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1.
Effects of copper salts containing different anions (SO(4)(2)(-), Cl(-), and NO(3)(-)) on the self-assembly of a designed peptide EAK16(II)GGH with affinity for Cu(2+) have been investigated. The peptide secondary structure, self-assembled nanostructures, and surface activity were observed to depend strongly on the type of anion. Over a salt concentration range from 0.05 to 10.0 mM, SO(4)(2)(-) induced long fiber formation, whereas Cl(-) and NO(3)(-) caused short fiber formation. The fiber length increased with copper sulfate concentration, but the concentration of copper chloride and copper nitrate did not affect the peptide nanostructures significantly. Analysis by Fourier transform infrared spectroscopy (FTIR) revealed that the addition of the copper salts tended to cause the peptide conformation to change from alpha-helix/random coil to beta-sheet, the extent to which depended on the anion type. This evidence of the anion effect was also supported by surface tension measurements using the axisymmetric drop shape analysis-profile (ADSA-P) technique. An explanation for the effect of anions on the peptide self-assembly was proposed. The divalent anion SO(4)(2)(-) might serve as a bridge by electrostatically interacting with two lysine residues from different peptide molecules, promoting beta-sheet formation. The extensive beta-sheet formation may further promote peptide self-assembly into long fibers. On the other hand, monovalent anions Cl(-) and NO(3)(-) may only electrostatically interact with one charged residue of the peptide; hence, a mixed secondary structure of alpha-helix/random coil and beta-sheet was observed. This observation might explain the predominant formation of short fibers in copper chloride and copper nitrate solutions.  相似文献   

2.
The influence of environmental conditions (pH, NaCl, CaCl2, and temperature) on the properties and stability of oil-in-water (O/W) emulsions containing oil droplets surrounded by one-, two-, or three-layer interfacial membranes has been investigated. Three oil-in-water emulsions were prepared with the same droplet concentration and buffer (5 wt % corn oil, 5 mM phosphate buffer, pH 6) but with different biopolymers: (i) primary emulsion: 0.5 wt % beta-Lg; (ii) secondary emulsion: 0.5 wt % beta-Lg, 0.1 wt % iota-carrageenan; (iii) tertiary emulsion: 0.5 wt % beta-Lg, 0.1 wt % iota-carrageenan, 0-2 wt % gelatin. The secondary and tertiary emulsions were prepared by electrostatic deposition of the charged biopolymers onto the surfaces of the oil droplets so as to form two- and three-layer interfacial membranes, respectively. The stability of the emulsions to pH (3-8), sodium chloride (0-500 mM), calcium chloride (0-12 mM), and thermal processing (30-90 degrees C) was determined. We found that multilayer emulsions had better stability to droplet aggregation than single-layer emulsions under certain environmental conditions and that one or more of the biopolymer layers could be made to desorb from the droplet surfaces in response to specific environmental changes (e.g., high salt or high temperature). These results suggest that the interfacial engineering technology used in this study could lead to the creation of food emulsions with improved stability to environmental stresses or to emulsions with triggered release characteristics.  相似文献   

3.
The influence of droplet flocculation on the creaming stability of monodisperse n-hexadecane oil-in-water emulsions was studied. The creaming velocity of emulsions with different droplet radii (0.43 and 0.86 μm), droplet concentrations (1-67 vol%), and sodium dodecyl sulfate (SDS) concentrations (7-80 mM) were measured. Depletion flocculation was observed in the emulsions when the aqueous phase SDS concentration exceeded a particular level ( approximately 40 mM for 0.43-μm droplets and approximately 15 mM for 0.86-μm droplets). Creaming was monitored by measuring the back-scattered light from an emulsion as a function of its height. The creaming velocity increased with increasing flocculation and decreased with increasing droplet concentration. These results have important implications for the formulation of emulsion-based materials. Copyright 2000 Academic Press.  相似文献   

4.
We used atomic force microscopy (AFM) to study the deformation and wetting behavior of large (50-250 microm) emulsion droplets upon mechanical loading with a colloidal glass probe. Our droplets were obtained from water-in-oil emulsions. By adding gelatin to the water prior to emulsification, also droplets with a bulk elasticity were prepared. Systematic variations of surfactant and gelatin concentrations were made, to investigate their effect on the deformation and wetting behavior of the droplets and to identify the contributions of interfacial tension, bulk elasticity, and expelled water. The AFM experiments were performed in force--distance mode and showed on approach a repulsive regime which in many cases was terminated by a jump-in of the probe. In the case of pure water (i.e. gelatin-free) droplets, the repulsive part of the curve showed a good linearity, thus allowing the extraction of an effective droplet spring constant. This quantity was found to decrease on raising the surfactant concentration from below the critical micelle concentration (cmc) to well above the cmc, and its numerical values were found to correspond remarkably well to literature values for the interfacial tension. Our findings indicate that, on gelatin increase inside the droplets, the bulk elasticity gradually becomes dominant and the droplets' stiffness does not depend anymore on surfactant concentration. Also the stability of the droplet interface against wetting, as measured by the force at which the jump-in instability occurs, was enhanced by gelatin. For gelatin concentrations of > or =15 wt %, the droplets were found to behave like purely elastic bodies. Both gelatin and surfactant contribute positively to the stability against interface breakup.  相似文献   

5.
The effects of sulfur dioxide (SO(2)), sodium chloride (NaCl), and peroxymonosulfate or oxone (2KHSO(5).KHSO(4).K(2)SO(4) with active ingredient, HSO(5)(-)) on the sonochemical removal of nitric oxide (NO) have been studied in a bubble column reactor. The initial concentration of NO studied ranged from about 500 to 1040 ppm. NaCl in the concentration range of 0.01-0.5 M was used as the electrolyte to study the effect of ionic strength. At the low NaCl concentration (0.01 M), the percent fractional removal of NO with initial concentration of 1040 ppm was enhanced significantly, while as the NaCl concentration increased, the positive effects were less pronounced. The presence of approximately 2520 ppm SO(2) in combination with 0.01 M NaCl further enhanced NO removal. However, with a NO initial concentration of 490 ppm, the addition of NaCl was detrimental to NO removal at all NaCl concentration levels. The combinative effect of sonication and chemical oxidation using 0.005-0.05 M oxone was also studied. While the lower concentrations of HSO(5)(-) enhanced NO removal efficiency, higher concentrations were detrimental depending on the initial concentration of NO. It was also demonstrated that in the presence of ultrasound, the smallest concentration of oxone was needed to obtain optimal fractional conversion of NO.  相似文献   

6.
An oil-in-water emulsion (5 wt% corn oil, 0.5 wt% beta-lactoglobulin (beta-Lg), 0.1 wt% iota-carrageenan, 5 mM phosphate buffer, pH 6.0) containing anionic droplets stabilized by interfacial membranes comprising of beta-lactoglobulin and iota-carrageenan was produced using a two-stage process. A primary emulsion containing anionic beta-Lg coated droplets was prepared by homogenizing oil and emulsifier solution together using a high-pressure valve homogenizer. A secondary emulsion containing beta-Lg-iota-carrageenan coated droplets was formed by mixing the primary emulsion with an aqueous iota-carrageenan solution. The stability of primary and secondary emulsions to sodium chloride (0-500 mM), calcium chloride (0-12 mM), and thermal processing (30-90 degrees C) were analyzed using zeta-potential, particle size and creaming stability measurements. The secondary emulsion had better stability to droplet aggregation than the primary emulsion at NaCl 相似文献   

7.
镉离子在H2SO4溶液中极谱行为的研究   总被引:1,自引:0,他引:1  
周本省  吴瑞鉴 《化学学报》1983,41(12):1121-1126
本文研究了在没有动物胶的0.5M H_2SO_4溶液中镉离子的极谱行为,得到了如下的结果:(1)在0.050~20.0mM CdSO_4 0.5M H_2SO_4的十种溶液中测得的电流-电位曲线都有良好的波形、恒定的极限扩散电流和易于确定的半波电位.这些曲线上都没有极谱极大出现;其极限扩散电流(波高)与镉离子的浓度成正比.在镉离子低浓度(0.050~0.20mM)时,半波电位保持不变,在镉离子高浓度(1.00~20.0mM)时,也仅有很小的变化.故镉离子在0.5MH_2SO_4,溶液中的电流-电位曲线可供定量和定性测定之用.(2)镉离子在低浓度时的极谱波是一种可逆波.(3)前人在H_2SO_4溶液中研究镉离子时之所以没有能得到令人满意的极谱行为的原因是他们在H_2SO4溶液中添加了动物胶的缘故.(4)作者从得到的波形良好的电流-电位曲线上,测定了25±0.2℃时镉离子在0.5M H_2SO_4溶液中的扩散电流常数、半波电位和电极反应中得失的电子数.结果如下: i_d/cm~(2/3)t~(1/6)=3.97μA/mM·mg~(2/3)·s~(-1/2) E_(1/2)=-1.011V(0.5M硫酸亚汞电极)=-0.559V(饱和甘汞电极) n=2 这些数据比Lingane的数据,扩散电流常数2.6μA/mM·mg~(2/3)·s~(-1/2)和半波电位-0.59V(饱和甘汞电极)],要合理些.  相似文献   

8.
The quantitative influence of Cu(II) on the interaction of eukaryotic DNA with sulfite (SO(3)(2-)), which is a derivative of sulfur dioxide in the human body, was studied using ultraviolet (UV) absorption spectrometry. The results showed that under physiological pH conditions, SO(3)(2-) reacted weakly with DNA at concentrations of up to 10(-1)M, at which point a rapid increase in the reaction constant and the reaction number of SO(3)(2-) with DNA was observed. The addition of Cu(II) at concentrations ranging from 6.67 x 10(-4) to 3.33 x 10(-3)M to DNA-SO(3)(2-) binary systems increased the reaction constant of SO(3)(2-) with DNA 41- to 115-fold at a low concentration of SO(3)(2-) (10(-3)M), and 4- to 84-fold at an intermediate concentration of SO(3)(2-) (10(-2)M), but had little influence on the reaction number of SO(3)(2-) with DNA compared with the absence of Cu(II). When the concentration of SO(3)(2-) reached 10(-1)M, the presence of Cu(II) reduced the reaction number but had no effect on the reaction constant of SO(3)(2-) with DNA. These results show that the efficiency of SO(3)(2-) is increased in the presence of Cu(II) at high concentrations of SO(3)(2-).  相似文献   

9.
Hern JA  Rutherford GK  Vanloon GW 《Talanta》1983,30(9):677-682
The analytical performance characteristics of a single-column ion chromatography system are reported. The data were obtained by using conductivity detection as well as by an indirect ultraviolet technique. The method has been applied to the determination of Cl(-), NO(3)(-) and SO(4)(2-) in samples of rain, sewer water, and soil-pore water. Also described are two methods which allow ion Chromatographic analysis of CaS0(4)-extractable nitrate in soils, and total sulphur in soils, marine sediments and plant tissue.  相似文献   

10.
Fog and rain water samples were collected at the same time in the Akita Hachimantai mountain range in northern Japan from June to September in 1998 and 1999. The various ion concentrations in these samples were analyzed, and the fog droplet sizes were measured for each fog event. As the fog droplet size increased, the ion concentration decreased. The slope of log-log plots of the concentration versus the droplet size differed with the kind of ion. In order to characterize the air pollutant, moreover, these data were quantitatively analyzed by an oblique rotational factor analysis. We found that three factors were extracted as the air pollutant source: (NH4)2SO4, acids (HNO3 + H2SO4) and sea-salt. Combining the factor analysis with the 72 h back-trajectory at 850 hPa level, we found that the contribution of each factor varied with the transport pattern of air masses.  相似文献   

11.
The electrical conductivities of aqueous solutions of Na(2)SO(4), H(2)SO(4), and their mixtures have been measured at 373-673 K at 12-28 MPa in dilute solutions for molalities up to 10(-2) mol kg(-1). These conductivities have been fit to the conductance equation of Turq et al.(1) with a consensus mixing rule and mean spherical approximation activity coefficients. Provided the concentration is not too high, all of the data can be fitted by a solution model that includes ion association to form NaSO(4)(-), Na(2)SO(4)(0), HSO(4)(-), H(2)SO(4)(0), and NaHSO(4)(0). The adjustable parameters of this model are the dissociation constants of the SO(4)(-) species and the H(+), SO(4)(-2), and HSO(4)(-) conductances (ion mobilities) at infinite dilution. For the 673 K and 230 kg m(-3) state point with the lowest dielectric constant, epsilon = 3.5, where the Coulomb interactions are the strongest, this model does not fit the experimental data above a solution molality of 0.016. Including the species H(9)(SO(4))(5)(-) gave satisfactory fits to the conductance data at the higher concentrations.  相似文献   

12.
In this work a new electrochemical sensor based on an Ag-doped zeolite-expanded graphite-epoxy composite electrode (AgZEGE) was evaluated as a novel alternative for the simultaneous quantitative determination of nitrate and nitrite in aqueous solutions. Cyclic voltammetry was used to characterize the electrochemical behavior of the electrode in the presence of individual or mixtures of nitrate and nitrite anions in 0.1 M Na2SO4 supporting electrolyte. Linear dependences of current versus nitrate and nitrite concentrations were obtained for the concentration ranges of 1-10 mM for nitrate and 0.1-1 mM for nitrite using cyclic voltammetry (CV), chronoamperometry (CA), and multiple-pulsed amperometry (MPA) procedures. The comparative assessment of the electrochemical behavior of the individual anions and mixtures of anions on this modified electrode allowed determining the working conditions for the simultaneous detection of the nitrite and nitrate anions. Applying MPA allowed enhancement of the sensitivity for direct and indirect nitrate detection and also for nitrite detection. The proposed sensor was applied in tap water samples spiked with known nitrate and nitrite concentrations and the results were in agreement with those obtained by a comparative spectrophotometric method. This work demonstrates that using multiple-pulse amperometry with the Ag-doped zeolite-expanded graphite-epoxy composite electrode provides a real opportunity for the simultaneous detection of nitrite and nitrate in aqueous solutions.  相似文献   

13.
Coprecipitation of nitrate and sulfate by barium has probably resulted in significant error in numerous studies dealing with the oxygen isotopic composition of natural sulfates using chemical/thermal conversion of BaSO(4) and analysis by isotope ratio mass spectrometry. In solutions where NO(3) (-)/SO(4) (2-) molar ratios are above 2 the amount of nitrate coprecipitated with BaSO(4) reaches a maximum of approximately 7% and decreases roughly linearly as the molar ratio decreases. The fraction of coprecipitated nitrate appears to increase with decreasing pH and is also affected by the nature of the cations in the precipitating solution. The size of the oxygen isotope artifact in sulfate depends both on the amount of coprecipitated nitrate and the delta(18)O and Delta(17)O values of the nitrate, both of which can be highly variable. The oxygen isotopic composition of sulfate extracted from atmospheric aerosols or rain waters are probably severely biased because photochemical nitrate is usually also present and it is highly enriched in (18)O (delta(18)O approximately 50-90 per thousand) and has a large mass-independent isotopic composition (Delta(17)O approximately 20-32 per thousand). The sulfate delta(18)O error can be 2-5 per thousand with Delta(17)O artifacts reaching as high as 4.0 per thousand. Copyright (c) 2008 John Wiley & Sons, Ltd.  相似文献   

14.
The reaction of bromite with aqueous S(IV) is first order in both reactants and is general-acid catalyzed. The reaction half-lives vary from 5 ms (p[H+] 5.9) to 210 s (p[H+] 13.1) for 0.7 mM excess S(IV) at 25 degrees C. The proposed mechanism includes a rapid reaction (k(1) = 3.0 x 10(7) M(-1) s(-1)) between BrO(2)(-) and SO(3)(2-) to form a steady-state intermediate, (O(2)BrSO(3))(3-). General acids assist the removal of an oxide ion from (O(2)BrSO(3))(3-) to form OBrSO(3)(-), which hydrolyzes rapidly to give OBr(-) and SO(4)(2-). Subsequent fast reactions between HOBr/OBr(-) and SO(3)(2-) give Br(-) and SO(4)(2-) as final products. In contrast, the chlorite reactions with S(IV) are 5-6 orders of magnitude slower. These reactions are specific-acid, not general-acid, catalyzed. In the proposed mechanism, ClO(2)(-) and SO(3)H(-)/SO(2) react to form (OClOSO(3)H)(2)(-) and (OClOSO(2))(-) intermediates which decompose to form OCl(-) and SO(4)(2-). Subsequent fast reactions between HOCl/OCl(-) and S(IV) give Cl- and SO(4)(2-) as final products. SO(2) is 6 orders of magnitude more reactive than SO(3)H-, where k(5)(SO(2)/ClO(2)(-)) = 6.26 x 10(6) M(-1) s(-1) and k(6)(SO(3)H(-)/ClO(2)(-)) = 5.5 M(-1) s(-1). Direct reaction between ClO(2)(-) and SO(3)(2-) is not observed. The presence or absence of general-acid catalysis leads to the proposal of different connectivities for the initial reactive intermediates, where a Br-S bond forms with BrO(2)(-) and SO(3)(2-), while an O-S bond forms with ClO(2)(-) and SO(3)H-.  相似文献   

15.
Kim D  Goldberg IB  Judy JW 《The Analyst》2007,132(4):350-357
An electrochemical system that consists of a silver electrode in 0.01 M sodium hydroxide electrolyte was investigated in an effort to develop a sensitive in situ analytical method for nitrate. Cyclic voltammetry demonstrated that the proposed system has a high normalized sensitivity (2.47 A s(1/2) V(-1/2) M(-1) cm(-2)), compared to more complex electroanalytical schemes. Double-potential-step chronocoulometry was used to maximize the signal-to-noise ratio (SNR), and minimize interference from dissolved oxygen in the electrolyte. The integration period for double-potential-step chronocoulometry was determined by optimizing the extended Cottrell equation. The integrated current is proportional to nitrate up to 10 mM and the average detection limit is approximately 1.7 microM. Dissolved oxygen does not degrade performance. To examine the potential interference of other ions when analyzing nitrate, we measured the electrode response to 1000 microM each of NO(2-), Cl(-), PO(4)(3-), SO(4)(2-), F(-), CO(3)(2-), BO(2-), K(+), Ca(2+), and Sr(2+) with and without 1000 microM nitrate. Interference is negligible for most of the ions when nitrate is absent (i.e. <1% of the response to equimolar nitrate). However, interference is substantial (>20% increase or decrease in the electrode response to nitrate) for PO(4)(3-), Ca(2+), and Sr(2+) when equimolar nitrate is present.  相似文献   

16.
Monodisperse poly(dl-lactic acid) (PLA) particles of diameters between 11 and 121 μm were fabricated in flow focusing glass microcapillary devices by evaporation of dichloromethane (DCM) from emulsion droplets at room temperature. The dispersed phase was 5% (w/w) PLA in DCM containing 0.1-2 mM Nile Red and the continuous phase was 5% (w/w) poly(vinyl alcohol) in reverse osmosis water. Particle diameter was 2.7 times smaller than the diameter of the emulsion droplet template, indicating very low particle porosity. Monodisperse droplets have only been produced under dripping regime using a wide range of dispersed phase flow rates (0.002-7.2 cm(3)·h(-1)), continuous phase flow rates (0.3-30 cm(3)·h(-1)), and orifice diameters (50-237 μm). In the dripping regime, the ratio of droplet diameter to orifice diameter was inversely proportional to the 0.39 power of the ratio of the continuous phase flow rate to dispersed phase flow rate. Highly uniform droplets with a coefficient of variation (CV) below 2% and a ratio of the droplet diameter to orifice diameter of 0.5-1 were obtained at flow rate ratios of 4-25. Under jetting regime, polydisperse droplets (CV > 6%) were formed by detachment from relatively long jets (between 4 and 10 times longer than droplet diameter) and a ratio of the droplet size to orifice size of 2-5.  相似文献   

17.
Iqbal M  Qureshi MA  Ejaz M 《Talanta》1978,25(7):371-376
5-(4-Pyridyl)nonane dissolved in benzene has been applied to the extraction of zinc, down to very low concentration (< 10(-6)M), from aqueous thiocyanate solutions. The metal can be quantitatively extracted from neutral and acidic thiocyanate solutions (up to 5M HCl, 0.25M HNO(3) or 0.25M H(2)SO(4)) in a single extraction. Equilibration times of 5 min are sufficient for almost complete extraction. The optimum thiocyanate concentration range is 0.05-0.5M. Among the common anions chloride exerts a slight depressing effect on extraction from neutral solution when present in high concentration. The extraction mechanism and the composition of the extracted complexes of zinc are discussed. The metal is predominantly extracted by means of a solvate mechanism. The effect of chloride, nitrate, sulphate, acetate, citrate, oxalate and ascorbate ions on the extraction of zinc is described. Several elements, including those of interest in separation of zinc, have been tested for extraction from O.1M KSCN at the optimal concentrations of the mineral acids, and the separation factors estimated.  相似文献   

18.
丙烯酰胺在聚乙二醇水溶液中聚合产品的微观形态   总被引:2,自引:0,他引:2  
采用偶氮类水溶性引发剂2,2′-偶氮二异丙基咪唑啉二盐酸盐(VA044)引发丙烯酰胺(AM)在聚乙二醇(PEG)水溶液中的双水相聚合;研究了引发剂、单体、聚乙二醇浓度及温度对最终产品中聚丙烯酰胺(PAM)液滴形态、尺寸的影响.随着引发剂浓度的增加,液滴由球状变为细长条状;随着温度的上升,球状液滴逐渐趋于条状,然后又重新趋于球状;在初始单体浓度较低时,PAM液滴滴径分布较窄,当其浓度增加后,滴径呈多峰分布;随着PEG浓度的增加,聚合物液滴趋于球状。  相似文献   

19.
The main objective of the present study is to specify the chemical properties of individual rain droplets. For this purpose, we have combined the collodion replication method and the SR-XRF microprobe technique. The dry residual materials retained in a single rain droplet, which correspond to the former cloud condensation nuclei and the scavenged particles during droplet falling, were successively reconstructed by the multiple elemental maps using SR-XRF microprobe analytical system. Also the SR-XRF microprobe system allows us to quantify the masses of ultra trace elements in residues of individual rain droplet with fg level. The proposed combination method in the present study is found to be helpful to understand the physicochemical properties of individual rain droplets.  相似文献   

20.
Common complexing ligands such as chloride and sulfate can significantly impact the sorption of Hg(II) to particle surfaces in aqueous environmental systems. To examine the effects of these ligands on Hg(II) sorption to mineral sorbents, macroscopic Hg(II) uptake measurements were conducted at pH 6 and [Hg](i)=0.5 mM on goethite (alpha-FeOOH), gamma-alumina (gamma-Al(2)O(3)), and bayerite (beta-Al(OH)(3)) in the presence of chloride or sulfate, and the sorption products were characterized by extended X-ray absorption fine structure (EXAFS) spectroscopy. The presence of chloride resulted in reduced uptake of Hg(II) on all three substrates over the Cl(-) concentration ([Cl(-)]) range 10(-5) to 10(-2) M, lowering Hg surface coverages on goethite, gamma-alumina, and bayerite from 0.42 to 0.07 micromol/m(2), 0.06 to 0.006 micromol/m(2), and 0.55 to 0.39 micromol/m(2) ([Cl(-)]=10(-5) to 10(-3) M only), respectively. This reduction in Hg(II) uptake is primarily a result of the formation of stable, nonsorbing aqueous HgCl(2) complexes in solution, limiting the amount of free Hg(II) available to sorb. At higher [Cl(-)] beam reduction of Hg(II) to Hg(I) was observed, resulting in the possible formation of aqueous Hg(2)Cl(2) species and the precipitation of calomel, Hg(2)Cl(2(s)). The presence of sulfate caused enhanced Hg(II) uptake over the sulfate concentration ([SO(4)(2-)]) range 10(-5) to 0.9 M, increasing Hg surface coverages on goethite, gamma-alumina, and bayerite from 0.39 to 0.45 micromol/m(2), 0.11 to 0.38 micromol/m(2), and 0.36 to 3.33 micromol/m(2), respectively. This effect is likely due to the direct sorption or accumulation of sulfate ions at the substrate interface, effectively reducing the positive surface charge that electrostatically inhibits Hg(II) sorption. Spectroscopic evidence for ternary surface complexation was observed in isolated cases, specifically in the Hg-goethite-sulfate system at high [SO(4)(2-)] and in the Hg-goethite-chloride system.  相似文献   

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