Salt-induced aggregation in cationic liposome aqueous suspensions resulting in multi-step self-assembling complexes

The interaction of uni-univalent salt with cationic liposomes in aqueous suspension has been investigated by means of dynamic light scattering measurements and the hydrodynamic radius of the resulting aggregates has been evaluated for different ionic strengths. We observe the simultaneous presence of two different steady-state structures, in the 100–500 nm and 5 μm range, respectively, whose relative concentrations depend on the salt content. This behavior differs from that observed in usual charge stabilized colloidal suspensions and that giving rise to lipoplex formation in presence of polynucleotides. This peculiar behavior is briefly discussed in the light of Derjaguin–Landau–Verwey–Overbeek (DLVO) colloidal stability theory.     

Synthesis and characterizations of a novel zwitterionic hybrid copolymer containing both sulfonic and carboxylic groups via sulfonation and zwitterionic process

A novel zwitterionic hybrid copolymer containing both sulfonic and carboxylic groups was synthesized via sulfonation, zwitterionic process and sol-gel reaction. The properties of the step products were characterized by FT-IR spectra, thermal analyses, MALDI measurements and SEM morphologies. FT-IR spectra confirmed the related reactions. TGA and DrTGA analyses showed that their thermal stability enhanced with an increase in the zwitterionic extent. DSC curves revealed that both the glass transition temperature and the melting temperature elevated with the rising content of ion pairs. MALDI measurements suggested that the molecular structure of the zwitterionic hybrid PEG-[Si(OEt)₃]₂SO₃HCOOH was more stable than that of neutral hybrid PEG-[Si(OEt)₃]₂ or that of negatively charged hybrid PEG-[Si(OEt)₃]₂SO₃H. SEM image of the sulfonated polymer film indicated that the pore size was within 2.4-6.1 μm; whereas SEM of the zwitterionized copolymer film displayed that its pore size was less than 1 μm. This shrinkage in pore size can be ascribed to the introduction of carboxylic groups into the copolymer chains. Compared with that observed in the unionized polymer film, the large difference in the morphology of the ionized copolymer films demonstrated that ionization could alter these copolymer’s characteristics. Due to its excellent pore-creating performance, this zwitterionic hybrid copolymer expects to be employed to prepare nanofiltration and ultrafiltration membranes.     

Structural and dynamical properties of aqueous mixtures of pectin and chitosan

In this study phase separation, structure, and dynamics of aqueous pectin-chitosan mixtures of different ratios and a pure aqueous pectin sample have been investigated under various conditions by turbidimetry, SANS and dynamic light scattering (DLS). Only the mixture with r = 0.75 gelled upon decreasing the temperature ((r ≡ m_pectin/(m_pectin + m_chitosan), where m denotes the mass of the considered component). The pure pectin sample (r = 1) did not gel and the decrease in temperature seemed to promote phase separation. The addition of chitosan reduced the tendency of pectin to phase separate in the mixtures of pectin and chitosan. The general trend when cooling the samples was that the turbidity and the growth of the turbidity became more pronounced as the amount of pectin in the mixture was increased. The wavelength dependence of the turbidity indicated a change of the conformation of pectin chains from an extended form to a more compact structure in pectin solutions without chitosan as the temperature decreased. This was not observed for the mixture of pectin and chitosan. SANS measurements revealed excess scattered intensity in the low wave vector area with the strongest upturn for the pure pectin sample (r = 1). DLS experiments showed longer slow relaxation times after a temperature quench for all samples, with the most pronounced effect for the mixture of pectin and chitosan with r = 0.75. The synergism between pectin and chitosan at high pectin contents (r = 0.75) generated large association complexes over time.     

Dielectric relaxation pattern of dilute colloidal suspensions

An immediate method of analysis of the relaxation characteristics of a colloidal suspension, like of any dielectric, is based on the so-called Cole-Cole representation (imaginary part versus real part) of its complex dielectric constant in a wide frequency range. In this work, we show theoretical plots calculated according to the models developed by DeLacey and White (J Chem Soc Faraday Trans 2 77:2007–2039), and by Rosen et al. (J Chem Phys 98: 4183–4194; this model uses the dynamic Stern layer theory). Both theoretical approaches to the dielectric relaxation pattern of a colloidal suspension are compared to each other, and to experimental data obtained on polystyrene suspensions. Although no significant differences are found between the theoretical predictions of the relaxation patterns (except for the values of the dielectric constant; the DSL model yields higher polarizabilities of the suspensions), none of the models can exactly reproduce the frequency dependence of the dielectric constant of a colloidal system. We propose a modification of DeLacey and White's model to include the possibility that the ionic drag coefficients depend on the ion position in the double layer. The final results show that the general trends of the frequency dependence of the quantities involved are not modified, irregardless of the changes in ionic drag coefficients.     

Synthesis, characterization and flocculation performance of zwitterionic copolymer of acrylamide and 4-vinylpyridine propylsulfobetaine

A novel zwitterionic polyacrylamide AMVPPS copolymer containing sulfobetaine groups was synthesized by copolymerizing acrylamide (AM) and 4-vinylpyridine propylsulfobetaine (4-VPPS) in 0.5 mol/L NaCl solution with potassium persulfate (K₂S₂O₈) and sodium bisulfite (NaHSO₃) as initiator. The structure and composition of AMVPPS copolymer were characterized by FT-IR spectroscopy, ¹H NMR and elemental analyses. Thermal stability and solution properties of AMVPPS copolymer were studied by thermogravimetry analysis (TGA) and viscometry. Anti-polyelectrolyte behavior was observed and was found to be enhanced with increasing 4-VPPS content in copolymer. The flocculation performance for 2.5 g/L kaolin suspension and 2.5 g/L hematite suspension was evaluated by transmittance measurement and phase contrast microscopy. The effects of 4-VPPS content in the copolymer, intrinsic viscosity and the added salt on the flocculation performance were investigated. It was found that AMVPPS copolymer was a good flocculant for both anionic kaolin and cationic hematite suspensions and the flocculation performance of copolymer was much better than that of pure polyacrylamide (PAM). A very wide range of the optimum flocculation concentration, named as “flocculation window”, was found for both suspensions. These flocculation characteristics were mainly dependent on the charge neutralization, the intragroup conformation transition from water to NaCl solution and then the interchain bridging of the zwitterionic AMVPPS copolymer.     

Dielectric properties of quaternary ammonium ion-exchange beads dispersed in aqueous phases

Dielectric measurements were carried out for dense sediments of quaternary ammonium type anion-exchange resin beads dispersed in deionized water over a frequency range of 30 Hz to 130 MHz. According to a method proposed in previous studies the relative permittivities and electrical conductivities of ion-exchange beads were evaluated from the relaxation data observed in a megahertz region on the basis of a theory of interfacial polarization. The permittivities of the ion-exchange beads were found to be unchanged irrespectively of the salt form and somewhat lower than that of a continuous medium, while the conductivities of the ion-exchange beads were characteristic of the salt form. The equivalent ionic conductances of different counter anions in the beads were estimated from the conductivities of the ion-exchange beads. These results indicate an ion-binding effect in the resin beads.     

Spontaneous vesicle formation in aqueous solution of zwitterionic and anionic surfactant mixture

Vesicles form spontaneously in the aqueous mixtures of dodecyl sulfonate betaine (DSB) and sodium bis(2-ethylhexyl) sulfosuccinate (Aerosol OT (AOT)) at certain mixing ratios, which has been demonstrated by microcalorimeter, negative-staining transmission electronic microscopy (TEM) and quasi-elastic light scattering (QELS) methods. The addition of NaCl will expand the range of vesicle formation, and monodispersed vesicles are obtained in the solution from the salinity of 0.03 to 0.09 M at the mixing molar ratio of 7/3 (DSB/AOT, mol/mol), with the polydispersity of the system lower than 0.1. To learn more about the structural change in the mixture, ultrasonic was employed finally. Meanwhile analysis was made from the viewpoint of molecular geometry structure.     

Novel approaches for the preparation of silica-based zwitterionic hybrid copolymers

Two novel routes for the preparation of silica-based zwitterionic hybrid copolymers were proposed. A series of zwitterionic hybrid copolymers were prepared by the sulfonation of phenyl groups and the quaternary amination of tertiary amine groups alternately. Both FT-IR and ¹H NMR spectra confirm the step products. TGA and DrTGA analyses indicate that the thermal stability of these zwitterionic hybrid copolymers is higher than 400 °C. The determination of sulfonation degree reveals that the zwitterionic hybrid copolymer (c) from sulfonation-quarteramination (Route I) has the minimal value; meanwhile the anion-exchange capacity exhibits that the zwitterionic hybrid copolymer (e) from quarteramination-sulfonation (Route II) has the minimal value. These findings demonstrate the impact of electrostatic effect on the charge content of ionic groups. MALDI-TOF mass spectra exhibit that the decrease in the stability of the charged hybrid copolymers can be ascribed to the electrostatic effect between the molecular chains. The surface SEM images demonstrate that the surface of zwitterionic hybrid copolymer (e) from quarteramination-sulfonation (Route II) has some aggregated particles and form clusters regions in the hybrid matrix, which can also be attributed to the ionic interactions between those charged groups.     

Dielectric properties of thermally degraded chloroprene rubber

We performed dielectric measurements on thermally aged carbon-black-filled chloroprene rubber (CR). Primary and secondary processes were observed in unaged and thermally aged CR. The primary process is due to the cooperative motion of chloroprene chains in CR, and the secondary process is due to the local motion of chloroprene chains. For the primary process, the relaxation time slightly increases and symmetric shape parameter of the loss spectrum decreases with increasing aging time. For the secondary process, the relaxation strength decreases with increasing aging time, and reaches zero after 50 h. These changes in the dielectric relaxation parameters are due to the progress of the dehydrochlorination reaction at the chloroprene chains.     

Dynamic light scattering from micelle complexes of cetyltrimethylammonium bromide-sodium salicylate in aqueous solutions

The diffusion coefficient of cetyltrimethylammonium bromide-sodium salicylate in aqueous solutions has been determined, using the dynamic light-scattering technique, as a function of sodium salicylate concentration, as well as of temperature. Using a gel model the results are discussed in terms of intermicellar pseudo-linkages, entanglements of threadlike micelles, and formation of pseudo-network.     

稀薄细胞悬浊系模型的介电解析法

对稀薄细胞粒子是浊液体系进行了介电模型化,在导出的描述该体系介电行为的理论公式的基础上,确立了从实验观察到的介电参数获得体系相参数的精确解析方法,对该体系可能产生介电弛豫的原因进行了现象论的分析,并以一个微胶囊作为细胞模型进行了介电测量和解析,获得了合理的结果.     

Stability of the normal, zwitterionic neutral and anionic forms of aspartic acid in gas phase and aqueous media

Aspartic acid has a place of special importance among amino acids in view of its property to racemize from the - to the -form in living and nonliving systems which can be used to determine age. Molecular geometries of two isomeric normal neutral forms (called A and B forms), isomeric zwitterionic neutral forms (called A(Z) and B(Z) forms) and anions of these forms of aspartic acid were optimized at the RHF/6-31+G^* level. The geometries of hydrogen bonded complexes of each of the above species with one, two and three water molecules were also optimized at the same level. All these systems were solvated in bulk water using the polarized continuum model (PCM) of the self-consistent reaction field (SCRF) theory at the RHF/6-31+G^* level using the gas phase optimized geometries. It is found that in gas phase, the normal neutral A and B forms of aspartic acid would coexist while the zwitterionic A(Z) and B(Z) forms of the same would be absent. On the other hand, in bulk aqueous media, the normal neutral A and B forms of aspartic acid would not occur while the zwitterionic A(Z) and B(Z) forms would be present. Further, the abundance of the A(Z) form would be much more than that of the B(Z) form in bulk water. If the solution pH is adjusted appropriately so that a monoanion is formed, the anion of aspartic acid obtained from the neutral zwitterionic form by deprotonating O₈ would occur dominantly.     

Temperature-induced association and gelation of aqueous solutions of pectin. A dynamic light scattering study

Dynamic light scattering (DLS) measurements were carried out on aqueous solutions of low-methoxyl pectin at different temperatures and polymer concentration. Low temperature and increased polymer concentration promote the formation of multichain aggregates. The time correlation data obtained from the DLS experiments revealed, for all polymer solutions, the existence of two relaxation modes, one single exponential at short times followed by a stretched exponential at longer times. In the semidilute regime, a temperature reduction induced enhanced chain associations in the solutions with high values of the slow relaxation time and a strong wave vector dependence of the slow mode. These features could be rationalized in the framework of the coupling model of Ngai. At low temperatures (10 °C), gelation occurs in the semidilute regime and a transparent gel is formed. In this state, the profile of the correlation function changes and nonergodic signs are observed. The conjecture is that the association complexes and the gel network are stabilized through intermolecular hydrogen bonds, which are broken-up at higher temperatures. The hydrogen-bonded structures are formed in a process where the polymer chains have been “zipped” together in a cooperative manner.     

Conformational search for zwitterionic leucine and hydrated conformers of both the canonical and zwitterionic leucine using the DFT-CPCM model

The stable conformations for zwitterionic leucine have been searched for in solution as well as in gas phase. A total of 54 trial structures were generated by considering possible combinations of single bond rotamers. It is observed that zwitterions are not stable in gas phase. In order to investigate the zwitterions of leucine in solution, the calculations for all trial structures of zwitterions were performed initially at the PM3 level and 14 the lowest energy structures were reoptimized at the B3LYP/6-311G(d) level using the CPCM model. Seven of these conformers of zwitterionic leucine were found to be stable in solution. The five most stable conformers were then reoptimized at the B3LYP/6-311++G(d, p) level. The energy ordering of the canonical leucine(neutral) conformers were also considered on the basis of single point energy calculations at the B3LYP/6-311++G(d, p) level using the CPCM model. The chemical hardness, chemical potential, vertical ionization energy and vertical electron affinity were calculated for a few of the most stable canonical leucine and its zwitterions in solution. The effects of explicit addition of water molecules (microsolvation) on the structure and the energy of both canonical and zwitterionic conformers of leucine were investigated. It is noted that in gas phase, the singly and doubly hydrated canonical (neutral) forms are more stable than their zwitterionic counterparts. The solvated zwitterions and canonical structures of leucine were further investigated using the discrete/SCRF model with zero, one and two water molecules. In solution, the continuum solvent model shows that the bare zwitterionic form is more stable than the bare canonical form by 1.6 kcal/mol. This energy separation is increased to 3.8 and 4.8 kcal/mol with inclusion of one and two water molecules, respectively. The optimized structural parameters for the most stable zwitterionic leucine with zero, one and two water molecules in solution were compared with those reported for l-leucine crystal, which shows a close agreement between the optimized geometrical parameters of the zwitterionic leucine with two water molecules in solution with the experimental geometrical parameters for l-leucine crystal. It is also observed that when the structures of zwitterions with one and two explicit water molecules are optimized in solution, the geometrical parameters and their relative energies are found to be appreciably modified. We have also calculated the vibrational spectra of the most stable solvated zwitterionic leucine as well as for the most stable structure of zwitterionic leucine with one and two water molecules in solution.     

Dielectric properties of ion-exchange beads of sulfonic acid type dispersed in aqueous solutions — effect of fixed charge density

Ion-exchange beads with different densities of fixed charges were prepared by sulfoethylation of dextran gel beads. The relative permittivities and the electrical conductivities of the ion-exchange beads in a sodium form were evaluated by a dielectric technique consisting of the following two procedures proposed in a previous study (2): (a) Dielectric measurements for densely packed sediments of the ion-exchange beads; (b) Analysis of the observed dielectric relaxations by means of a theoretical equation of interfacial polarization for suspensions of spherical particles. The deduced permittivities of the ionexchange beads in equilibrium with water were about 60, which is lower than those of outer aqueous phases. The deduced conductirities were of the order of 1 to 10 mS cm^–1 and were increased reasonably with the fixed charge density. Closer consideration on these deduced values indicates that no specific interaction exists between the counter ions and the fixed charges irrespective of changes in fixed charge density and temperature.     

Analytical applications of photon correlation spectroscopy for size distribution measurements of natural colloidal suspensions: capabilities and limitations

Particles are ubiquitous in all natural systems and play an important role in the control and fate of nutrients and pollutants. Currently, only limited information is available concerning particle number and size distributions, owing to the problems involved in their experimental determination. In the present paper, limitations and optimal conditions for particle size determinations of environmental samples using photon correlation spectroscopy are studied. The detection limit, the effects of polydispersity of the sample and the refractive index value are discussed based on results obtained with synthetic colloids. The photon correlation spectroscopic determination of particle size distributions in real aquatic systems is also presented in the second part of the paper.     

Degradation behaviors of star-shaped poly(ethylene glycol)-poly(?-caprolactone) nanoparticles in aqueous solution

Star-shaped poly(ethylene glycol) (PEG)-poly(?-caprolactone) (?-PCL) block copolymers were synthesized via a ring-opening polymerization. Nanoparticles prepared by the precipitation/solvent evaporation technique exhibit a core-shell structure. The hydrolytic degradation of 3-arm PEG-PCL copolymeric nanoparticles was studied by dynamic light scattering (DLS), nuclear magnetic resonance (NMR) and gel permeation chromatography (GPC). It was found that copolymers with shorter PCL block length degraded faster. The sizes of nanoparticles fluctuated during the initial degradation period, and then increased slightly before finally dropping off. The degradation mainly occurred at CL-CL linkages firstly then at the EO-CL linkages. The CL/EO molar ratios and the molecular weights of copolymers decreased as degradation time and a zero-order degradation behavior was observed.     

Dielectric spectroscopy on aqueous solutions of pyridine and its derivatives

The complex (dielectric) permittivity has been measured as a function of frequency between 1 MHz and 40 GHz for aqueous solutions of pyridine, 2- and 3-methylpyridine, as well as 2,4- and 2,6-dimethylpyridine at various temperatures and solute concentrations. Different relaxation spectral functions are used to analytically represent the data, in particular the Cole-Cole function. The solute contribution to the extrapolated static permittivity has been calculated to show that, in correspondence with other aqueous solutions of organic molecules and ions, the permittivity of the solvent seems to be enhanced with respect to the pure water value. Also in accordance with other aqueous systems it is found that the principal dielectric relaxation time for equimolar solutions of stereo isomers at the same temperature may significantly differ from one another. A further result is the finding of an unusually strong temperature dependence in the relaxation time of the 1 molar solution of 2,6-dimethylpyridine.     

Theory of dielectric relaxations due to the interfacial polarization for two-component suspensions of spheres

A theoretical formula of dielectric relaxation in a form of complex relative permittivity is derived for dilute suspensions of spherical particles of two kinds on the basis of the Maxwell-Wagner theory of interfacial polarization. Another theoretical formula is derived further for concentrated suspensions of spheres of two kinds on condition that the formula derived above holds for the infinitesimally increasing process in concentration of the dispersed spheres. Furthermore a theoretical formula is derived for concentrated suspensions of shelled spheres of two kinds as the extension of the formula for concentrated suspensions. By use of the theoretical formulas proposed, values of the permittivities and the conductivities of the two-component suspensions were calculated for some examples with different sets of phase parameters. Results of the numerical calculation demonstrates dielectric relaxation profiles full of variety and characteristic of the suspensions containing two kinds of spheres covered with or without shells.     

Synthesis and catalytic properties of microemulsion-derived cerium oxide nanoparticles

The synthesis of cerium dioxide nanoparticles using an inverse microemulsion technique and precipitation method was investigated. Cerium hydroxide nanoparticles were synthesized by adding diluted ammonia to n-heptane–surfactant–cerium nitrate system. The micelle and particle size in the range of 5–12 nm were controlled by varying the molar water to surfactant ratio and analyzed by dynamic light scattering (DLS), small angle X-ray scattering (SAXS) and high-resolution transmission electron microscopy (HRTEM). Cerium hydroxide nanoparticles were isolated and subsequently treated at 100–600 °C to obtain nanoscale ceria. Crystallite sizes of cerium dioxide in the range of 6–16 nm were estimated by Scherrer analysis by X-ray diffraction (XRD) and HRTEM. The catalytic activity of particles annealed at 400 and 600 °C in soot combustion reactions was characterized by temperature-programmed oxidation (TPO) indicating a size-dependant activity. Crystallite sizes and catalytic stability of elevated ceria systems were tested in second combustion cycles.