Modulation of surface charge, particle size and morphological properties of chitosan-TPP nanoparticles intended for gene delivery

This work investigates the polyanion initiated gelation process in fabricating chitosan-TPP (tripolyphosphate) nanoparticles in the size range of 100-250 nm intended to be used as carriers for the delivery of gene or protein macromolecules. It demonstrates that ionic gelation of cationic chitosan molecules offers a flexible and easily controllable process for systematically and predictably manipulating particle size and surface charge which are important properties in determining gene transfection efficacy if the nanoparticles are used as non-viral vectors for gene delivery, or as delivery carriers for protein molecules. Variations in chitosan molecular weight, chitosan concentration, chitosan to TPP weight ratio and solution pH value were examined systematically for their effects on nanoparticle size, intensity of surface charge, and tendency of particle aggregation so as to enable speedy fabrication of chitosan nanoparticles with predetermined properties. The chitosan-TPP nanoparticles exhibited a high positive surface charge across a wide pH range, and the isoelectric point (IEP) of the nanoparticles was found to be at pH 9.0. Detailed imaging analysis of the particle morphology revealed that the nanoparticles possess typical shapes of polyhedrons (e.g., pentagon and hexagon), indicating a similar crystallisation mechanism during the particle formation and growth process. This study demonstrates that systematic design and modulation of the surface charge and particle size of chitosan-TPP nanoparticles can be readily achieved with the right control of critical processing parameters, especially the chitosan to TPP weight ratio. (c) 2005 Elsevier B.V. All rights reserved.

Resistance of Staphylococcus aureus to the cationic antimicrobial agent poly(2-(dimethylamino ethyl)methacrylate) (pDMAEMA) is influenced by cell-surface charge and hydrophobicity

Cationic antimicrobial agents may prevent device-associated infections caused by Staphylococcus epidermidis and Staphylococcus aureus. This study reports that the cationic antimicrobial polymer poly(2-(dimethylamino ethyl)methacrylate) (pDMAEMA) was more effective at antagonizing growth of clinical isolates of S. epidermidis than of S. aureus. Importantly, mature S. epidermidis biofilms were significantly inactivated by pDMAEMA. The S. aureus isolates tested were generally more hydrophobic than the S. epidermidis isolates and had a less negative charge, although a number of individual S. aureus and S. epidermidis clinical isolates had similar surface hydrophobicity and charge values. Fluorescence spectroscopy and flow cytometry revealed that fluorescently labelled pDMAEMA interacted strongly with S. epidermidis compared with S. aureus. S. aureus Delta dltA and Delta mprF mutants were less hydrophobic and therefore more susceptible to pDMAEMA than wild-type S. aureus. Although the different susceptibility of S. epidermidis and S. aureus isolates to pDMAEMA is complex, influenced in part by surface hydrophobicity and charge, these findings nevertheless reveal the potential of pDMAEMA to treat S. epidermidis infections.

Density functional theory study of the interaction between CO and on a Pt surface:CO/Pt(111), O/Pt(111), and CO/O/Pt(111)

Ab initio total energy calculations within the Density Functional Theory framework were carried out for Pt(111), Pt(111)-p(2x2)-CO, Pt(111)-p(2x2)-O, and Pt(111)-p(2x2)-(CO+O) to provide an insight into the interaction between CO and O on metal surfaces, an important issue in CO oxidation, and also in promotion and poisoning effects of catalysis. The geometrical structures of these systems were optimized with respect to the total energy, the results of which agree with existing experimental values very well. It is found that (i) the local structures of Pt(111)-p(2x2)-(CO+O), such as the bond lengths of C-O, C-Pt, and O-Pt (chemisorbed O atom with Pt), are almost the same as that in Pt(111)-p(2x2)-CO and Pt(111)-p(2x2)-O, respectively, (ii) the total valence charge density distributions in Pt(111)-p(2x2)-(CO+O) are very similar to that in Pt(111)-p(2x2)-CO, except in the region of the chemisorbed oxygen atom, and also nearly identical to that in Pt(111)-p(2x2)-O, apart from in the region of the chemisorbed CO, and (iii) the chemisorption energy of CO on a precovered Pt(111)-p(2x2)-O and the chemisorption energy of O on a precovered Pt(111)-p(2x2)CO are almost equal to that in Pt(111)-p(2x2)-CO and Pt(111)-p(2x2)-O, respectively. These results indicate that the interaction between CO and chemisorbed oxygen on a metal surface is mainly shore range in nature. The discussions of Pt-CO and Pt-O bonding and the interaction between CO and the chemisorbed oxygen atom on Pt(111) are augmented by local densities of states and real space distributions of quantum states.

Standardisation and comparison of methods employed for microbial cell surface hydrophobicity and charge determination

Whilst there are a number of methods available to characterise the cell surface hydrophobicity (CSH) and cell surface charge (CSC) of microorganisms, there is still debate concerning the correlation of results between individual methods. In this study, the techniques of bacterial adherence to hydrocarbons (BATH) and hydrophobic interaction chromatography (HTC) were used to measure CSH. Electrostatic interaction chromatography (ESIC) and zeta potential (ZP) measurements were used to determine CSC. To allow meaningful comparisons between the BATH and HIC tests, between ESIC and ZP and also between CSH and CSC, the buffer systems employed in each test were standardised (phosphate buffered saline, pH 7.3, 0.01 mM). Isolates of Staphylococcus epidermidis derived from microbial biofilm were used as the test organism in this study. The isolates examined exhibited primarily medium to high CSH and a highly negative CSC. Good correlation of CSH measurement was observed between the BATH and HIC tests (r = 0.89). Good correlation was observed between ESIC (anionic exchange column) and ZP measurements. No correlations were observed between isolate CSC and either increased or decreased CSH. It is recommended that whenever comparisons of various methods to determine either CSC or CSH (by partitioning methods), the buffer systems should remain constant throughout to achieve consistency of results.

Structure and dynamics of a confined ionic liquid. topics of relevance to dye-sensitized solar cells

The behavior of a model ionic liquid (IL) confined between two flat parallel walls was studied at various interwall distances using computer simulations. The results focus both on structural and dynamical properties. Mass and charge density along the confinement axis reveal a structure of layers parallel to the walls that leads to an oscillatory profile in the electrostatic potential. Orientational correlation functions indicate that cations at the interface orient tilted with respect to the surface and that any other orientational order is lost thereafter. The diffusion coefficients of the ions exhibit a maximum as a function of the confinement distance, a behavior that results from a combination of the structure of the liquid as a whole and a faster molecular motion in the vicinity of the walls. We discuss the relevance of the present results and elaborate on topics that need further attention regarding the effects of ILs in the functioning of IL-based dye-sensitized solar cells.

Switchable Induced Polarization in LaAlO3/SrTiO3 Heterostructures

Demonstration of a tunable conductivity of the LaAlO3/SrTiO3 interfaces drew significant attention to the development of oxide electronic structures where electronic confinement can be reduced to the nanometer range. While the mechanisms for the conductivity modulation are quite different and include metal insulator phase transition and surface charge writing, generally it is implied that this effect is a result of electrical modification of the LaAlO3 surface (either due to electrochemical dissociation of surface adsorbates or free charge deposition) leading to the change in the two-dimensional electron. gas (2DEG) density at the LaAlO3/SrTiO3 (LAO/STO) interface. In this paper, using piezoresponse force microscopy we demonstrate a switchable electromechanical response of the LAO overlayer, which we attribute to the motion of oxygen vacancies through the LAO layer thickness. These electrically induced reversible changes in bulk stoichiometry of the LAO layer are a signature of a possible additional mechanism for nanoscale oxide 2DEG control on LAO/STO interfaces.

Nonlinearly coupled localized plasmon resonances: Resonant second-harmonic generation

The efficient resonant nonlinear coupling between localized surface plasmon modes is demonstrated in a simple and intuitive way using boundary integral formulation and utilizing second-order optical nonlinearity. The nonlinearity is derived from the hydrodynamic description of electron plasma and originates from the presence of material interfaces in the case of small metal particles. The coupling between fundamental and second-harmonic modes is shown to be symmetry selective and proportional to the spatial overlap between polarization dipole density of the second-harmonic mode and the square of the polarization charge density of the fundamental mode. Particles with high geometrical symmetry will convert a far-field illumination into dark nonradiating second-harmonic modes, such as quadrupoles. Effective second-harmonic susceptibilities are proportional to the surface-to-volume ratio of a particle, emphasizing the nanoscale enhancement of the effect.

Turning Indium Oxide into a Superior Electrocatalyst:Deterministic Heteroatoms

The efficient electrocatalysts for many heterogeneous catalytic processes in energy conversion and storage systems must possess necessary surface active sites. Here we identify, from X-ray photoelectron spectroscopy and density functional theory calculations, that controlling charge density redistribution via the atomic-scale incorporation of heteroatoms is paramount to import surface active sites. We engineer the deterministic nitrogen atoms inserting the bulk material to preferentially expose active sites to turn the inactive material into a sufficient electrocatalyst. The excellent electrocatalytic activity of N-In2O3 nanocrystals leads to higher performance of dye-sensitized solar cells (DSCs) than the DSCs fabricated with Pt. The successful strategy provides the rational design of transforming abundant materials into high-efficient electrocatalysts. More importantly, the exciting discovery of turning the commonly used transparent conductive oxide (TCO) in DSCs into counter electrode material means that except for decreasing the cost, the device structure and processing techniques of DSCs can be simplified in future.

A DFT study of the transition metal promotion effect on ethylene chemisorption on Co(0001)

Transition metals are often introduced to a catalyst as promoters to improve catalytic performance. In this work, we study the promotion effect of transition metals on Co, the preferred catalytic metal for Fischer-Tropsch synthesis because of its good compromise of activity, selectivity and stability, for ethylene chemisorption using density functional theory (DFT) calculations, aiming to provide some insight into improving the alpha-olefin selectivity. In order to obtain the general trend of influence on ethylene chemisorption, twelve transition metals (Zr, Mn, Re, Ru, Rh, It, Ni, Pd, Pt, Cu, Ag and Au) are calculated. We find that the late transition metals (e.g. Pd and Cu) can decrease ethylene chemisorption energy. These results suggest that the addition of the late transition metals may improve alpha-olefin selectivity. Electronic structure analyses (both charge density distributions and density of states) are also performed and the understanding of calculated results is presented. (C) 2009 Elsevier B.V. All rights reserved.

A density functional theory study of CO oxidation on Ru(0001) at low coverage

We have performed ab initio density functional theory calculations with the generalized gradient approximation to investigate CO oxidation on Ru(0001). Several reaction pathways and transition states are identified. A much higher reaction barrier compared to that on Pt(111) is determined, confirming that the Ru is very inactive for CO oxidation under UHV conditions. The origin of the reaction barrier was analyzed. It is found that in the transition state the chemisorbed O atom sits in an unfavorable bonding site and a significant competition for bonding with the same substrate atoms occurs between the CO and the chemisorbed O, resulting in the high barrier. Ab initio molecular dynamics calculations show that the activation of the chemisorbed O atom from the initial hcp hollow site (the most stable site) to the bridge site is the crucial step for the reaction. The CO oxidation on Ru(0001) via the Eley-Rideal mechanism has also been investigated. A comparison with previous theoretical work has been made. (C) 2000 American Institute of Physics. [S0021-9606(00)31223-5].

Simple preparation of positively charged silver nanoparticles for detection of anions by surface-enhanced Raman spectroscopy

Modification of citrate and hydroxylamine reduced Ag colloids with thiocholine bromide, a thiol functionalized quaternary ammonium salt, creates particles where the zeta potential is switched from the normal values of ca. -50 mV to ca. + 50 mV. These colloids are stable but can be aggregated with metal salts in much the same way as the parent colloids. They are excellent SERS substrates for detection of anionic targets since their positive zeta potentials promote adsorption of negatively charged ions. This is important because the vast majority of published SERS studies involve cationic or neutral targets. Moreover, the fact that the modifier is a quaternary ammonium ion means that the negative surface charge is maintained even at alkaline pH. The modified colloids can be used to detect compounds which cannot be detected using conventional negatively-charged citrate or hydroxylamine reduced metal nanoparticles, for example the detection limit was 5.0 x 10(-5) M for perchlorate and

Current-driven magnetic rearrangements in spin-polarized point contacts

A method for investigating the dynamics of atomic magnetic moments in current-carrying magnetic point contacts under bias is presented. This combines the nonequilibrium Green's function (NEGF) method for evaluating the current and the charge density with a description of the dynamics of the magnetization in terms of quasistatic thermally activated transitions between stationary configurations. This method is then implemented in a tight-binding (TB) model with parameters chosen to simulate the main features of the electronic structures of magnetic transition metals. We investigate the domain wall (DW) migration in magnetic monoatomic chains sandwiched between magnetic leads, and for realistic parameters find that collinear arrangement of the magnetic moments of the chain is always favorable. Several stationary magnetic configurations are identified, corresponding to a different number of Bloch walls in the chain and to a different current. The relative stability of these configurations depends on the geometrical details of the junction and on the bias; however, we predict transitions between different configurations with activation barriers of the order of a few tens of meV. Since different magnetic configurations are associated with different resistances, this suggests an intrinsic random telegraph noise at microwave frequencies in the I-V curves of magnetic atomic point contacts at room temperature. Finally, we investigate whether or not current-induced torques are conservative.

Polarization Relaxation in an Ionic Liquid Confined between Electrified Walls

The response of a room temperature molten salt to an external electric field when it is confined to a nanoslit is studied by molecular dynamics simulations. The fluid is confined between two parallel and oppositely charged walls, emulating two electrified solid-liquid interfaces. Attention is focused on structural, electrostatic, and dynamical properties, which are compared with those of the nonpolarized fluid. It is found that the relaxation of the electrostatic potential, after switching the electric field off, occurs in two stages. A first, subpicosecond process accounts for 80% of the decay and is followed by a second subdiffusive process with a time constant of 8 ps. Diffusion is not involved in the relaxation, which is mostly driven by small anion translations. The relaxation of the polarization in the confined system is discussed in terms of the spectrum of charge density fluctuations in the bulk.

Characterisation of two calmodulin-like proteins from the liver fluke, Fasciola hepatica.

Calmodulin is a calcium ion-sensing signalling protein found in eukaryotics. Two calmodulin-like gene sequences were identified in an EST library from adult liver flukes. One codes for a protein (FhCaM1) homologous to mammalian calmodulins (98% identity), whereas the other protein (FhCaM2) has only 41% identity. These genes were cloned into expression vectors and the recombinant proteins were expressed in Escherichia coli. Gel shift assays showed that both proteins bind to calcium, magnesium and zinc ions. Homology models have been built for both proteins. As expected, FhCaM1 has a highly similar structure to other calmodulins. Although FhCaM2 has a similar fold, its surface charge is higher than FhCaM1. One of the potential metal ion-binding sites has lower metal-ion co-ordination capability, while another has an adjacent lysine residue, both of which may decrease the metal-binding affinity. These differences may reflect a specialised role for FhCaM2 in the liver fluke.

Thermodynamic Studies of Ionic Interactions in Aqueous Solutions of Imidazolium-Based Ionic Liquids [Emim][Br] and [Bmim][Cl]

Experimental measurements of density at different temperatures ranging from 293.15 to 313.15 K, the speed of sound and osmotic coefficients at 298.15 K for aqueous solution of 1-ethyl-3-methylimidazolium bromide ([Emim][Br]), and osmotic coefficients at 298.15 K for aqueous solutions of 1-butyl-3-methylimidazolium chloride ([Bmim][Cl]) in the dilute concentration region are taken. The data are used to obtain compressibilities, expansivity, apparent and limiting molar properties, internal pressure, activity, and activity coefficients for [Emim][Br] in aqueous solutions. Experimental activity coefficient data are compared with that obtained from Debye-Hückel and Pitzer models. The activity data are further used to obtain the hydration number and the osmotic second virial coefficients of ionic liquids. Partial molar entropies of [Bmim][Cl] are also obtained using the free-energy and enthalpy data. The distance of the closest approach of ions is estimated using the activity data for ILs in aqueous solutions and is compared with that of X-ray data analysis in the solid phase. The measured data show that the concentration dependence for aqueous solutions of [Emim][Br] can be accounted for in terms of the hydrophobic hydration of ions and that this IL exhibits Coulombic interactions as well as hydrophobic hydration for both the cations and anions. The small hydration numbers for the studied ILs indicate that the low charge density of cations and their hydrophobic nature is responsible for the formation of the water-structure-enforced ion pairs.