Capsule permeability via polymer and protein ingress/egress.

Static incubation tests, where microcapsules and beads are contacted with polymer and protein solutions, have been developed for the characterization of permselective materials applied for bioartificial organs and drug delivery. A combination of polymer ingress, detected by size-exclusion chromatography, and protein ingress/ egress, assessed by gel electrophoresis, provides information regarding the diffusion kinetics, molar mass cutoff(MMCO) and permeability. This represents an improvement over existing permeability measurements that are based on the diffusion of a single type of solute. Specifically, the permeability of capsules based on alginate, cellulose sulfate, polymethylene-co-guanidine were characterized as a function of membrane thickness. Solid alginate beads were also evaluated. The MMCO of these capsules was estimated to be between 80 and 90 kDa using polymers, and between 116-150 kDa with proteins. Apparently, the globular shape of the proteins (radius of gyration (Rg) of 4.2-4.6 nm) facilitates their passage through the membrane, comparatively to the polysaccharide coil conformation (Rg of 6.5-8.3 nm). An increase of the capsule membrane thickness reduced these values. The MMCO of the beads, which do not have a membrane limiting their permselective properties, was higher, between 110 and 200 kDa with dextrans, and between 150 and 220 kDa with proteins. Therefore, although the permeability estimated with biologically relevant molecules is generally higher due to their lower radius of gyration, both the MMCO of synthetic and natural watersoluble polymers correlate well, and can be used as in vitro metrics for the immune protection ability of microcapsules and microbeads. This article shows, to the authors' knowledge, the first reported concordance between permeability measures based on model natural and biological macromolecules.

Investigations of a thermosensitive gel to temporarily occlude crural arteries in femoro-distal bypass surgery.

OBJECTIVES: Long occlusions in calcified crural arteries are a major cause of endovascular technical failure in patients with critical limb ischaemia. Therefore, distal bypasses are mainly performed in patients with heavily calcified arteries and with consequently delicate clamping. A new reverse thermosensitive polymer (RTP) is an alternative option to occlude target vessels. The aim of the study is to report our technical experience with RTP and to assess its safety and efficiency to temporarily occlude small calcified arteries during anastomosis time. METHODS: Between July 2010 and December 2011, we used RTP to occlude crural arteries in 20 consecutive patients with 20 venous distal bypasses. We recorded several operative parameters, such as volume of injected RTP, duration of occlusion and anastomotic time. Quality of occlusion was subjectively evaluated. Routine on-table angiography was performed to search for plug emboli. Primary patency, limb salvage and survival rates were reported at 6 months. RESULTS: In all patients, crural artery occlusion was achieved with the RTP without the use of an adjunct occlusion device. Mean volume of RTP used was 0.3 ml proximally and 0.25 ml distally. Mean duration of occlusion was 14.4 ± 4.5 min, while completion of the distal anastomosis lasted 13.4 ± 4.3 min. Quality of occlusion was judged as excellent in eight cases and good in 12 cases. Residual plugs were observed in two patients and removed with an embolectomy catheter, before we amended the technique for dissolution of RTP. At 6 months, primary patency rate was 75% but limb salvage rate was 87.5%. The 30-day mortality rate was 10%. CONCLUSIONS: This study shows that RTP is safe when properly dissolved and effective to occlude small calcified arteries for completion of distal anastomosis.

Phase behavior and rheological analysis of reverse liquid crystals and W/I2, W/H2 gel emulsions using an amphiphilic block copolymer.

This article reports the phase behavior determi- nation of a system forming reverse liquid crystals and the formation of novel disperse systems in the two-phase region. The studied system is formed by water, cyclohexane, and Pluronic L-121, an amphiphilic block copolymer considered of special interest due to its aggregation and structural proper- ties. This system forms reverse cubic (I2) and reverse hexagonal (H2) phases at high polymer concentrations. These reverse phases are of particular interest since in the two-phase region, stable high internal phase reverse emulsions can be formed. The characterization of the I2 and H2 phases and of the derived gel emulsions was performed with small-angle X-ray scattering (SAXS) and rheometry, and the influence of temperature and water content was studied. TheH2 phase experimented a thermal transition to an I2 phase when temperature was increased, which presented an Fd3m structure. All samples showed a strong shear thinning behavior from low shear rates. The elasticmodulus (G0) in the I2 phase was around 1 order of magnitude higher than in theH2 phase. G0 was predominantly higher than the viscousmodulus (G00). In the gel emulsions,G0 was nearly frequency-independent, indicating their gel type nature. Contrarily to water-in-oil (W/O) normal emulsions, in W/I2 and W/H2 gel emulsions, G0, the complex viscosity (|η*|), and the yield stress (τ0) decreased with increasing water content, since the highly viscous microstructure of the con- tinuous phase was responsible for the high viscosity and elastic behavior of the emulsions, instead of the volumefraction of dispersed phase and droplet size. A rheological analysis, in which the cooperative flow theory, the soft glass rheology model, and the slip plane model were analyzed and compared, was performed to obtain one single model that could describe the non-Maxwellian behavior of both reverse phases and highly concentrated emulsions and to characterize their microstructure with the rheological properties.

Study of the diffusion in polymer solutions and hydrogels by NMR spectroscopy and NMR imaging

Afin d'étudier la diffusion et la libération de molécules de tailles inférieures dans un gel polymère, les coefficients d'auto-diffusion d'une série de polymères en étoile avec un noyau d'acide cholique et quatre branches de poly(éthylène glycol) (PEG) ont été déterminés par spectroscopie RMN à gradient de champ pulsé dans des solutions aqueuses et des gels de poly(alcool vinylique). Les coefficients de diffusion obtenus ont été comparés avec ceux des PEGs linéaires et dendritiques pour étudier l'effet de l'architecture des polymères. Les polymères en étoile amphiphiles ont des profils de diffusion en fonction de la concentration similaires à leurs homologues linéaires dans le régime dilué. Ils diffusent plus lentement dans le régime semi-dilué en raison de leur noyau hydrophobe. Leurs conformations en solution ont été étudiées par des mesures de temps de relaxation spin-réseau T1 du noyau et des branches. L'imagerie RMN a été utilisée pour étudier le gonflement des comprimés polymères et la diffusion dans la matrice polymère. Les comprimés étaient constitués d'amidon à haute teneur en amylose et chargés avec de l'acétaminophène (de 10 à 40% en poids). Le gonflement des comprimés, ainsi que l'absorption et la diffusion de l'eau, augmentent avec la teneur en médicament, tandis que le pourcentage de libération du médicament est similaire pour tous les comprimés. Le gonflement in vitro des comprimés d'un complexe polyélectrolyte à base d'amidon carboxyméthylé et de chitosane a également été étudié par imagerie RMN. Ces comprimés sont sensibles au pH : ils gonflent beaucoup plus dans les milieux acides que dans les milieux neutres en raison de la dissociation des deux composants et de la protonation des chaînes du chitosane. La comparaison des résultats avec ceux d'amidon à haute teneur en amylose indique que les deux matrices ont des gonflements et des profils de libération du médicament semblables dans les milieux neutres, alors que les comprimés complexes gonflent plus dans les milieux acides en raison de la dissociation du chitosane et de l'amidon.

Fluorescence characterization and gain studies on a dye-doped graded index polymer optical-fiber preform

Preparation of an appropriate optical-fiber preform is vital for the fabrication of graded-index polymer optical fibers (GIPOF), which are considered to be a good choice for providing inexpensive high bandwidth data links, for local area networks and telecommunication applications. Recent development of the interfacial gel polymerization technique has caused a dramatic reduction in the total attenuation in GIPOF, and this is one of the potential methods to prepare fiber preforms for the fabrication of dye-doped polymer-fiber amplifiers. In this paper, the preparation of a dye-doped graded-index poly(methyl methacrylate) (PMMA) rod by the interfacial gel polymerization method using a PMMA tube is reported. An organic compound of high-refractive index, viz., diphenyl phthalate (DPP), was used to obtain a graded-index distribution, and Rhodamine B (Rh B), was used to dope the PMMA rod. The refractive index profile of the rod was measured using an interferometric technique and the index exponent was estimated. The single pass gain of the rod was measured at a pump wavelength of 532 nm. The extent of doping of the Rh B in the preform was studied by axially exciting a thin slice of the rod with white light and measuring the spatial variation of the fluorescence intensity across the sample.

Polymer-Plastics Technology and Engineering

Fine (approximately 18 nm) particles of nickel ferrite were synthesized by the sol-gel technique, and their structural properties were evaluated by X-ray diffraction. Neoprene-based rubber ferrite composites were prepared by incorporating these nickel ferrite powders in the rubber matrix according to a specific recipe. The cure characteristics were analyzed, and the samples were molded into particular shapes whose properties were determined according to ASTM standards. Magnetization studies were carried out using a Vibrating Sample Magnetometer. This study indicates that neoprene rubber-based flexible magnets with desired magnetic properties and appropriate mechanical properties can be prepared by incorporating an adequate amount of nanoscale nickel ferrite particles within the rubber matrix

Development of selected electro-active polymer-ceramic nanocomposites as pyroelectric thermal/infrared detector materials

The present work emphasises on the synthesis and characterization of electro-active polymer-ceramic nanocomposites which can be used for pyroelectric thermal/infrared detection applications. Two sets of samples belong to polymer-microcrystalline composites have also been investigated in the work. The polymers used in the work have been commercially available ones, but the nanoceramics have been synthesized following simple chemical routes and aqueous organic gel routes. After characterizing the nanoceramics for their structure by powder XRD, they have been dispersed in liquid polymer and sonicated for uniform dispersion. The viscous mixture so formed was cast in the form of films for experimentation. Samples with volume fraction of the ceramic phase varied from 0 to 0.25 have been prepared. Solution growth was followed to prepare microcrystalline samples for the polymer-microcrystalline composites. The physical properties that determine the pyroelectric sensitivity of a material are dielectric constant, dielectric loss, pyroelectric coefficient, thermal conductivity and specific heat capacity. These parameters have been determined for all the samples and compositions reported in this work.The pyroelectric figures of merit for all the samples were determined. The pyroelectric figures of merit that determine the pyroelectric sensitivity of a material are current sensitivity, voltage responsivity and detectivity. All these have been determined for each set of samples and reported in the thesis. In order to assess the flexibility and mouldability of the composites we have measured the Shore hardness of each of the composites by indentation technique and compared with the pyroelectric figures of merit. Some important factors considered during the material fabrication stages were maximum flexibility and maximum figures of merit for pyroelectric thermal/IR detection applications. In order to achieve these goals, all the samples are synthesized as composites of polymers and nano/microcrystalline particles and are prepared in the form of freestanding films. The selected polymer matrices and particle inclusions possess good pyroelectric coefficients, low thermal and dielectric properties, so that good pyroelectric figures of merit could be achieved. The salient features of the work include the particle size of the selected ceramic materials. Since they are in nanometer size it was possible to achieve high flexibility and moldability with high figures of merit for even low volume fractions of inclusions of the prepared nanocrystalline composites. In the case of microcrystalline TGS and DTGS, their composites in PU matrix protect them from fragility and humidity susceptibility and made them for environmental friendly applications.

New studies on the versatile roles of Polyaniline and its composites in polymer based optoelectronic and energy storage devices

From the early stages of the twentieth century, polyaniline (PANI), a well-known and extensively studied conducting polymer has captured the attention of scientific community owing to its interesting electrical and optical properties. Starting from its structural properties, to the currently pursued optical, electrical and electrochemical properties, extensive investigations on pure PANI and its composites are still much relevant to explore its potentialities to the maximum extent. The synthesis of highly crystalline PANI films with ordered structure and high electrical conductivity has not been pursued in depth yet. Recently, nanostructured PANI and the nanocomposites of PANI have attracted a great deal of research attention owing to the possibilities of applications in optical switching devices, optoelectronics and energy storage devices. The work presented in the thesis is centered around the realization of highly conducting and structurally ordered PANI and its composites for applications mainly in the areas of nonlinear optics and electrochemical energy storage. Out of the vast variety of application fields of PANI, these two areas are specifically selected for the present studies, because of the following observations. The non-linear optical properties and the energy storing properties of PANI depend quite sensitively on the extent of conjugation of the polymer structure, the type and concentration of the dopants added and the type and size of the nano particles selected for making the nanocomposites. The first phase of the work is devoted to the synthesis of highly ordered and conducting films of PANI doped with various dopants and the structural, morphological and electrical characterization followed by the synthesis of metal nanoparticles incorporated PANI samples and the detailed optical characterization in the linear and nonlinear regimes. The second phase of the work comprises the investigations on the prospects of PANI in realizing polymer based rechargeable lithium ion cells with the inherent structural flexibility of polymer systems and environmental safety and stability. Secondary battery systems have become an inevitable part of daily life. They can be found in most of the portable electronic gadgets and recently they have started powering automobiles, although the power generated is low. The efficient storage of electrical energy generated from solar cells is achieved by using suitable secondary battery systems. The development of rechargeable battery systems having excellent charge storage capacity, cyclability, environmental friendliness and flexibility has yet to be realized in practice. Rechargeable Li-ion cells employing cathode active materials like LiCoO2, LiMn2O4, LiFePO4 have got remarkable charge storage capacity with least charge leakage when not in use. However, material toxicity, chance of cell explosion and lack of effective cell recycling mechanism pose significant risk factors which are to be addressed seriously. These cells also lack flexibility in their design due to the structural characteristics of the electrode materials. Global research is directed towards identifying new class of electrode materials with less risk factors and better structural stability and flexibility. Polymer based electrode materials with inherent flexibility, stability and eco-friendliness can be a suitable choice. One of the prime drawbacks of polymer based cathode materials is the low electronic conductivity. Hence the real task with this class of materials is to get better electronic conductivity with good electrical storage capability. Electronic conductivity can be enhanced by using proper dopants. In the designing of rechargeable Li-ion cells with polymer based cathode active materials, the key issue is to identify the optimum lithiation of the polymer cathode which can ensure the highest electronic conductivity and specific charge capacity possible The development of conducting polymer based rechargeable Li-ion cells with high specific capacity and excellent cycling characteristics is a highly competitive area among research and development groups, worldwide. Polymer based rechargeable batteries are specifically attractive due to the environmentally benign nature and the possible constructional flexibility they offer. Among polymers having electrical transport properties suitable for rechargeable battery applications, polyaniline is the most favoured one due to its tunable electrical conducting properties and the availability of cost effective precursor materials for its synthesis. The performance of a battery depends significantly on the characteristics of its integral parts, the cathode, anode and the electrolyte, which in turn depend on the materials used. Many research groups are involved in developing new electrode and electrolyte materials to enhance the overall performance efficiency of the battery. Currently explored electrolytes for Li ion battery applications are in liquid or gel form, which makes well-defined sealing essential. The use of solid electrolytes eliminates the need for containment of liquid electrolytes, which will certainly simplify the cell design and improve the safety and durability. The other advantages of polymer electrolytes include dimensional stability, safety and the ability to prevent lithium dendrite formation. One of the ultimate aims of the present work is to realize all solid state, flexible and environment friendly Li-ion cells with high specific capacity and excellent cycling stability. Part of the present work is hence focused on identifying good polymer based solid electrolytes essential for realizing all solid state polymer based Li ion cells.The present work is an attempt to study the versatile roles of polyaniline in two different fields of technological applications like nonlinear optics and energy storage. Conducting form of doped PANI films with good extent of crystallinity have been realized using a level surface assisted casting method in addition to the generally employed technique of spin coating. Metal nanoparticles embedded PANI offers a rich source for nonlinear optical studies and hence gold and silver nanoparticles have been used for making the nanocomposites in bulk and thin film forms. These PANI nanocomposites are found to exhibit quite dominant third order optical non-linearity. The highlight of these studies is the observation of the interesting phenomenon of the switching between saturable absorption (SA) and reverse saturable absorption (RSA) in the films of Ag/PANI and Au/PANI nanocomposites, which offers prospects of applications in optical switching. The investigations on the energy storage prospects of PANI were carried out on Li enriched PANI which was used as the cathode active material for assembling rechargeable Li-ion cells. For Li enrichment or Li doping of PANI, n-Butyllithium (n-BuLi) in hexanes was used. The Li doping as well as the Li-ion cell assembling were carried out in an argon filled glove box. Coin cells were assembled with Li doped PANI with different doping concentrations, as the cathode, LiPF6 as the electrolyte and Li metal as the anode. These coin cells are found to show reasonably good specific capacity around 22mAh/g and excellent cycling stability and coulombic efficiency around 99%. To improve the specific capacity, composites of Li doped PANI with inorganic cathode active materials like LiFePO4 and LiMn2O4 were synthesized and coin cells were assembled as mentioned earlier to assess the electrochemical capability. The cells assembled using the composite cathodes are found to show significant enhancement in specific capacity to around 40mAh/g. One of the other interesting observations is the complete blocking of the adverse effects of Jahn-Teller distortion, when the composite cathode, PANI-LiMn2O4 is used for assembling the Li-ion cells. This distortion is generally observed, near room temperature, when LiMn2O4 is used as the cathode, which significantly reduces the cycling stability of the cells.

Development of smart variable stiffness actuators using polymer hydrogels

In this work, compliant actuators are developed by coupling braided structures and polymer gels, able to produce work by controlled gel swelling in the presence of water. A number of aspects related to the engineering of gel actuators were studied, including gel selection, modelling and experimentation of constant force and constant displacement behaviour, and response time. The actuator was intended for use as vibration neutralizer: with this aim, generation of a force of 10 N in a time not exceeding a second was needed. Results were promising in terms of force generation, although response time was still longer than required. In addition, the easiest way to obtain the reversibility of the effect is still under discussion: possible routes for improvement are suggested and will be the object of future work.

Ring-chain interconversion in high-performance polymer systems. 3. Cyclodepolymerization of poly(m-phenylene isophthalamide) (Nomex) and entropically driven ring-opening polymerization of the macrocyclic oligomers so produced

A homologous series of macrocyclic oligoamides has been prepared in high yield by reaction of isophthaloyl chloride with m-phenylenediamine under pseudo-high-dilution conditions. The products were characterized by infrared and H-1 NMR spectroscopies, matrix assisted laser desorption-ionization time-of-flight mass spectrometry, and gel permeation chromatography (GPC). A series of linear oligomers was prepared for comparison. The macrocycles ranged in size from the cyclic trimer up to at least the cyclic nonamer (90 ring atoms). The same homologous series of macrocyclic oligomers was prepared in high yield by the cyclodepolymerization of poly(m-phenylene isophthalamide) (Nomex). Cyclodepolymerization was best achieved by treating a 1% w/v solution of the polymer in dimethyl sulfoxide containing calcium chloride or lithium chloride with 3-4 mol % of sodium hydride or the sodium salt of benzanilide at 150 degreesC for 70 h. Treatment of a concentrated solution of the macrocyclic oligomers (25% w/v) with 4 mol % of sodium hydride or the sodium salt of benzanilide in a solution of lithium chloride in dimethyl sulfoxide at 170 degreesC for 6 h resulted in efficient entropically driven ring-opening polymerizations to give poly(m-phenylene isophthalamide), characterized by infrared and H-1 NMR spectroscopies and by GPC. The molecular weights obtained were comparable with those of the commercial polymer.

Polymer conformation structure of wheat proteins and gluten subfractions revealed by ATR-FTIR

The polymer conformation structure of gluten extracted from a Polish wheat cultivar, Korweta, and gluten subtractions obtained from 2 U.K. breadmaking and biscuit flour cultivars, Hereward and Riband, was investigated using attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR). The results showed the conformation of proteins varied between flour, hydrated flour, and hydrated gluten. The beta-sheet structure increased progressively from flour to hydrated flour and to hydrated gluten. In hydrated gluten protein fractions comprising gliadin, soluble glutenin, and gel protein, beta-sheet structure increased progressively from soluble gliadin and glutenin to gluten and gel protein; beta-sheet content was also greater in the gel protein from the breadmaking flour Hereward than the biscuit flour Riband.

NMR and conductivity study of gelatin-based polymer electrolytes

Nuclear Magnetic Resonance spectroscopy (NMR) and complex impedance spectroscopy have been used to study gelatin-based polymer electrolytes plasticized with glycerol and containing lithium perchlorate. The studied samples were prepared with salt concentration of 7.9 wt% and 10.3 wt%. Ionic conductivity of about 10(-5) S/cm was obtained at room temperature for both samples. Lithium (Li-7) and proton (H-1) lineshapes and spin-lattice relaxation times were measured as a function of temperature. The Li-7 NMR relaxation results indicate that the ionic mobility in this system is comparable to those found in other plasticized polymer electrolytes.

Amylopectin-rich starch plasticized with glycerol for polymer electrolyte application

This paper describes the preparation and characterization of a solid polymer electrolyte based on amylopectin-rich starch plasticized with glycerol. The samples were characterized through ionic conductivity (sigma) measurements, scanning electron microscopy, thermal analysis, and spectroscopy in the UV-Vis-NIR region. The results showed that the highest sigma (1.1 x 10(-4) Scm(-1) at 30 degrees C) was obtained for the sample with n = [O]/[Li] = 6.5 ratio. In addition, the samples plasticized with 30-35 wt.% of glycerol presented high ionic conductivity, transparency and conduction stability. The ionic conductivity measurements as a function of lithium salt contents showed a maximum for n=6.5. The ionic conductivity as a function of time for amylopectin-rich starch plasticized with 30 wt.% of glycerol and containing [O]/[Li] = 10 showed conduction stability over 6 months (sigma similar to 3.01 x 10(-5) S cm(-1)). (C) 2010 Elsevier B.V. All rights reserved.

Agar-based films for application as polymer electrolytes

New types of polymer electrolytes based on agar have been prepared and characterized by impedance spectroscopy, X-ray diffraction measurements, UV-vis spectroscopy and scanning electronic microscopy (SEMI). The best ionic conductivity has been obtained for the samples containing a concentration of 50 wt.% of acetic acid. As a function of the temperature the ionic conductivity exhibits an Arrhenius behavior increasing from 1.1 x 10(-4) S/cm at room temperature to 9.6 x 10(-4) S/cm at 80 degrees C. All the samples showed more than 70% of transparency in the visible region of the electromagnetic spectrum, a very homogeneous surface and a predominantly amorphous structure. All these characteristics imply that these polymer electrolytes can be applied in electrochromic devices. (C) 2009 Elsevier Ltd. All rights reserved.

Optimization of performances of gelatin/LiBF(4)-based polymer electrolytes by plasticizing effects

Gelatin is a cheap and abundant natural product with very good biodegradation properties and can be used to obtain acetic acid or LiClO(4)-based gel polymer electrolytes (GPEs) with high ionic conductivity and good stability. This article presents results of GPEs obtained by the plasticization of gelatin and addition of LiBF(4), where the optimization of the system was achieved by using a factorial design type 22 with two variables: glycerol and LiBF(4). From this analysis it was stated that the effect of glycerol as a plasticizer on the ionic conductivity results is much more important than the effect obtained by varying the lithium salt content or the effect of the interaction of both variables. Also all the samples were characterized by X-ray diffraction measurements, UV-vis-NIR spectroscopy and scanning electron microscopy (SEM) and impedance spectroscopy. The ionic conductivity results of all analyzed samples as a function of temperature obey predominantly an Arrhenius relationship and the samples are stable up to 160 degrees C. Good conductivity results combined with transparency and good adhesion to the electrodes have shown that gelatin-based GPEs are very promising materials to be used as solid electrolytes in electrochromic devices. (C) 2009 Elsevier Ltd. All rights reserved.