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Ionic Strength (ionic + strength)
Kinds of Ionic Strength Terms modified by Ionic Strength Selected AbstractsRole of Reduced Ionic Strength and Low pH in Gelation of Chicken Breast Muscle ProteinJOURNAL OF FOOD SCIENCE, Issue 1 2005S. Ke And ABSTRACT: Elastic gels with a high moisture content of 88% were prepared at an acidic pH and low ionic strength. The relationship among pH, ionic strength, water-holding capacity, and fold score of gels was investigated. A decrease of pH from 4.1 to 3.7 or below increased gel elasticity and significantly decreased water loss under pressure (P < 0.05). In the presence of sodium chloride, gels made at pH 3.5 to 3.7 had decreased elasticity and increased water loss under pressure. Prior freezing increased the water loss of gels under pressure. Gels made with phosphoric acid and hydrochloric acid lost less water under pressure than those made with citric acid. The percentage loss of water from cylindrical gels was inversely related to the height of the cylinders, suggesting that surface effects were involved. These results suggest that net positive charges on the protein molecules at low pH produced electrostatic repulsion, which was a major driving force for water uptake in the low-salt gels. [source] Role of pH and Ionic Strength on Water Relationships in Washed Minced Chicken-breast Muscle GelsJOURNAL OF FOOD SCIENCE, Issue 3 2003H.G. Kristinsson ABSTRACT The relationship between pH, ionic strength, and water balance of chicken-breast muscle gels was investigated. An increase in gel pH (pH 6.4 to 7.4) without added NaCl led to dramatic increases in water-holding capacity and water uptake (P < 0.05). Gels at 150 mM NaCl exhibited less ability to adsorb water than salt-free gels (P < 0.05 at pH 6.8 to 7.4) and had lower water-holding capacities (P < 0.05) and fold scores at and below pH 7. Varying salt concentration of the gel-bathing solutions had dramatic effect on the water uptake of the gels. The results show that strong water-absorbing gels can be produced at low ionic strengths and suggest that the negative charge of the muscle proteins is the driving force for water uptake and retention. [source] Large Mechanical Response of Single Dendronized Polymers Induced by Ionic Strength,ANGEWANDTE CHEMIE, Issue 25 2010Ionel Popa Dr. Die mechanischen Eigenschaften kationischer dendronisierter Einzelpolymere variieren stark in wässrigen Lösungen unterschiedlicher Ionenstärke. Indem es gelingt, ihre Elastizität über die Lösungseigenschaften einzustellen, bieten sich dendronisierte Polymere als Bausteine für molekulare Maschinen wie Aktuatoren oder Motoren an. [source] Charge Transport in Redox Polyelectrolyte Multilayer Films: The Dramatic Effects of Outmost Layer and Solution Ionic StrengthCHEMPHYSCHEM, Issue 13 2010Dr. Mario Tagliazucchi Abstract The redox switching kinetics, that is, charge transfer and transport in layer-by-layer-deposited electroactive polyelectrolyte multilayers is systematically studied with variable-scan-rate cyclic voltammetry. The experiments are performed with films finished in the redox polycation (an osmium pyridine,bipyridine derivatized polyallylamine, PAH-Os) and the polyanion (polyvinyl sulfonate, PVS), in solutions of different electrolyte concentrations. A modified diffusion model is developed to account for the experimentally observed dependence of the average peak potential with the scan rate. This model is able to describe both the redox peak potential and the current, providing information on the electron-transfer rate constants and the diffusion coefficient for the electron-hopping mechanism. While the former does not vary with the ionic strength or the nature of the outmost layer, polyanion-capped films present an electron-hopping diffusion coefficient at low ionic strength that is three orders of magnitude smaller than that for PAH-Os-capped films. The effect is offset at high ionic strength. We discuss the possible causes of the effect and the important consequences for electrochemical devices built by layer-by-layer self-assembly, such as amperometric biosensors or electrochromic devices. [source] Synthesis and characterization of metal sulfide clusters for toxicological studiesENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 4 2002Karl C. Bowles Abstract Zinc sulfide clusters were synthesized and characterized at low micromolar concentrations to assess the effect of metal-sulfide ligands on metal toxicity to aquatic organisms in oxic environments. Recommended preparation times are greater than 2 h initial reaction of equimolar sodium sulfide and zinc nitrate, followed by oxic aeration for 3 d. Ionic strength, pH, and anoxic stabilization time were found to be relatively unimportant in controlling the final yield. Adsorptive losses of zinc sulfide (ZnS) clusters to surfaces, however, were significant for a variety of vessel materials and membrane filters. Ionic strength and pH were found to be important factors controlling the extent of adsorptive losses with minimal loss for pHs greater than 9 and for soft waters. The Ag(I), Cu(II), and Hg(II) as metal sulfides completely suppress the analysis of sulfide, whereas Pb(II), Mn(II), and Co(II) partially suppress the analysis of sulfide by the methylene blue technique. Ultraviolet and fluorescence spectra are shown for synthesized ZnS clusters. [source] Inhibition of hydroxyapatite dissolution by whole casein: the effects of pH, protein concentration, calcium, and ionic strengthEUROPEAN JOURNAL OF ORAL SCIENCES, Issue 5 2008Michele E. Barbour Formulating drinks with reduced erosive potential is one approach for reducing dental erosion. In this study, whole casein was added to citric acid solutions representative of soft drinks, and the hydroxyapatite dissolution rate was assessed. Adding 0.02% (w/v) casein to acid solutions significantly reduced the hydroxyapatite dissolution rate by 51 ± 4% at pH values of 2.80, 3.00, 3.20, 3.40, and 3.60, although the baseline dissolution rates of course varied as a function of pH. The protein concentration [0.002, 0.02, and 0.2% (w/v) casein] had no significant effect on dissolution inhibition. Adding both casein and calcium to citric acid resulted in a further reduction in the dissolution rate at low and intermediate calcium concentrations (5 and 10 mM) but not at higher calcium concentrations (20 and 50 mM). Ionic strength had no significant impact on the efficacy of casein. Casein also significantly reduced the hydroxyapatite dissolution rate when the hydroxyapatite was coated with a salivary pellicle. The reduction in dissolution rate is ascribed to firmly adsorbed casein on the hydroxyapatite surface, which stabilizes the crystal surface and inhibits ion detachment. [source] Impact of physicochemical parameters on in vitro assembly and disassembly kinetics of recombinant triple-layered rotavirus-like particlesBIOTECHNOLOGY & BIOENGINEERING, Issue 4 2009Maria Candida M. Mellado Abstract Virus-like particles constitute potentially relevant vaccine candidates. Nevertheless, their behavior in vitro and assembly process needs to be understood in order to improve their yield and quality. In this study we aimed at addressing these issues and for that purpose triple- and double-layered rotavirus-like particles (TLP 2/6/7 and DLP 2/6, respectively) size and zeta potential were measured using dynamic light scattering at different physicochemical conditions, namely pH, ionic strength, and temperature. Both TLP and DLP were stable within a pH range of 3,7 and at 5,25°C. Aggregation occurred at 35,45°C and their disassembly became evident at 65°C. The isoelectric points of TLP and DLP were 3.0 and 3.8, respectively. In vitro kinetics of TLP disassembly was monitored. Ionic strength, temperature, and the chelating agent employed determined disassembly kinetics. Glycerol (10%) stabilized TLP by preventing its disassembly. Disassembled TLP was able to reassemble by dialysis at high calcium conditions. VP7 monomers were added to DLP in the presence of calcium to follow in vitro TLP assembly kinetics; its assembly rate being mostly affected by pH. Finally, DLP and TLP were found to coexist under certain conditions as determined from all reaction products analyzed by capillary electrophoresis. Overall, these results contribute to the design of new strategies for the improvement of TLP yield and quality by reducing the VP7 detachment from TLP. Biotechnol. Bioeng. 2009; 104: 674,686 © 2009 Wiley Periodicals, Inc. [source] Effect of antibody solution conditions on filter performance for virus removal filter PlanovaÔ 20NBIOTECHNOLOGY PROGRESS, Issue 4 2010Tomoko Hongo-Hirasaki Abstract We investigated the effect of antibody solution conditions (ionic strength, pH, IgG concentration, buffer composition, and aggregate level (dimer content)) on filter performance for a virus removal filtration process using the PlanovaÔ 20N, a virus removal filter. Ionic strength and pH affected the filter flux. A consistent high flux was maintained at an ionic strength greater than 10 mM and at pH 4,8 under a typical buffer composition (sodium chloride, citrate, acetate, and phosphate). Optimum IgG concentration was 10,20 mg/mL allowing for high throughput (kg/m2 of IgG). Dimer content negligibly affected the flux level. Under high throughput conditions, virus spiking did not affect flux whereas a parvovirus logarithmic reduction value greater than 5 was maintained. From the results of zeta potential analyses for IgG and the membrane, we considered that electrostatic interactions between antibodies and the membrane affect filter performance (flux level and throughput). These results indicate that the PlanovaÔ 20N filter is applicable for a wide range of solution conditions typically used in antibody processing. © 2010 American Institute of Chemical Engineers Biotechnol. Prog., 2010 [source] A MATLAB toolbox for solving acid-base chemistry problems in environmental engineering applicationsCOMPUTER APPLICATIONS IN ENGINEERING EDUCATION, Issue 4 2005Chetan T. Goudar Abstract A MATLAB toolbox incorporating several computer programs has been developed in an attempt to automate laborious calculations in acid-base chemistry. Such calculations are routinely used in several environmental engineering applications including the design of wastewater treatment systems and for predicting contaminant fate and transport in the subsurface. The computer programs presented in this study do not replace student thinking involved in formulating the problem solving strategy but are merely tools that simplify the actual problem solving process. They encompass a wide variety of acid-base chemistry topics including equilibrium constant calculations, construction of distribution diagrams for mono and multiprotic systems, ionic strength and activity coefficient calculations, and buffer index calculations. All programs are characterized by an intuitive graphical user interface where the user supplies input information. Program outputs are either numerical or graphical depending upon the nature of the problem. The application of this approach to solving actual acid-base chemistry problems is illustrated by computing the pH and equilibrium composition of a 0.1 M Na2CO3 system at 30°C using several programs in the toolbox. As these programs simplify lengthy computations such as ionization fraction and activity coefficient calculations, it is hoped they will help bring more complicated problems to the environmental engineering classroom and enhance student understanding of important concepts that are applicable to real-world systems. The programs are available free of charge for academic use from the authors. © 2005 Wiley Periodicals, Inc. Comput Appl Eng Educ 13: 257,265, 2005; Published online in Wiley InterScience (www.interscience.wiley.com); DOI 10.1002/cae.20051 [source] Kinetics and Mechanism of Ni(II) Chelation in Model and Real Solutions of Xylem Sap of Quercus ilexELECTROANALYSIS, Issue 22 2007Margarida, Maria Correia, Santos Abstract The kinetics of formation and dissociation of Ni(II) complexes with oxalic and citric acids was studied by cyclic voltammetry in model solutions of xylem sap of Q. ilex (the dominant tree growing on serpentine soils of Northeast Portugal) using representative concentrations, pH and ionic strength. The role of magnesium on complex formation was analyzed from solutions where Mg is present at concentration levels found in the xylem sap of Q. ilex growing on both nonserpentine and serpentine soils. Kinetics studies were also done in diluted solutions of real xylem sap samples, spiked with increasing amounts of magnesium. The values obtained for the apparent rate constants were those anticipated by the proposed model. To test the validity of the methodology and mechanisms, formation rate constants, kf (M,1 s,1) of Ni(II) complexes with citrate and oxalate were evaluated that compare with the values from Eigen mechanism. [source] Spatial Imaging of Cu2+ -Ion Release by Combining Alternating Current and Underpotential Stripping Mode Scanning Electrochemical MicroscopyELECTROANALYSIS, Issue 2-3 2007Dirk Ruhlig Abstract Anodic underpotential stripping voltammetry was integrated into SECM in order to characterize local corrosion of metallic copper deposits on metal surfaces as a model for copper containing alloys. Primarily, the alternating current mode of SECM was applied in an electrolyte of low ionic strength for localizing possible corrosion sites without any perturbation of the corroding surface, e.g., by the presence of any redox mediator. Sequentially, the release of Cu2+ -ions was confirmed and locally visualized at the previously detected electrochemically active sites by means of spatially resolved anodic underpotential stripping voltammetry performed during SECM scanning. Underpotential stripping voltammetry of Cu2+ -ions was performed at a specifically developed 15,,m gold-coated Pt microelectrode used as SECM tip with a detection limit of 0.15,nM Cu2+ (N=4, RSD=6%) for an accumulation of 45,s at ,0.4,V. SECM images of model samples such as copper coated microelectrodes and lacquered metallic copper workpieces demonstrated the feasibility and applicability of combining AC- and underpotential stripping mode of SECM for local visualization of Cu2+ -ion release from corroding surfaces. [source] Permselective and Preconcentration Properties of a Surfactant-Intercalated Clay Modified ElectrodeELECTROANALYSIS, Issue 22 2006E. Ngameni Abstract This work is focused on the voltammetric examination of the ion exchange properties of a smectite type clay, before and after its modification by the replacement of its native interlamellar cations (Na+, K+, Ca2+) by hexadecyltrimethylammonium cations (HDTMA+). The raw clay and its organically modified form were first characterized by X-ray diffraction (XRD) and N2 adsorption,desorption isotherms (BET method) that confirmed the modification via an intercalation process. These materials were subsequently coated onto glassy carbon surfaces, and the resulting modified electrodes were evaluated for the uptake of [Ru(NH3)6]3+ and [Fe(CN)6]3, ions used as redox probes. Some experimental parameters affecting the incorporation of the probes within the film, including the ionic strength, the surfactant loading and the solution pH are thoroughly examined, in order to highlight the mechanism of the process. The possibility of using the surfactant-intercalated clay modified electrode as an electrochemical sensor for [Fe(CN)6]3, is also evaluated. [source] Disposable Screen-Printed Edge Band Ultramicroelectrodes for the Determination of Trace Amounts of Nitrite IonELECTROANALYSIS, Issue 10 2006Jen-Lin Chang Abstract The application of linear scan voltammetry for sensitive determination of nitrite by using a disposable screen-printed edge band carbon ultramicroelectrode (designated as SPUME) was reported in this study. The measurement with the SPUME can be performed in solutions of low ionic strength, e.g., natural waters, because the ohmic loses are negligible. The limiting oxidation current of nitrite showed a wide linear range up to 3,mM at the SPUME. A relative standard deviation of 2.46% (n=5) for analyzing 5,,M nitrite indicated a detection limit (S/N=3) of 0.38,,M. Real sample analysis of mineral and ground water samples as well as bratwurst food product showed satisfactory results. Since the SPUME is low cost and easy for mass production, the disposable nature further offers to application in diverse field of electroanalytical chemistry. [source] Complex Formation in the Region of Metal Hydrolysis and M(OH)2 Precipitation.ELECTROANALYSIS, Issue 7 2006(AMPSO)x, (OH)y, (OH)y Systems, A Glass Electrode Potentiometric, Polarographic Study of Cd Abstract The interaction between cadmium or zinc and AMPSO was investigated by DCP and GEP, at fixed total ligand to total metal concentration ratios and various pH values, at 25.0,°C and 0.1,M KNO3 ionic strength. For Cd,(AMPSO)x,(OH)y system, CdL and CdL(OH) species, were identified, with stability constants values set to (as log,,): 2.1±0.1 and 6.2±0.2, respectively. For Zn,(AMPSO)x,(OH)y system, the proposed final model with stability constants set to (as log,,) is: ZnL=2.5±0.1 and ZnL(OH)2=12.9±0.2. For both systems, the fact that AMPSO deprotonation occurs in the metal hydrolysis and M(OH)2 precipitation and the complexes formed are not too strong added a real challenge to data interpretation. [source] Analysis of the Voltammetric Response of Electroactive Guests in the Presence of Non-Electroactive Hosts at Moderate ConcentrationsELECTROANALYSIS, Issue 18 2004Sandra Mendoza Abstract In this work, we present a method to analyze the voltammetric response of reversible redox systems involving molecules that, bearing m non-interactive electroactive sites, can undergo fast complexation equilibria with host molecules present at concentrations of the same order of magnitude as those of the electroactive guest. The approach focuses on systems for which the relative values of the binding constants for the oxidized and reduced forms of the guest result in the displacement of the voltammetric response of the electroactive molecule as the concentration of the host is increased in the electrolytic solution. This behavior is commonly known as "one wave shift behavior". Based on a series of assumptions, the method allows calculation of all the thermodynamic parameters that describe the electrochemical and complexation equilibria of a given host-guest system. The main strength of the suggested method, however, relies on the fact that it only requires cyclic voltammetry data and that it can be used for systems in which large concentrations of the host can not be employed either due to important changes of the ionic strength or to solubility problems. Although the accuracy of the obtained information is limited by the quality of the data provided by the technique, and by the assumptions employed, it certainly represents an excellent starting point for subsequent refinement either using digital simulations or an independent experimental technique. [source] Determination of Reserpine in Urine by Capillary Electrophoresis with Electrochemiluminescence DetectionELECTROANALYSIS, Issue 3 2004Weidong Cao Abstract A fast and sensitive approach to detect reserpine in urine using micellar electrokinetic capillary chromatography with electrochemiluminescence (ECL) of Ru(bpy)32+ detection is described. Using a 25,,m i.d. capillary as separation column, the ECL detector was coupled to the capillary in the absence of an electric field decoupler. Field-amplified injection was used to minimize the effect of ionic strength in the sample and to achieve high sensitivity. In this way, the sample was analyzed directly without any pretreatment. The method was validated for reserpine in the urine over the range of 1×10,6,1×10,4,mol/L with a correlation coefficient of 0.996. The RSD for reserpine at a level of 5,,mol/L was 4.3%. The LOD (S/N=3) was estimated to be 7.0×10,8,mol/L. The average recoveries for 10,,mol/L reserpine spiked in human urine were 94%. [source] The dependence of the electrophoretic mobility of small organic ions on ionic strength and complex formationELECTROPHORESIS, Issue 5 2010Stuart A. Allison Abstract The ionic strength dependence of the electrophoretic mobility of small organic anions with valencies up to ,3 is investigated in this study. Provided the anions are not too aspherical, it is argued that shape and charge distribution have little influence on mobility. To a good approximation, the electrophoretic mobility of a small particle should be equal to that of a model sphere with the same hydrodynamic radius and same net charge. For small ions, the relaxation effect (distortion of the ion atmosphere from equilibrium due to external electric and flow fields) is significant even for monovalent ions. Alternative procedures of accounting for the relaxation effect are examined. In order to account for the ionic strength dependence of a specific set of nonaromatic and aromatic anions in aqueous solution, it is necessary to include complex formation between the anion with species in the BGE. A number of possible complexes are considered. When the BGE is Tris-acetate, the most important of these involves the complex formed between anion and Tris, the principle cation in the BGE. When the BGE is sodium borate, an anion,anion (borate) complex appears to be important, at least when the organic anion is monovalent. An algorithm is developed to analyze the ionic strength dependence of the electrophoretic mobility. This algorithm is applied to two sets of organic anions from two independent research groups. [source] Interaction study of a lysozyme-binding aptamer with mono- and divalent cations by ACEELECTROPHORESIS, Issue 3 2010Marie Girardot Abstract Binding between an aptamer and its target is highly dependent on the conformation of the aptamer molecule, this latter seeming to be affected by a variety of cations. As only a few studies have reported on the interactions of monovalent or divalent cations with aptamers, we describe herein the use of ACE in its mobility shift format for investigating interactions between various monovalent (Na+, K+, Cs+) or divalent (Mg2+, Ca2+, Ba2+) cations and a 30-mer lysozyme-binding aptamer. This study was performed in BGEs of different natures (phosphate and MOPS buffers) and ionic strengths. First, the effective charges of the aptamer in 30,mM ionic strength phosphate and MOPS (pH 7.0) were estimated to be 7.4 and 3.6, respectively. Then, corrections for ionic strength and counterion condensation effects were performed for all studies. The effective mobility shift was attributed not only to these effects, but also to a possible interaction with the buffer components (binary or ternary complexes) as well as possible conformational changes of the aptamer. Finally, apparent binding constants were calculated for divalent cations with mathematical linearization methods, and the influence of the nature of the BGE was evidenced. [source] Measurement of electrophoretic mobility of cardiomyocytesELECTROPHORESIS, Issue 21 2009Ying Zhou Abstract The electrophoretic mobility (EPM) of rat cardiomyocytes with or without the treatment of neuraminidase was studied by cell electrophoresis. The EPM was found to change over a range from 0 to 8.67,,m,s,1/V,cm,1, depending on ionic strength, transmembrane potential, pH value, and/or surface charges. It is interesting that zero EPM was observed but reverse of the mobility was not. These results suggested that the negative charges carried on the cardiomyocyte surface might comprehensively consist of surface sialic acid, plasmalemma proteins, phospholipids, and transmembrane potential. The aberrant electrical double layer formed between the carried negative charges and adions had a big adsorption layer and a diffusion layer whose sizes changed circularly, making only negative charges be carried on the surface of living cardiomyocytes. The special structures on the surface of cardiomyocytes probably play a considerable role in the process of cardiac electrical activity. [source] Organic solvents in CEELECTROPHORESIS, Issue S1 2009Ernst Kenndler Abstract In this contribution some fundamental aspects are discussed serving for a critical reflection and elucidation of the role of organic solvents in CE. The implications of the solvent on the parameters governing peak resolution are discussed based on the concepts describing migration and zone broadening in capillary zone electrophoresis. This discussion includes the solvent-dependent influence of the ionic strength on the mobility. The role of the solvent on the plate number in case of the inevitable diffusional peak dispersion is outlined, and its effect on other peak broadening contributions is briefly examined. This paper also deals with the problems of conductance, applicable voltage and analysis time upon application of organic solvents, and tries to clarify some misunderstandings common in the literature. [source] Electrophoretic behaviors of human hepatoma HepG2 cellsELECTROPHORESIS, Issue 9 2009Jyh-Ping Hsu Abstract The electrophoretic mobility of HepG2 cells was measured and a charge-regulated model was proposed to simulate the results obtained. Here, a cell was simulated by a rigid core and an ion-penetrable membrane layer containing both acidic and basic functional groups. The influences of the key parameters, including the pH, the ionic strength, the thickness of the membrane layer of a cell, the density and the dissociation constant of the dissociable functional groups in the membrane layer, and the binding constant of divalent cations on the electrophoretic mobility of a cell were investigated. In particular, the role of the buffer used in the experiment was discussed; this effect was neglected in almost all the relevant theoretical analyses in the literature. We showed that the binding ability of divalent cations to the dissociated functional groups in the membrane layer of a cell ranks as Ca2+>Mg2+>hexamethonium. [source] Methacrylate-based monolithic column with mixed-mode hydrophilic interaction/strong cation-exchange stationary phase for capillary liquid chromatography and pressure-assisted CECELECTROPHORESIS, Issue 19 2008Jian Lin Abstract A novel porous polymethacrylate-based monolithic column by in situ copolymerization of 3-sulfopropyl methacrylate (SPMA) and pentaerythritol triacrylate in a binary porogenic solvent consisting of cyclohexanol/ethylene glycol was prepared. The monolith possessed in their structures bonded sulfonate groups and hydroxyl groups and was evaluated as a hydrophilic interaction and strong cation-exchange stationary phases in capillary liquid chromatography (cLC) and pressure-assisted CEC using small polar neutral and charged solutes. While the SPMA was introduced as multifunctional monomer, the pentaerythritol triacrylate was used to replace ethylene glycol dimethacrylate as cross-linker with much more hydrophilicity due to a hydroxyl sub-layer. The different characterization of monolithic stationary phases were specially designed and easily prepared by altering the amount of SPMA in the polymerization solution as well as the composition of the porogenic solvent for cLC and pressure-assisted CEC. The resulting monolith showed the different trends about the effect of the permeabilities on efficiency in the pressure-assisted CEC and cLC modes. A typical hydrophilic interaction chromatography mechanism was observed at higher organic solvent content (ACN%>70%) for polar neutral analytes. For polar charged analytes, both hydrophilic interaction and electrostatic interaction contributed to their retention. Therefore, for charged analytes, selectivity can be readily manipulated by changing the composition of the mobile phase (e.g., pH, ionic strength and organic modifier). With the optimized monolithic column, high plate counts reaching greater than 170,000,plates/m for pressure-assisted CEC and 105,000 plates/m for cLC were easily obtained, respectively. [source] The zeta potential of surface-functionalized metallic nanorod particles in aqueous solutionELECTROPHORESIS, Issue 5 2008George M. Dougherty Abstract Metallic nanoparticles suspended in aqueous solutions and functionalized with chemical and biological surface coatings are important elements in basic and applied nanoscience research. Many applications require an understanding of the electrokinetic or colloidal properties of such particles. We describe the results of experiments to measure the zeta potential of metallic nanorod particles in aqueous saline solutions, including the effects of pH, ionic strength, metallic composition, and surface functionalization state. Particle substrates tested include gold, silver, and palladium monometallic particles as well as gold/silver bimetallic particles. Surface functionalization conditions included 11-mercaptoundecanoic acid (MUA), mercaptoethanol (ME), and mercaptoethanesulfonic acid (MESA) self-assembled monolayers (SAMs), as well as MUA layers subsequently derivatized with proteins. For comparison, we present zeta potential data for typical charge-stabilized polystyrene particles. We compare experimental zeta potential data with theoretically predicted values for SAM-coated and bimetallic particles. The results of these studies are useful in predicting and controlling the aggregation, adhesion, and transport of functionalized metallic nanoparticles within microfluidic devices and other systems. [source] System peaks in micellar electrophoresis: I. Utilization of system peaks for determination of critical micelle concentrationELECTROPHORESIS, Issue 5 2008Jana Lokajová Abstract A new way to determine the critical micelle concentration (CMC) based on the mobilities of system peaks is presented. A general approach for the CMC determination is based on the change of the slope or on finding the inflection point in the plot of a physical property of solution as a function of surfactant concentration. The determination of CMC by system peaks in CE utilizes a "jump" instead of a continuous change in the measured quantity. This phenomenon was predicted by the program PeakMaster, which was modified for simulation of micellar systems. The simulation of the steep change in mobilities of the anionic system peaks showing the CMC value was verified experimentally in a set of measurements, where the concentration of the surfactant was varied while the ionic strength was kept constant. The experimental work fully proved our model. A comparative electric current measurement was carried out. The proposed method seems to offer easier CMC determination as compared to the standard methods. [source] Temperature gradient focusing in a PDMS/glass hybrid microfluidic chipELECTROPHORESIS, Issue 24 2007Takuya Matsui Abstract This paper reports the application of temperature gradient focusing (TGF) in a PDMS/glass hybrid microfluidic chip. With TGF, by the combination of a temperature gradient along a microchannel, an applied electric field, and a buffer with a temperature-dependent ionic strength, analytes are focused by balancing their electrophoretic velocities against the bulk velocity of the buffer containing the analytes. In this work, Oregon Green 488 carboxylic acid was concentrated approximately 30 times as high as the initial concentration in 45,s at moderate electric strength of 70,V/cm and a temperature gradient of 55°C across the PDMS/glass hybrid microfluidic chip with a 1,cm long capillary. [source] CEC separation of heterocyclic amines using methacrylate monolithic columnsELECTROPHORESIS, Issue 11 2007Elena Barceló-Barrachina Abstract Two methacrylate-based monolithic columns, one with a negatively charged group (sulfonic group) and another with a new monomer N,N -dimethylamino ethyl acrylate (DMAEA), were prepared and tested for the separation of basic compounds by CEC. This new monolithic stationary phase was prepared by the in situ polymerization of DMAEA with butyl methacrylate and ethylene dimethacrylate, using a ternary porogenic solvent consisting of water, 1-propanol and 1,4-butanediol. The performance of this column was evaluated by means of the analysis of a family of heterocyclic amines. Separation conditions such as pH, amount of organic modifier, ionic strength and elution mode (normal or counterdirectional flow) were studied. At the optimal running electrolyte composition, and using the counterdirectional mode, symmetrical electrochromatographic peaks were obtained, with the number of theoretical plates up to 30,000 and a good resolution between closely related peaks. The 2-acrylamido-2-methyl-1-propane-sulfonic acid column was used for CEC-MS, taking advantage of the compatibility of its elution mode (normal flow) with the MS coupling. [source] Determination of dissociation constants of folic acid, methotrexate, and other photolabile pteridines by pressure-assisted capillary electrophoresisELECTROPHORESIS, Issue 17 2006Zoltán Szakács Abstract Pressure-assisted CE (PACE) was applied to determine the previously inaccessible complete set of pK values for folic acid and eight related multiprotic compounds. PACE allowed the determination of all acidity macroconstants at low (,0.1,mM) concentration without interferences of selfassociation or photodegradation throughout the pH range. The accuracy of the constants was verified by NMR-pH, UV-pH, and potentiometric titrations and the data could be converted into physiological ionic strength. It was shown that even three overlapping pK values can be determined by CE with good precision (<0.06) and accuracy if an appropriately low sample throughput is used. Experimental aspects of PACE for the quantitation of acid,base properties are analyzed. The site-specific basicity data obtained for folic acid and methotrexate (MTX) reveal that apparently slight constitutional differences between folic acid and MTX carry highly different proton-binding propensities at analogous moieties, especially at the pteridine N1,locus, providing straightforward explanation for the distinctive binding to dihydrofolate reductase at the molecular level. [source] Application of polymeric surfactants in micellar electrokinetic chromatography-electrospray ionization mass spectrometry of benzodiazepines and benzoxazocine chiral drugsELECTROPHORESIS, Issue 5-6 2006Jingguo Hou Abstract Chiral micellar EKC (CMEKC) coupled to ESI-MS using polymeric surfactants as pseudostationary phases is investigated for simultaneous enantioseparation of two benzodiazepines, (±)-oxazepam ((±)-OXA) and (±)-lorazepam ((±)-LOR), and one benzoxazocine, (±)-nefopam ((±)-NEF). First, enantioselectivity and electrospray sensitivity of six chiral polymeric surfactants for all three chiral compounds are compared. Second, using poly(sodium N -undecenoyl- L -leucinate) as pseudostationary phase, the organic modifiers (methanol (MeOH), isopropanol, and ACN) are added into the running buffer to further improve chiral resolution (RS). Next, a CMEKC-ESI-MS method for the simultaneous enantioseparation of two benzodiazepines is further developed by using a dipeptide polymeric surfactant, poly(sodium N -undecenoxy carbonyl- L,L -leucyl-valinate) (poly- L,L -SUCLV). The CMEKC conditions including nebulizer pressure, capillary length, ammonium acetate concentration, pH, poly- L,L -SUCLV concentration, and capillary temperature were optimized to achieve maximum chiral RS and highest sensitivity of MS detection. The spray chamber parameters (drying gas temperature and drying gas flow rate) as well as sheath liquid conditions (MeOH content, pH, flow rate, and ionic strength) were found to significantly influence MS S/N of both (±)-OXA and (±)-LOR. Finally, a comparative study between simultaneous UV and MS detection showed high plate numbers, better chiral RS, and enhanced detectability with CMEKC-MS. However, speed of analysis was faster using CMEKC-UV. [source] Enantioseparation in capillary electrophoresis using 2- O -(2-hydroxybutyl)-,-CD as a chiral selectorELECTROPHORESIS, Issue 20 2005Xiuli Lin Abstract The resolving ability of 2- O -(2-hydroxybutyl)-,-CD (HB-,-CD) with different degrees of substitution (DS,=,2.9 and 4.0) as a chiral selector in CZE is reported in this work. Fourteen chiral drugs belonging to different classes of compounds of pharmaceutical interest such as ,-agonists, antifungal agents, ageneric agents, etc., were resolved. The effects of the DS of HB-,-CD on separations were also investigated. The chiral resolution (Rs) was strongly influenced by the concentrations of the CD derivative, the BGE, and the pH of the BGE. Under the conditions of 50,mmol/L Tris-phosphate buffer at pH,2.5 containing 5,mmol/L HB-,-CD, all 14 analytes were separated. The very low concentration necessary to obtain separation was particularly impressive. The DS had a significant effect on the resolution of the chiral drugs and the ionic strength of the separation media; hence, the use of a well-characterized CD derivative is crucial. [source] Chiral separation of N -imidazole derivatives, aromatase inhibitors, by cyclodextrin-capillary zone electrophoresis.ELECTROPHORESIS, Issue 16 2004Mechanism of enantioselective recognition Abstract Baseline separation of ten new, substituted [1-(imidazo-1-yl)-1-phenylmethyl)] benzothiazolinone and benzoxazolinone derivatives with one chiral center was achieved using cyclodextrin-capillary zone electrophoresis (CD-CZE). A method for the enantiomeric resolution of these compounds was developed using neutral CDs (native ,-, ,-, ,-CDs or ,-, ,-, ,-hydroxypropyl (HP)-CDs) as chiral selectors. Operational parameters including the nature and concentration of the chiral selectors, pH, ionic strength, organic modifiers, temperature, and applied voltage were investigated. The use of neutral CDs provides enantiomeric resolution by inclusion of compounds in the CD cavity. The HP-,-CD and HP-,-CD were found to be the most effective complexing agents and allowed efficient enantiomeric resolutions. Optimal separation of N -imidazole derivatives was obtained using 50 mM phosphate buffer at pH 2.5 containing either HP-,-CD or HP-,-CD (7.5,12.5 mM) at 25°C, with an applied field of 0.50 kV·cm,1 giving resolution factors Rs superior to 1.70 with migration times of the second enantiomer less than 13 min. The same enantiomer migration order observed for all molecules can be related to a close interaction mechanism with CDs. The influence of structural features of the solutes on Rs and tm was studied. The lipophilic character (log kw) of the solutes and the apparent and averaged association constants of inclusion complexes for four compounds with the six different CDs led us to rationalize the enantioseparation mechanisms. The conclusions were corroborated with reversed-phase high-performance liquid chromatography (HPLC) on chiral stationary phases (CSPs) based on CDs. [source] |