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Evaluation of weak ion association between tetraalkylammonium ions and inorganic anions in aqueous solutions by capillary zone electrophoresis.

The evaluation of weak ion association between eleven (11) inorganic anions (charge -1 to -3) and five n-tetraalkylammonium ions, R4N+ (R: methyl, Me; ethyl, Et; propyl, Pr; butyl, Bu; pentyl, Am) in aqueous media at 25 degrees C was studied. The analysis of ion association equilibria was carried out under acidic condition (formate buffer, pH 3.5) at low separating potential (-10 kV) using a coated capillary with suppressed electroosmotic flow (micro = 4 x 10(-5) cm2 V(-1) s(-1)). Direct UV detection was done at anode (lambda = 220 nm). The combination of the aforementioned conditions ensured that ion association constants, Kass, between n-tetraalkylammonium ion and the small inorganic anions were reliably determined after a non-linear least squares (NLLS) treatment of the measured anion's mobility. Like their larger counterparts, small anions showed increased interaction with an increase in size of pairing ions. Moreover, for a specific cation, the interaction of small anions increased with an increase in size of the hydrated anions as reflected by the relationship between the Kass and the Stokes' radius. A favourable comparison exists between the results presented in this work and those previously documented from other analytical techniques like conductometry. Qualitatively, the mobility of the anions appeared to obey the Hückel's model more closely than the more elaborate Zwanzig and Hubbard-Onsager models.

Anions↗

Electrokinetic fingerprinting of grafted polyelectrolyte layers--a theoretical approach.

Electrokinetic fingerprinting (EF) was introduced by Marlow and Rowell [Marlow BJ, Rowel RL. Langmuir 1990;6:1088] for the comprehensive characterization of charged particle surfaces. Afterwards, EF was applied by many groups for the characterization of "hard" (i.e. non-swelling) surfaces. However, the advantages of EF could not yet utilized for the characterization of grafted polyelectrolyte layers (PL) since the theoretical background was not yet elaborated. A theory for the characterization of PL at complete dissociation of the functional groups was developed by Ohshima [Adv Colloid Interface Sci 1995;62:189] and later extended by Dukhin et al. [Dukhin S, Zimmermann R, Werner C. J Colloid Interface Sci 2005;286:761] for any degree of dissociation. Further progress in the characterization of soft surfaces may be achieved by combining EF and surface conductivity (SC) measurements. Both theory and experiment demonstrate that integrated measurements of SC and apparent zeta potential zeta(a) in broad ranges of pH and ionic strength provide information about Donnan potential Psi(D), surface charge, pK and surface potential Psi(0), while the interpretation is more uncertain, when only zeta(a) is measured. This advanced method of PL characterization is established for PL grafted on flat surfaces. When PL are formed on spherical particles, the SC may be measured by means of conductometry and/or dielectric spectroscopy. However, the current theories can only be applied within a rather narrow range of the practically relevant conditions. To overcome this limitation, an unified approach to the theory of electrophoresis for spherical particles with grafted PL was elaborated taking into account the existence of two different electrokinetic models for soft surfaces. While one model is focused on hydrodynamic permeability of soft surface and disregards surface current, another model considers the surface current and disregards electrokinetic water transport within the soft surface layer. Unification became possible through generalization of the capillary osmosis theory over soft surfaces.

Electric Conductivity↗

Effect of the spacer length on the association and adsorption behavior of dissymmetric gemini surfactants.

A series of dissymmetric gemini surfactants with the general formula [C12H25(CH3)2N(CH2)sN(CH3)2C14H29]Br2 designed as 12-s-14, where s=2, 6, and 10, were synthesized and their physicochemical properties investigated. The effect of spacer length on Krafft temperature, adsorption at the air/solution interface, and association in aqueous solution was studied by tensiometry, conductometry, and cryo-transmission electron microscopy. The Krafft temperature was found to increase linearly with spacer length. In the submicellar concentration range the dissymmetric 12-s-14 surfactants display ion pairing and premicellar association. Adsorption at air/solution interfaces and micellization in aqueous solution are similar to the behavior of their symmetric counterparts and depend strongly on spacer length.

Journal Article↗

Self-aggregation of binary mixtures of alkyltriphenylphosphonium bromides: a critical assessment in favor of more than one kind of micelle formation.

The micellization behavior of binary combinations of alkyltriphenylphosphonium bromides (ATPBs) with alkyl chain carbons 10, 12, 14, and 16 has been studied by conductometry and calorimetry. The combinations C(10)-C(12), C(10)-C(14), C(10)-C(16), C(12)-C(14), C(12)-C(16), and C(14)-C(16) were found to form two cmc's by both the methods, with good agreement, except C(14)-C(16)TPB, which has evidenced only a single cmc by calorimetry for all combinations. The combinations C(10)-C(12) (for both cmc(1) and cmc(2)) and C(10)-C(14)TPB (for cmc(2)) formed ideal mixtures, whereas the rest were nonideal. In the nonideal binary mixtures, the ATPB components showed antagonistic interaction with each other. The cmc, interaction parameter (beta), mixed micellar composition, extent of counterion binding, and thermodynamic parameters for the micellization process have been reported and discussed. The enthalpy of mixed micelle formation has been found to have a fair correlation with a Clint-type relation applicable to ideal binary mixtures of surfactants.

Journal Article↗

Selective hypoxia-cytotoxins based on vanadyl complexes with 3-aminoquinoxaline-2-carbonitrile-N1,N4-dioxide derivatives.

A new vanadyl complex with the formula VO(L1)2, where L1=3-amino-6(7)-chloroquinoxaline-2-carbonitrile N(1), N(4)-dioxide, has been synthesized and characterized by elemental analyses, conductometry, fast atom bombardment mass spectroscopy (FAB-MS) and electronic, Fourier transform infrared (FTIR), Raman, nuclear magnetic resonance (NMR) and electron paramagnetic resonance (EPR) spectroscopies. Results were compared with those previously reported for analogous vanadium complexes with other 3-aminoquinoxaline-2-carbonitrile N1,N4-dioxide derivatives as ligands. As an effort to develop novel metal-based selective hypoxia-cytotoxins and to improve bioavailability and pharmacological and toxicological properties of aminoquinoxaline carbonitrile N-dioxides bioreductive prodrugs, the new complex and VO(L)2 complexes, with L=3-amino-6(7)-bromoquinoxaline-2-carbonitrile N1,N4-dioxide (L2) and 3-amino-6(7)-methylquinoxaline-2-carbonitrile N1,N4-dioxide (L3), were subjected to cytotoxic evaluation in V79 cells in hypoxic and aerobic conditions. The complexes resulted in vitro more potent cytotoxins than the free ligands (i.e. potencies P(VO(L1)2)=3.0, P(L1)=9.0 microM) and Tirapazamine (P=30.0 microM) and showed excellent selective cytotoxicity in hypoxia, being no cytotoxic in oxia. In addition, the solubility in hydrophilic solvents resulted significantly higher for the vanadyl complexes than for the free ligands. These results could be indicative that complexation of the quinoxaline-2-carbonitrile N1,N4-dioxide derivatives with vanadium could improve their bioavailability. In addition, a new aspect of the series has been investigated. A detailed comparison of the electrochemical behavior of the free ligands and the complexes has been performed searching for a correlation between reduction potentials of the complexes and their activities and hypoxia selectivities.

Antineoplastic Agents↗

Reversibility of structural rearrangements in the negative vesicular membrane upon electrostatic adsorption/desorption of the polycation.

Interaction of small unilamellar vesicles (SUVs), composed of negative diphosphatidylglycerol (cardiolipin, CL(2-)) and neutral dipalmitoylphosphatidylcholine (DPPC), with poly(N-ethyl-4-vinylpyridinium bromide) (PEVP) was studied in water solution above and below the vesicular membrane melting point by means of differential scanning calorimetry, photon correlation spectroscopy, microelectrophoresis, conductometry, and fluorescence techniques. It has been found that CL(2-) species are homogeneously distributed within DPPC-CL(2-) SUV membrane leaflets and between them. Interaction of PEVP with DPPC-CL(2-) SUVs led to drastic structural rearrangements in the membrane if it was in the fluid state (liquid SUVs). Negative CL(2-) molecules migrated from the inner to the outer membrane leaflet and segregated in the vicinity of adsorbed PEVP chains. In addition, PEVP adsorption terminated completely the exchange of lipid molecules between the SUVs. At the same time, the integrity of liquid SUVs contacting PEVP remained unchanged. Since the interaction of PEVP with liquid SUVs was predominantly electrostatic in nature, the polycation could be completely removed from the vesicular membrane by addition of an excess of polyacrylic acid (PAA) polyanions forming a more stable electrostatic complex with PEVP. Removal of PEVP resulted in complete resumption of the original distribution of lipids in lateral and transmembrane directions as well as intervesicular lipid exchange. In contrast, PEVP interacting with DPPC-CL(2-) SUVs formed defects in the vesicular membrane if it was in the gel state (solid SUVs). Such interaction was contributed not only by electrostatic but most likely by hydrophobic interactions involving the defected membrane sites. PEVP kept contacting solid SUVs in the presence of an abundant amount of PAA. The established phenomena may be important for understanding the biological effects of polycations.

1,2-Dipalmitoylphosphatidylcholine↗

Fundamental comments on cell polarography according to Velazquez and Rosado.

Some fundamental comments are made on cell polarography according to Velázquez and Rosado (Fertil Steril 23:562, 1972). The results which they have obtained cannot be reliable because fundamental mistakes are made against the principles of the electroanalytic techniques used. We comment upon the conductometry, the amperometric titrations, and the alternating-current polarography as carried out by Velázquez and Rosado.

Electrophysiology↗

Wet deposition in Germany: long-term trends and the contribution of heavy metals.

As part of the program of the German Environmental Specimen Bank (ESB), precipitation is sampled on a weekly basis from eight sites in different ecosystems throughout Germany. The samples are analyzed for Na+, NH4+, K+, Mg2+, Ca2+, Cl-, NO3-, and SO4(2-) using ion chromatography with conductometrie detection Mn, Co, Ni, Cu, Zn, Cd, Pb, and Tl are determined by ICP-MS. In addition, pH and conductivity of the samples are measured. In this paper, the weekly and annual deposition in 1994 is compared for the different sampling sites and with literature data.

Biological Specimen Banks↗

On iontophoretic delivery enhancement: ionization and transport properties of lidocaine hydrochloride in aqueous propylene glycol.

The ionization and transport properties of lidocaine hydrochloride (LidHCl) in aqueous propylene glycol (PG) containing 20% PG by weight was studied by means of electrical precision conductometry. For drug concentrations exceeding about 1.7 mM a slight formation of LidH(+)Cl(-) ion-pairs is indicated; ion-pair association constant, K(p)=1.73 (molar scale). A two variable analysis of the experimental data yielded K(a)=1.5x10(-8) for the acid dissociation constant of LidH(+), i.e. pK(a)=7.82, and the limiting ionic conductivity, lambda(o)(LidH(+))=21.73 cm(2) S mol(-1). To enable evaluation of single ion conductivities the proton transport number of HCl in the present solvent mixture was determined using the moving boundary method.

Anesthetics, Local↗

Complexation studies of iodides of trivalent uranium and lanthanides (Ce and Nd) with 2,2'-bipyridine in anhydrous pyridine solutions.

In anhydrous pyridine solution at 294 K, U(III) and Ce(III) triiodides were found to form both 1:1 (ML) and 1:2 (ML(2)) complexes with bipyridine (bipy = L) while Nd(III) triodide formed only a 1:2 complex. The 1:3 (ML(3)) complexes were identified at low temperature with a large excess of L. Conductometry measurements showed for U(III) a large increase in the conductivity when increasing the molar ratio L:U. The complex UL(2) was found to be a 1:1 electrolyte and the species UI(2)(+) was more reactive toward L in comparison with UI(3). For Ce(III) and Nd(III), MI(2)(+) and MI(3) present about the same affinity for L. The stability of the complexes is limited, and U(III) possesses a slightly higher affinity for bipy than the trivalent lanthanides. Interestingly, a preference for the formation of ML(2) complex was shown for all the studied M(III) ions. The driving force for complex formation was always the enthalpy, and, surprisingly for a bidendate ligand (bipy), no favorable entropy contribution to complex formation was observed. The X-ray crystal structures of [CeI(3)(bipy)(2)(py)](4).5py.bipy and UI(3)(bipy)(2)(py).2py were determined. The structures of the molecules MI(3)(bipy)(2)(py) are almost identical for U and Ce. The mean M(III)-N(bipy) bond distances are equal to 2.67(3) A for Ce(III) and 2.65(4) A for U(III). The slightly smaller M(III)-N(bipy) distances observed for U(III) would reflect a slightly more important covalent character of the U(III)-N(bipy) bonds, in agreement with the slightly better affinity of U(III) than Ce(III) or Nd(III) toward bipy observed in solution and with the fact that the enthalpy is the driving force for complex formation.

Journal Article↗

Cation/anion recognition by a partially substituted lower rim calix[4]arene hydroxyamide, a ditopic receptor.

The complexation ability of a partially substituted lower rim calix[4]arene hydroxyamide derivative, 25,27-bis[N-(2-hydroxy-1,1-bishydroxymethylethyl)amino- carbonylmethoxy]calix[4]arene-26,28-diol, 1, for cations and anions was investigated through (1)H NMR, conductometry, spectrophotometry, and calorimetry in dipolar aprotic media. (1)H NMR studies of 1 in the deuterated solvents (acetonitrile, methanol, and dimethylsulfoxide) reflect ligand-solvent interactions in methanol and dimethylsulfoxide. As far as the cations are concerned, a selectivity peak is found when standard Gibbs energies of complexation of 1 with cations (alkaline-earth, zinc, and lead) are plotted against corresponding data for cation hydration. This finding reflects the key role played by the desolvation and binding processes in the overall complexation of this receptor and these cations in acetonitrile. This is also interpreted in terms of enthalpy and entropy data. Factors such as, the nature and the arrangement of donor atoms in the hydrophilic cavity of the ligand on cation complexation process, are discussed. This paper also addresses anion complexation processes. It is found that 1 interacts through hydrogen bond formation with fluoride, dihydrogen phosphate, and pyrophosphate in acetonitrile and N,N-dimethylformamide. The thermodynamics associated with these processes is fully discussed taking into account literature data involving calix[4]pyrroles and these anions in these solvents. Previous work regarding the water solubility of these ligands is discussed. It is concluded that 1 behaves as a ditopic ligand in dipolar aprotic media.

Journal Article↗

Conductometric study of precursor compound formation during wet-chemical synthesis of nanocrystalline hydroxyapatite.

Conductometry was employed to study the phase evolution of calcium phosphate compounds during the wet-chemical synthesis of hydroxyapatite (HA). Calcium hydroxide and orthophosphoric acid were used to prepare HA at various temperatures ranging from 30 to 95 degrees C. The electrical conductivity and pH of the reaction mixture were measured at regular intervals of time during acid addition, and the rate of change of conductivity was used to decipher the end point of the reaction. Our previous studies have shown that the end product of this reaction route yields mildly carbonated crystalline HA. The trend of the change in conductivity with time was similar at all temperatures. The conductivity curves were divided into three regions based on the variation in slope of the curves. The slope of the curves decreased with increasing temperatures in the first two regions, and the slope is greater in the second region than in the first. From the conductivity and pH measurement results, the possible precursor phase was identified and it had the composition Ca(3)(PO(4))(2). The kinetics of phase transformation was also analyzed and compared to previous work. The similarities between this work and the traditionally adapted experimental work for phase formation and transformation kinetics are highlighted, and the novelty in the current work is discussed.

Acids↗

Microcalorimetric and conductivity studies with micelles prepared from multi-headed pyridinium surfactants.

A set of novel single-chain surfactants bearing one (P1), two (P2), and three (P3) pyridinium headgroups have been synthesized in an attempt to achieve control over the aggregate properties. The critical micellar concentrations (cmc's) and the degrees of counterion dissociation (alpha) of micelles of these surfactants were determined by conductometry. The cmc and the alpha values increased with increase in the number of headgroups of the surfactant. The thermodynamics of micellization of these surfactants were investigated by microcalorimetry, and the results were compared with that of well-known single-chain/single-headgroup surfactant, cetylpyridinium bromide (CPB). The relationship between the cmc of surfactant in solution and its free energy of micellization (deltaG(o)m) was derived for each surfactant. Exothermic enthalpies of micellization (deltaH(o)m) and positive entropies of micellization (deltaS(o)m) were observed for all the surfactants. deltaH(o)m values were found to be more negative for CPB than P1, and it increased with a negative sign from P1 to P2 and decreased for P3. In contrast the deltaS(o)m values decreased with increase in the number of headgroups. The deltaG(o)m values progressively became less negative with increase in the number of headgroups. This implies that micelle formation becomes less favorable as more headgroups are incorporated in the surfactant.

Journal Article↗

Thermodynamics of micellization of multiheaded single-chain cationic surfactants.

The energetics of micelle formation of three single-chain cationic surfactants bearing single (h = 1), double (h = 2), and triple (h = 3) trimethylammonium [(+)N(CH(3))(3)] headgroups have been investigated by microcalorimetry. The results were compared with the microcalorimetric data obtained from well-known cationic surfactant, cetyl trimethylammonium bromide (CTAB), bearing a single chain and single headgroup. The critical micellar concentrations (cmc's) and the degrees of counterion dissociation (alpha) of micelles of these surfactants were also determined by conductometry. The cmc and the alpha values increased with the increase in the number of headgroups of the surfactant. The relationship between the cmc of the surfactant in solution and its free energy of micellization (DeltaG(m)) was derived for each surfactant. Exothermic enthalpies of micellization (DeltaH(m)) and positive entropies of micellization (DeltaS(m)) were observed for all the surfactants. Negative DeltaH(m) values increased from CTAB to h = 1 to h = 2 and decreased for h = 3 whereas DeltaS(m) values decreased with increase in the number of headgroups. The DeltaG(m) values progressively became less negative with the increase in the number of headgroups. This implies that micelle formation becomes progressively less favorable as more headgroups are incorporated in the surfactant. From the steady-state fluorescence measurements using pyrene as a probe, the micropolarities sensed by the probe inside various micelles were determined. These studies suggest that the micelles are more hydrated with multiheaded surfactants and the micropolarity of micelles increases with the increase in the number of headgroups.

Cations↗

Interactions of bovine serum albumin with aluminum polyoxocations and aluminum hydroxide.

Interactions of aqueous solutions of aluminum polyoxocations (Al13-mers and Al30-mers) and aluminum hydroxide suspensions of varying particle sizes (26, 55, and 82 nm) with a model protein, bovine serum albumin (BSA), have been investigated using potentiometry, conductometry, viscometry, 27Al solution NMR, UV-vis spectroscopy, dynamic light scattering, zeta-potential measurements, thermogravimetry, X-ray diffraction, and scanning electron microscopy. Increasing amounts of BSA partially convert Al13-mers and, to a larger extent, Al30-mers into amorphous Al hydroxide without gel formation. At the same time, BSA molecules can form unstable aggregates in the Al polyoxocation solutions which redisperse easily upon standing. In the case of Al hydroxide sols, BSA addition causes substantial gelation, the extent of which is proportional to the amount of BSA added and inversely related to the Al hydroxide particle size. Upon freeze-drying or centrifugation of Al species-BSA solutions, an interesting sheetlike morphology with 150-200 nm wide nanoribbons is observed for pure Al hydroxide nanoparticles and for solutions of Al polyoxocations with the highest amount of BSA studied. On the basis of the combined solution, colloidal and solid-state characterization of model Al species-BSA systems, a qualitative model of possible interactions in the Al polyoxocation-BSA and Al hydroxide-BSA systems is proposed wherein core-shell hybrid nanoparticles are formed from protein "core" and Al polyoxocation "shell" or Al hydroxide "core" and protein "shell".

Aluminum↗

Decreased hydration state of the stratum corneum and reduced amino acid content of the skin surface in patients with seasonal allergic rhinitis.

Recent studies of the stratum corneum (SC) in patients with atopic dermatitis (AD) have disclosed various functional impairments even in clinically unaffected skin. However, it has not been clear whether the presence of atopic background itself has any influence on the function of the SC. In this study, we conducted functional studies of the SC in the mid-portion of the flexor surface of the forearm of 49 skin lesion-free patients with allergic rhinitis to Japanese cedar pollen (atopic respiratory disease; ARD) in early spring, their disease-active season, by comparing the findings obtained with those in 28 patients with AD and 57 age-matched healthy control subjects. The results showed that the patients with ARD had significantly lower skin surface hydration levels assessed by high-frequency conductometry than those of the healthy control subjects. These levels were, however, not as low as those noted in moderately or severely affected patients with AD. Moreover, by measuring the amounts of water-soluble amino acids contained in the superficial portions of the SC, we found that these are also decreased at a marginal level (P = 0.051) in patients with ARD compared with levels in healthy control subjects. In contrast, the water barrier function of the SC evaluated by measurements of transepidermal water loss in patients with ARD was not different from that of the healthy control subjects. These results suggest that, although their skin appears normal clinically, the SC of the patients with ARD has functional deficiency in water-holding capacity.

Adult↗

Effects of surfactant micelles on viscosity and conductivity of poly(ethylene glycol) solutions.

The neutral polymer-micelle interaction is investigated for various surfactants by viscometry and electrical conductometry. In order to exclude the well-known necklace scenario, we consider aqueous solutions of low molecular weight poly(ethylene glycol) (2-20)x10(3), whose radial size is comparable to or smaller than micelles. The single-tail surfactants consist of anionic, cationic, and nonionic head groups. It is found that the viscosity of the polymer solution may be increased several times by micelles if weak attraction between a polymer segment and a surfactant exists, epsilon<k(B)T. Similarly, ion migration in polymer solutions may be significantly hindered by cooperative interactions between polymers and micelles. Even though epsilon is small, the interaction energy between a macromolecule and a micelle can be a few k(B)T due to many contacts, and thus leads to polymer adsorption on micelles' surfaces. The rapid growth of the viscosity with surfactant concentration is therefore attributed to the considerable cross links among micelles and polymers (transient network). In addition to substantial alteration of the transport properties, this weak interaction also influences the onset point of thermodynamic instability associated with polymer-surfactant solutions. The examples include the decrease of critical aggregation concentration for ionic surfactant and clouding point for nonionic surfactant due to PEG addition.

Journal Article↗

Shewanella putrefaciens adhesion and biofilm formation on food processing surfaces.

Laboratory model systems were developed for studying Shewanella putrefaciens adhesion and biofilm formation under batch and flow conditions. S. putrefaciens plays a major role in food spoilage and may cause microbially induced corrosion on steel surfaces. S. putrefaciens bacteria suspended in buffer adhered readily to stainless steel surfaces. Maximum numbers of adherent bacteria per square centimeter were reached in 8 h at 25 degrees C and reflected the cell density in suspension. Numbers of adhering bacteria from a suspension containing 10(8) CFU/ml were much lower in a laminar flow system (modified Robbins device) (reaching 10(2) CFU/cm(2)) than in a batch system (reaching 10(7) CFU/cm(2)), and maximum numbers were reached after 24 h. When nutrients were supplied, S. putrefaciens grew in biofilms with layers of bacteria. The rate of biofilm formation and the thickness of the film were not dependent on the availability of carbohydrate (lactate or glucose) or on iron starvation. The number of S. putrefaciens bacteria on the surface was partly influenced by the presence of other bacteria (Pseudomonas fluorescens) which reduced the numbers of S. putrefaciens bacteria in the biofilm. Numbers of bacteria on the surface must be quantified to evaluate the influence of environmental factors on adhesion and biofilm formation. We used a combination of fluorescence microscopy (4',6'-diamidino-2-phenylindole staining and in situ hybridization, for mixed-culture studies), ultrasonic removal of bacteria from surfaces, and indirect conductometry and found this combination sufficient to quantify bacteria on surfaces.

Bacterial Adhesion↗