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.

The removal of dyes from textile wastewater: a study of the physical characteristics and adsorption mechanisms of diatomaceous earth

The feasibility of using diatomite for the removal of the problematic reactive dyes as well as basic dyes from textile wastewater was investigated. Methylene blue, Cibacron reactive black and reactive yellow dyes were considered. Physical characteristics of diatomite such as pH(solution), pH(ZPC), surface area, Fourier transform infrared, and scanning electron microscopy were investigated. The surface area of diatomite was found to be 27.80 m(2) g(-1) and the pH(ZPC) occurred around pH of 5.4. The results indicated that the surface charge of diatomite decreased as the pH of the solution increased with the maximum methylene blue removal from aqueous solution occurring at basic pH of around (1011). Adsorption isotherms of diatomite with methylene blue, hydrolysed reactive black and yellow dyes were constructed at different pH values, initial dye concentrations and particle sizes. The experimental results were fitted to the Langmuir, Freundlich, and Henry models. The study indicated that electrostatic interactions play an important role in the adsorption of dyes onto diatomite. A model of the adsorption mechanism of methylene blue onto diatomite is proposed. (C) 2003 Elsevier Ltd. All rights reserved.

Characterisation of fluidised bed granulation processes using in situ Raman spectroscopy

Previous work by the authors Walker et al. [2007b. Fluidised bed characterisation using Raman spectroscopy: applications to pharmaceutical processing. Chemical Engineering Science 62, 3832–3838] illustrated that Raman spectroscopy could be used to provide 3-D maps of the concentration and chemical structure of particles in motion in a fluidised bed, within a relatively short (120 s) time window. Moreover, we reported that the technique, as outlined, has the potential to give detailed in-situ information on how the structure and composition of granules/powders within the fluidised bed (dryer or granulator) vary with the position and evolve with time. In this study we extended the original work by shortening the time window of the Raman spectroscopic analysis to 10 s, which has allowed the in-situ real-time characterisation of a fluidised bed granulation process. Here we show an important new use of the technique which allows in-situ measurement of the composition of the material within the fluidised bed in three spatial dimensions and as a function of time. This is achieved by recording Raman spectra using a probe positioned within the fluidised bed on a long-travel x–y–z stage. In these experiments the absolute Raman intensity is used to provide a direct measure of the amount of any given material in the probed volume, i.e. a particle density. Particle density profiles have been calculated over the granulation time and show how the volume of the fluidised bed decreases with an increase mean granule size. The Raman spectroscopy analysis indicated that nucleation/coalescence in this co-melt fluidised hot melt granulation system occurred over a relatively short time frame (t<30 s). The Raman spectroscopic technique demonstrated accurate correlation with independent granulation experiments which provided particle size distribution analysis. The similarity of the data indicates that the Raman spectra accurately represent solids ratios within the bed, and thus the techniques quantitative capabilities for future use in the pharmaceutical industry.

SERS enhancement by aggregated Au colloids: effect of particle size

Aggregated Au colloids have been widely used as SERS enhancing media for many years but to date there has been no systematic investigation of the effect of the particle size on the enhancements given by simple aggregated Au colloid solutions. Previous systematic studies on isolated particles in solution or multiple particles deposited onto surfaces reported widely different optimum particle sizes for the same excitation wavelength and also disagreed on the extent to which surface plasmon absorption spectra were a good predictor of enhancement factors. In this work the spectroscopic properties of a range of samples of monodisperse Au colloids with diameters ranging from 21 to 146 nm have been investigated in solution. The UV/visible absorption spectra of the colloids show complex changes as a function of aggregating salt (MgSO4) concentration which diminish when the colloid is fully aggregated. Under these conditions, the relative SERS enhancements provided by the variously sized colloids vary very significantly across the size range. The largest signals in the raw data are observed for 46 nm colloids but correction for the total surface area available to generate enhancement shows that particles with 74 nm diameter give the largest enhancement per unit surface area. The observed enhancements do not correlate with absorbance at the excitation wavelength but the large differences between differently sized colloids demonstrate that even in the randomly aggregated particle assemblies studied here, inhomogeneous broadening does not mask the underlying changes due to differences in particle diameter.

LDL particle size in habitual exercisers, lean sedentary men and abdominally obese sedentary men

Habitual exercisers enjoy considerable protection from coronary heart disease (CHD). Often, however, only modest differences in traditional CHD risk factors are apparent between habitual exercisers and their sedentary counterparts. For this reason, there is increasing interest in novel predictors of CHD, such as a preponderance of small, dense low-density lipoprotein (LDL) particles. Polyacrylamide gel electrophoresis was used to separate lipoprotein subfractions in 32 lean exercisers, 36 lean sedentary men and 21 obese sedentary men aged 30-45 years. Well-validated equations were used to determine LDL concentration and peak particle diameter. Waist girth was used to identify lean (<100 cm) and obese ( >= 100cm) individuals. LDL concentration was lower in lean exercisers than in lean sedentary men (2.64 +/- 0.44 vs. 3.76 +/- 0.79 mmol.l(-1), p <0.001), suggesting that habitual exercise influences this risk factor. In contrast, there were no significant differences in LDL peak particle diameter between lean exercisers, lean sedentary men and obese sedentary men (27.92 +/- 0.67, 28.09 +/- 0.62 and 27.77 +/- 0.77 nm, respectively). In multiple linear regression analysis, triglyceride concentration was the only significant predictor of LDL PPD. These data suggest that habitual exercise influences LDL concentration but does not influence LDL particle size in men aged 30-45 years.

Design, optimisation and characterisation of polymeric microneedle arrays prepared by a novel laser-based micromoulding technique.

PURPOSE:
Design and evaluation of a novel laser-based method for micromoulding of microneedle arrays from polymeric materials under ambient conditions. The aim of this study was to optimise polymeric composition and assess the performance of microneedle devices that possess different geometries.
METHODS:
A range of microneedle geometries was engineered into silicone micromoulds, and their physicochemical features were subsequently characterised.
RESULTS:
Microneedles micromoulded from 20% w/w aqueous blends of the mucoadhesive copolymer Gantrez® AN-139 were surprisingly found to possess superior physical strength than those produced from commonly used pharma polymers. Gantrez® AN-139 microneedles, 600 µm and 900 µm in height, penetrated neonatal porcine skin with low application forces (>0.03 N per microneedle). When theophylline was loaded into 600 µm microneedles, 83% of the incorporated drug was delivered across neonatal porcine skin over 24 h. Optical coherence tomography (OCT) showed that drug-free 600 µm Gantrez® AN-139 microneedles punctured the stratum corneum barrier of human skin in vivo and extended approximately 460 µm into the skin. However, the entirety of the microneedle lengths was not inserted.
CONCLUSION:
In this study, we have shown that a novel laser engineering method can be used in micromoulding of polymeric microneedle arrays. We are currently carrying out an extensive OCT-informed study investigating the influence of microneedle array geometry on skin penetration depth, with a view to enhanced transdermal drug delivery from optimised laser-engineered Gantrez® AN-139 microneedles.

Nonlinear theory of solitary waves associated with longitudinal particle motion in lattices - Application to longitudinal grain oscillations in a dust crystal

The nonlinear aspects of longitudinal motion of interacting point masses in a lattice are revisited, with emphasis on the paradigm of charged dust grains in a dusty plasma (DP) crystal. Different types of localized excitations, predicted by nonlinear wave theories, are reviewed and conditions for their occurrence (and characteristics) in DP crystals are discussed. Making use of a general formulation, allowing for an arbitrary (e.g. the Debye electrostatic or else) analytic potential form phi(r) and arbitrarily long site-to-site range of interactions, it is shown that dust-crystals support nonlinear kink-shaped localized excitations propagating at velocities above the characteristic DP lattice sound speed v(0). Both compressive and rarefactive kink-type excitations are predicted, depending on the physical parameter values, which represent pulse- (shock-)like coherent structures for the dust grain relative displacement. Furthermore, the existence of breather-type localized oscillations, envelope-modulated wavepackets and shocks is established. The relation to previous results on atomic chains as well as to experimental results on strongly-coupled dust layers in gas discharge plasmas is discussed.

Physicochemical characterisation and drug release properties of celecoxib hot melt extruded glass solutions

Formulation of Celecoxib into solid dosage forms is difficult due to the physical properties of the drug powder. However for the first time, this paper reports on the drug delivery characteristics glass solutions of celecoxib and polyvinylpyrrolidone prepared by hot melt extrusion, together with use of supercritical carbon dioxide to achieve a porous structure, in order to achieve a stable and enhanced drug release.

Berry phase for a spin 1/2 particle in a classical fluctuating field

The effect of fluctuations in the classical control parameters on the Berry phase of a spin 1/2 interacting with an adiabatically cyclically varying magnetic field is analyzed. It is explicitly shown that in the adiabatic limit dephasing is due to fluctuations of the dynamical phase.

Preparation and characterisation of cellulose nanofibres

Two different procedures were compared for the preparation of cellulose nanofibres from flax and microcrystalline cellulose (MCC). The first involved a combination of high energy ball milling, acid hydrolysis and ultrasound, whilst the second employed a high pressure homogenisation technique, with and without various pre-treatments of the fibrous feedstock. The geometry and microstructure of the cellulose nanofibres were observed by SEM and TEM and their particle size measured using image analysis and dynamic light scattering. Aspect ratios of nanofibres made by microfluidisation were orders of magnitude greater than those achieved by acid hydrolysis. FTIR, XRD and TGA were used to characterise changes to chemical functionality, cellulose crystallinity and thermal stability resulting from the approaches used for preparing the cellulose nanofibres. Hydrolysis using sulphuric acid gave rise to esterification of the cellulose nanofibres, a decrease in crystallinity with MCC, but an increase with flax, together with an overall reduction in thermal stability. Increased shear history of flax subjected to multiple passes through the microfluidiser, raised both cellulose nanofibril crystallinity and thermal stability, the latter being strongly influenced by acid, alkaline and, most markedly, silane pretreatment.

Examination of the physical state of chlorhexidine within viscoelastic, bioadhesive semisolids using Raman spectroscopy

This study examined the effects of polymeric components on the physical state of chlorhexidine within bioadhesive, semisolid formulations using Raman spectroscopy. Semisolid formulations were prepared in which chlorhexidine base (CHX, 5%w/w, particle size

Characterisation of the photocatalyst Pilkington Activ (TM): a reference film photocatalyst?

Pilkington Glass Activ(TM) represents a possible suitable successor to P25 TiO2, especially as a benchmark photocatalyst film for comparing other photocatalyst or PSH self-cleaning films. Activ(TM) is a glass product with a clear, colourless, effectively invisible, photocatalytic coating of titania that also exhibits PSH. Although not as active as a film of P25 TiO2, Activ(TM) vastly superior mechanical stability, very reproducible activity and widespread commercial availability makes it highly attractive as a reference photocatalytic film. The photocatalytic and photo-induced superhydrophilitic (PSH) properties of Activ(TM) are studied in some detail and the results reported. Thus, the kinetics of stearic acid destruction (a 104 electron process) are zero order over the stearic acid range 4-129 monolayers and exhibit formal quantum efficiencies (FQE) of 0.7 X 10(-5) and 10.2 x 10(-5) molecules per photon when irradiated with light of 365 +/- 20 and 254 nm, respectively; the latter appears also to be the quantum yield for Activ(TM) at 254 nm. The kinetics of stearic acid destruction exhibit Langmuir-Hinshelwood-like saturation type kinetics as a function of oxygen partial pressure, with no destruction occurring in the absence of oxygen and the rate of destruction appearing the same in air and oxygen atmospheres. Further kinetic work revealed a Langmuir adsorption type constant for oxygen of 0.45 +/- 0.16 kPa(-1) and an activation energy of 19 +/- 1 Kj mol(-1). A study of the PSH properties of Activ(TM) reveals a high water contact angle (67) before ultra-bandgap irradiation reduced to 0degrees after prolonged irradiation. The kinetics of PSH are similar to those reported by others for sol-gel films using a low level of UV light. The kinetics of contact angle recovery in the dark appear monophasic and different to the biphasic kinetics reported recently by others for sol-gel films [J. Phys. Chem. B 107 (2003) 1028]. Overall, Activ(TM) appears a very suitable reference material for semiconductor film photocatalysis. (C) 2003 Elsevier Science B.V All rights reserved.

Preparation and characterisation of novel thick sol-gel titania film photocatalysts

The preparation and characterization of thick (9 mum), clear, mechanically robust and photocatalytically active films of nanocrystalline anatase titania are described. XRD and SEM analysis show the films comprise 13 nm particles of anatase TiO2. Thin (54 nm) films of the 'paste' TiO2, along with sol-gel titania films made by a more traditional route are also prepared and characterised. All titania films mediate the photocatalytic destruction of stearic acid with a quantum yield of 0.0016 +/- 0.0003. using either 365 nm (i.e. BLB) or 254 nm (germicidal) light. P25 TiO2 films also appear to mediate the same process with a similar formal quantum efficiency. Of all the films tested, the thick paste TiO2 films are the most ideally suited for use with near UV light, for reasons which are discussed. All the titania films tested exhibit photoinduced superhydrophilicity.