Using an additive to control the electrospinning of fibres of poly(epsilon-caprolactone)

Electrospinning is a route to polymer fibres with diameters considerably smaller than available from most fibre-producing techniques. We explore the use of a low molecular weight compound as an effective control additive during the electrospinning of poly(epsilon-caprolactone). This approach extends the control variables for the electrospinning of nanoscale fibres from the more usual ones such as the polymer molecular weight, solvent and concentration. We show that through the use of dual solvent systems, we can alter the impact of the additive on the electrospinning process so that finer as well as thicker fibres can be prepared under otherwise identical conditions. As well as the size of the fibres and the number of beads, the use of the additive allows us to alter the level of crystallinity as well as the level of preferred orientation of the poly(epsilon-caprolactone) crystals. This approach, involving the use of a dual solvent and a low molar mass compound, offers considerable potential for application to other polymer systems. (C) 2010 Society of Chemical Industry

Nonspherical assemblies generated from polystyrene-b-poly(L-lysine) polyelectrolyte block copolymers

This report describes the aqueous solution self-assembly of a series of polystyrene(m)-b-poly(L-lysine)n block copolymers (m = 8-10; n = 10-70). The polymers are prepared by ring-opening polymerization of epsilon-benzyloxycarbonyl-L-lysine N-carboxyanhydride using amine terminated polystyrene macroinitiators, followed by removal of the benzyloxycarbonyl side chain protecting groups. The critical micelle concentration of the block copolymers determined using the pyrene probe technique shows a parabolic dependence on peptide block length exhibiting a maximum at n = approximately 20 (m = 8) or n = approximately 60 (m = 10). The shape and size of the aggregates has been studied by dynamic and static light scattering, small-angle neutron scattering (SANS), and analytical ultracentrifugation (AUC). Surprisingly, Holtzer and Kratky analysis of the static light scattering results indicates the presence of nonspherical, presumably cylindrical objects independent of the poly(L-lysine)n block length. This is supported by SANS data, which can be fitted well by assuming cylindrical scattering objects. AUC analysis allows the molecular weight of the aggregates to be estimated as several million g/mol, corresponding to aggregation numbers of several 10s to 100s. These aggregation numbers agree with those that can be estimated from the length and diameter of the cylinders obtained from the scattering results.

Highly asymmetric phase diagram of a poly(1,2-octylene oxide)-poly(ethylene oxide) diblock copolymer system comprising a brush-like poly(1,2-octylene oxide) block

The phase diagram of a series of poly(1,2-octylene oxide)-poly(ethylene oxide) (POO-PEO) diblock copolymers is determined by small-angle X-ray scattering. The Flory-Huggins interaction parameter was measured by small-angle neutron scattering. The phase diagram is highly asymmetric due to large conformational asymmetry that results from the hexyl side chains in the POO block. Non-lamellar phases (hexagonal and gyroid) are observed near f(PEO) = 0.5, and the lamellar phase is observed for f(PEO) >= 0.5.

Mechanisms of femtosecond laser-induced refractive index modification of poly(methyl methacrylate)

The mechanisms of refractive index change in poly(methyl methacrylate) by frequency doubled femtosecond laser pulses are investigated. It is demonstrated that positive refractive index modificaton can be caused by a combination of depolymerization and crosslinking.

Liquid flow over a substrate structured by seeded nanoparticles

Recent experiments have demonstrated that nanoparticles which sparsely distributed over a solid substrate can substantially change the flow conditions at the solid surface in the presence of slip. Inspired by these observations, the flow past tiny particles seeded on a solid substrate is investigated theoretically in the framework of an interface formation model. It has been shown, that even a single seeded nanoparticle can reduce significantly the measurable tangential component of hydrodynamic velocity at the substrate and affect the amount of the observed apparent slippage of the liquid. The effect from the particle manifests in a form of a long relaxation tail defined by the characteristic time of the interface formation process. A comparison with experiments has demonstrated a good agreement between theoretically predicted and experimentally observed values of the relaxation tail length scale.

Molecular dynamics simulation of interactions between a sodium dodecyl sulfate micelle and a poly(ethylene oxide) polymer

We have performed atomistic molecular dynamics simulations of an anionic sodium dodecyl sulfate (SDS) micelle and a nonionic poly(ethylene oxide) (PEO) polymer in aqueous solution. The micelle consisted of 60 surfactant molecules, and the polymer chain lengths varied from 20 to 40 monomers. The force field parameters for PEO were adjusted by using 1,2-dimethoxymethane (DME) as a model compound and matching its hydration enthalpy and conformational behavior to experiment. Excellent agreement with previous experimental and simulation work was obtained through these modifications. The simulated scaling behavior of the PEO radius of gyration was also in close agreement with experimental results. The SDS-PEO simulations show that the polymer resides on the micelle surface and at the hydrocarbon-water interface, leading to a selective reduction in the hydrophobic contribution to the solvent-accessible surface area of the micelle. The association is mainly driven by hydrophobic interactions between the polymer and surfactant tails, while the interaction between the polymer and sulfate headgroups on the micelle surface is weak. The 40-monomer chain is mostly wrapped around the micelle, and nearly 90% of the monomers are adsorbed at low PEO concentration. Simulations were also performed with multiple 20-monomer chains, and gradual addition of polymer indicates that about 120 monomers are required to saturate the micelle surface. The stoichiometry of the resulting complex is in close agreement with experimental results, and the commonly accepted "beaded necklace" structure of the SDS-PEO complex is recovered by our simulations.

Carnauba wax nanoparticles enhance strong systemic and mucosal cellular and humoral immune responses to HIV-gp140 antigen

Induction of humoral responses to HIV at mucosal compartments without inflammation is important for vaccine design. We developed charged wax nanoparticles that efficiently adsorb protein antigens and are internalized by DC in the absence of inflammation. HIV-gp140-adsorbed nanoparticles induced stronger in vitro T-cell proliferation responses than antigen alone. Such responses were greatly enhanced when antigen was co-adsorbed with TLR ligands. Immunogenicity studies in mice showed that intradermal vaccination with HIV-gp140 antigen-adsorbed nanoparticles induced high levels of specific IgG. Importantly, intranasal immunization with HIV-gp140-adsorbed nanoparticles greatly enhanced serum and vaginal IgG and IgA responses. Our results show that HIV-gp140-carrying wax nanoparticles can induce strong cellular/humoral immune responses without inflammation and may be of potential use as effective mucosal adjuvants for HIV vaccine candidates.

Double-gyroid morphology of a polystyrene-block-poly(ferrocenylethylmethylsilane) diblock copolymer: a route to ordered bicontinuous nanoscale architectures

A polystyrene-block-poly(ferrocenylethylmethylsilane) diblock copolymer, displaying a double-gyroid morphology when self-assembled in the solid state, has been prepared with a PFEMS volume fraction phi(PFMS)=0.39 and a total molecular weight of 64 000 Da by sequential living anionic polymerisation. A block copolymer with a metal-containing block with iron and silicon in the main chain was selected due to its plasma etch resistance compared to the organic block. Self-assembly of the diblock copolymer in the bulk showed a stable, double-gyroid morphology as characterised by TEM. SAXS confirmed that the structure belonged to the Ia3d space group.

Application of interpolymer complexation to coat solid and soft surfaces

Water-soluble polymers are often capable of forming interpolymer complexes in solutions and at interfaces, which offers an excellent opportunity for surface modification. The complex formation may be driven by H-bonding between poly(carboxylic acids) and non-ionic polymers or by electrostatic attraction between oppositely-charged polyelectrolytes. In the present communication the following applications of interpolymer complexation in coating technologies will be considered: (1) Complexation between poly(acrylic acid) and non-ionic polymers via H-bonding was used to coat glass surfaces. It was realised using layer-by-layer deposition of IPC on glass surfaces with subsequent cross-linking of dry multilayers by thermal treatment. Depending on the glass surface functionality this complexation resulted in detachable and non-detachable hydrogel films; (2) Electrostatic layer-by-layer self-assembly between glycol chitosan and bovine serum albumin (BSA) was used to coat magnetic nanoparticles. It was demonstrated that the native structure of BSA remains unaffected by the self-assembling process.

Thiolated mucoadhesive and PEGylated nonmucoadhesive organosilica nanoparticles from 3-Mercaptopropyltrimethoxysilane

A novel approach has been developed to synthesize thiolated sub-100 nm organosilica nanoparticles from 3-mercaptopropyltrimethoxysilane (MPTS) through its self-condensation in dimethylsulfoxide in contact with atmospheric oxygen. The formation of MPTS nanoparticles proceeds through the condensation of methoxysilane groups and simultaneous disulfide bridging caused by partial oxidation of thiol groups. These nanoparticles showed excellent colloidal stability in dilute aqueous dispersions but underwent further self-assembly into chains and necklaces at higher concentrations. They exhibited very good ability to adhere to ocular mucosal surfaces, which can find applications in drug delivery. The thiolated nanoparticles could also be easily modified through PEGylation resulting in a loss of their mucoadhesive properties.

Remarkable dynamics of nanoparticles in the urban atmosphere

Nanoparticles emitted from road traffic are the largest source of respiratory exposure for the general public living in urban areas. It has been suggested that the adverse health effects of airborne particles may scale with the airborne particle number, which if correct, focuses attention on the nanoparticle (less than 100 nm) size range which dominates the number count in urban areas. Urban measurements of particle size distributions have tended to show a broadly similar pattern dominated by a mode centred on 20–30 nm diameter particles emitted by diesel engine exhaust. In this paper we report the results of measurements of particle number concentration and size distribution made in a major London park as well as on the BT Tower, 160 m high. These measurements taken during the REPARTEE project (Regents Park and BT Tower experiment) show a remarkable shift in particle size distributions with major losses of the smallest particle class as particles are advected away from the traffic source. In the Park, the traffic related mode at 20–30 nm diameter is much reduced with a new mode at <10 nm. Size distribution measurements also revealed higher number concentrations of sub-50 nm particles at the BT Tower during days affected by higher turbulence as determined by Doppler Lidar measurements and indicate a loss of nanoparticles from air aged during less turbulent conditions. These results suggest that nanoparticles are lost by evaporation, rather than coagulation processes. The results have major implications for understanding the impacts of traffic-generated particulate matter on human health.

Crystallization and stereocomplexation behavior of poly(D- and L-lactide)-b-poly(N,N-dimethylamino-2-ethyl methacrylate) block copolymers

The thermal properties, crystallization, and morphology of amphiphilic poly(D-lactide)-b-poly(N,N-dimethylamino- 2-ethyl methacrylate) (PDLA-b-PDMAEMA) and poly (L-lactide)-b-poly(N,N-dimethylamino-2-ethyl methacrylate) (PLLA-b-PDMAEMA) copolymers were studied and compared to those of the corresponding poly(lactide) homopolymers. Additionally, stereocomplexation of these copolymers was studied. The crystallization kinetics of the PLA blocks was retarded by the presence of the PDMAEMA block. The studied copolymers were found to be miscible in the melt and the glassy state. The Avrami theory was able to predict the entire crystallization range of the PLA isothermal overall crystallization. The melting points of PLDA/PLLA and PLA/PLA-b-PDMAEMA stereocomplexes were higher than those formed by copolymer mixtures. This indicates that the PDMAEMA block is influencing the stability of the stereocomplex structures. For the low molecular weight samples, the stereocomplexes particles exhibited a conventional disk-shape structure and, for high molecular weight samples, the particles displayed unusual star-like shape morphology.

Effect of water-soluble polymers, polyethylene glycol and poly(vinylpyrrolidone),on the gelation of aqueous micellar solutions of Pluronic copolymer F127

The micellization of F127 (E98P67E98) in dilute aqueous solutions of polyethylene glycol (PEG6000 and PEG35000) and poly(vinylpyrrolidone) (PVP K30 and PVP K90) is studied. The average hydrodynamic radius (rh,app) obtained from the dynamic light scattering technique increased with increase in PEG concentration but decreased on addition of PVP, results which are consistent with interaction of the micelles with PEG and the formation of micelles clusters, but no such interaction occurs with PVP. Tube inversion was used to determine the onset of gelation. The critical concentration of F127 for gelation increased on addition of PEG and of PVP K30 but decreased on addition of PVP K90. Small-angle X-ray scattering (SAXS) was used to show that the 30 wt% F127 gel structure (fcc) was independent of polymer type and concentration, as was the d-spacing and so the micelle hard-sphere radius. The maximum elastic modulus (G0 max) of 30 wt% F127 decreased from its value for water alone as PEG was added, but was little changed by adding PVP. These results are consistent with the packed-micelles in the 30 wt% F127 gel being effectively isolated from the polymer solution on the microscale while, especially for the PEG, being mixed on the macroscale.

Rheological and thermal behaviour of poly(N-isopropylacrylamide)/alginate smart polymeric networks

Interpenetrating polymeric networks based on sodium alginate and poly(N-isopropylacrylamide) (PNIPAAm) covalently crosslinked with N,N′-methylenebisacrylamide have been investigated using rheology, thermogravimetry, differential scanning calorimetry, X-ray diffraction measurements and scanning electron microscopy (SEM). An improved elastic response of the samples with a higher PNIPAAm content and increased amount of crosslinking agent was found. The temperature-responsive behaviour of the hydrogel samples was evidenced by viscoelastic measurements performed at various temperatures. It is shown that the properties of these gels can be tuned according to composition, amount of crosslinking agent and temperature changes. X-ray scattering analysis revealed that the hydrophobic groups are locally segregated even in the swollen state whilst cryo-SEM showed the highly heterogeneous nature of the gels.

Development of orientation during electrospinning of fibres of poly(ε-caprolactone)

We explore the influence of a rotating collector on the internal structure of poly(ε-caprolactone) fibres electrospun from a solution in dichloroethane. We find that above a threshold collector speed, the mean fibre diameter reduces as the speed increases and the fibres are further extended. Small-angle and wide-angle X-ray scattering techniques show a preferred orientation of the lamellar crystals normal to the fibre axis which increases with collector speed to a maximum and then reduces. We have separated out the processes of fibre alignment on the collector and the orientation of crystals within the fibres. There are several stages to this behaviour which correspond to the situations (a) where the collector speed is slower than the fibre spinning rate, (b) the fibre is mechanically extended by the rotating collector and (c) where the deformation leads to fibre fracture. The mechanical deformation leads to a development of preferred orientation with extension which is similar to the prediction of the pseudo-affine deformation model and suggests that the deformation takes place during the spinning process after the crystals have formed.