle concentration(CMC),critical aggregation concentration(CAC),polymer saturation point(PSP),degree of ionization(α) and counter ion binding(β). Dynamic light scattering experiments were performed to check the changes in physiochemical properties of the block copolymer micelles taken place due to the interactions of diblock copolymers with ionic surfactants.The ratio of the first and third vibronic peaks(I1/I3) indicated the polarity of the pyrene micro environment and was used for the detection of micelle as well as polymer-surfactant interactions.Aggregation number(N),number of binding sites(n) and free energy of binding (△Gb) for pure surfactants as well as for polymer-surfactant mixed micellar systems were determined by the fluorescence quenching method.  相似文献   

20.
An αεβ fish-like phase diagram of three phase microemulsions was proposed and used to investigate the phase behavior of the microemulsion systems sodium dodecyl sulfate (SDS)/alcohol/oil/water at various oil/water ratios. Related physicochemical properties of the microemulsion systems were calculated. As the oil/water mass ratio increases, the solubility (ε B) of the alcohol increases, while both the mass fraction of alcohol in the interfacial layer (A S) and the solubilization ability (SP ) decrease. The effect of oils on the properties of the microemulsion systems was investigated.  相似文献   

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