Yes / A transflectance near infra red (NIR) spectroscopy approach has been used to simultaneously measure drug and plasticiser content of polymer melts with varying opacity during hot melt extrusion. A high temperature reflectance NIR probe was mounted in the extruder die directly opposed to a highly reflective surface. Carbamazepine (CBZ) was used as a model drug, with polyvinyl pyrollidone-vinyl acetate co-polymer (PVP-VA) as a matrix and polyethylene glycol (PEG) as a plasticiser. The opacity of the molten extrudate varied from transparent at low CBZ loading to opaque at high CBZ loading. Particulate amorphous API and voids formed around these particles were found to cause the opacity. The extrusion process was monitored in real time using transflectance NIR; calibration and validation runs were performed using a wide range of drug and plasticiser loadings. Once calibrated, the technique was used to simultaneously track drug and plasticiser content during applied step changes in feedstock material. Rheological and thermal characterisations were used to help understand the morphology of extruded material. The study has shown that it is possible to use a single NIR spectroscopy technique to monitor opaque and transparent melts during HME, and to simultaneously monitor two distinct components within a formulation.

Yes / In this paper we study the effectiveness of three well known polymers: inulin, Soluplus and PVP in stabilizing amorphous form of nimesulide (NMS) drug. The re-crystallization tendency of pure drug as well as measured drug-polymer systems were examined at isothermal conditions by using broadband dielectric spectroscopy (BDS), and at non-isothermal conditions by differential scanning calorimetry (DSC). Our investigation has shown that the crystallization half-life time of pure NMS at 328 K is equal to 33 minutes. We found that this time can be prolonged to 40 years after adding to NMS 20% of PVP polymer. This polymer proved to be the best NMS’s stabilizer, while the worst stabilization effect was found after adding the inulin to NMS. Additionally, our DSC, BDS and FTIR studies indicate that for suppression of NMS’s re-crystallization in NMS-PVP system, the two mechanisms are responsible: the polymeric steric hindrances as well as the antiplastization effect excerted by the excipient. / The authors J.K., Z.W., K.G. and M.P., are grateful for the financial support received within the Project No. 2015/16/W/NZ7/00404 (SYMFONIA 3) from the National Science Centre, Poland. H.M. and L.T. are supported by Science Foundation Ireland under grant No. 12/RC/2275 (Synthesis and Solid State Pharmaceuticals Centre).

Les nanoparticules métalliques (MNPs) ont un grand succès dans les dernières décennies dû à la variété d'applications dans différents domaines (microélectronique, matériaux, catalyse). Mis à part les solvants organiques, les liquides ioniques, l'eau, le CO2 supercritique et les polyols, en particulier le glycérol, ont démontré leur capacité à stabiliser et immobiliser les nanoparticules métalliques. Ces milieux évitent l'agglomération des MNPs et facilitent leur recyclage. Des nanoparticules de Pd(0) et Ni(0) dans le glycérol, sphériques, petites en taille et bien dispersées, ont été synthétisées avec succès à partir d'une méthodologie simple sous pression d'hydrogène, en présence de différents stabilisants (alkaloïdes, phosphine, polymer). La caractérisation complète de ces matériaux en solution et à l'état solide, ainsi que la possibilité de faire des synthèses à grande échelle et de stocker les solutions catalytiques longtemps, montrent la grande stabilité de ces solutions colloïdales. Les nanoparticules dans le glycérol ont été impliquées dans une large variété de transformations : hydrogénations, hydrodéhalogénations, couplages de Hiyama, additions conjuguées et hydrosilylations. De plus, nous avons étudié l'effet du stabilisant sur la réactivité catalytique, nous permettant de contrôler l'état de surface des nanoparticules et moduler ainsi leur réactivité. Nous avons montré, de même, la capacité du glycérol pour immobiliser les catalyseurs, ce qui s'est traduit par la possibilité de recycler la phase catalytique entre 4 et 10 fois sans perte de metal. En parallèle, nous avons évalué le comportement du Ni(OAc)2 libre de ligands dans le glycérol, en tant que catalyseur alternatif pour des couplages C-C et C-hétéroélément. Nous présentons aussi une étude en flux continu, en collaboration avec la Maison Européenne des Procédés Innovants (MEPI), pour l'hydrogénation de différents groupes fonctionnels, en utilisant les PdNPs dans le glycérol synthétisées préalablement. / Metal nanoparticles (MNPs) have been largely studied in the last decades due to their interesting properties which found applications in several fields (microelectronics, materials and catalysis, among others). In contrast to common organic solvents, ionic liquids, water, supercritical CO2, polyols such as glycerol, represent innovative solvents for the immobilization of MNPs, avoiding their agglomeration and facilitating their recycling. Small, spherical, and well-dispersed Pd(0) and Ni(0) nanoparticles were synthesized under hydrogen pressure in glycerol, in the presence of different kinds of stabilizers (cinchona-based alkaloids, phosphine, polymer). The high stability of these colloidal solutions permitted the full characterization both in solution and at solid state, large-scale synthesis, and stocking the solutions for months. These colloidal catalysts were applied in a large variety of transformations including hydrogenations, hydrodehalogenations, Hiyama C-C couplings, hydrosilylation reactions, and Michael conjugate additions. Furthermore, we conducted a comparative study exhibiting the differences in catalytic reactivity by effect of the stabilizer, allowing us tuning the surface-state of the nanoparticles. Moreover, we showed the ability of glycerol to immobilize metal nanoparticles permitting the recycle of the catalytic phase between 4 and 10 times, without metal leaching. Additionally, we studied the behavior of ligand-free Ni(OAc)2 in glycerol as an alternative catalyst for C-C and C-heteroatom couplings. Also, we developped a continuous flow study, in collaboration with the Maison Européenne des Procédés Innovants (MEPI), for the hydrogenation of different functional groups, using PdNPs in glycerol

Made available in DSpace on 2016-03-15T19:36:29Z (GMT). No. of bitstreams: 1 Isabella Tereza Ferro Barbosa.pdf: 1500669 bytes, checksum: 82ebaab9bd4deeb9abb1fde076f7951a (MD5) Previous issue date: 2011-03-03 / Fundo Mackenzie de Pesquisa / The use of hydrogels combined with various additives in tissue regeneration and wound scarring, injuries and burnings has been an option in treatments of difficult scarring, infected-bleeding wounds, burnings and other diseases whose treatments, moist and sterilized resources are required. The hydrogels based on poly (N-vinyl-2-pyrrolidone) are membranes that form an effective barrier over the wound. It protects against the intrusion of external bacteria. It allows the passage in and out of oxygen and medicaments, since they are permeable to them. Pseudobohemite obtained by the sol-gel process are nanoparticles that present a highly superficial area, with expressive characteristic of bleeding absorption. They can adsorb large concentrations of medicaments released gradually in a site containing large amount of water, as it is the case of hydrogel membranes. The therapeutical attributes of hydrogel membranes are highly influenced by the presented concentration of water, about 85 to 90%, which determines the useful life and mechanical attributes of the product. Hydrogel based on PVP presents poor mechanical properties, which makes more difficult the handling of larger curatives. The objective of the study in obtaining hydrogel, based on PVP containing sodium alginate and nanoparticles of pseudobohemite obtained by sol-gel process consists in getting membranes with better mechanical properties and possible to incorporate suitable drugs to each kind of injures. In this study, were obtained and characterized membranes PVP based hydrogels (10%) containing sodium alginate nanoparticles pseudoboehmite concentrations of 1% and 3% respectively. The membranes were obtained by ionizing radiation dose of 25 kGy. The characterization of the membranes was performed by means of tensile tests and the physical-chemical gel fraction / fraction of the sun, swelling, dehydration isotherm is a function of time and thermal analysis. The results showed that the membranes of PVP containing sodium alginate showed higher degree of crosslinking (gel fraction higher), greater strength, greater degree of dehydration as a function of time and gel fraction higher water absorption compared to traditional membranes, only based PVP. / O uso de hidrogéis combinados com diversos aditivos na regeneração de tecidos e cicatrizações em ferimentos, lesões e queimaduras vem sendo uma opção em tratamentos de difícil cicatrização, em ferimentos infeccionados com exsudação e outras enfermidades cujos tratamentos necessitam de meios úmidos e estéreis. Os hidrogéis a base de poli (N-vinil-2- pirrolidona) são membranas que formam uma barreira efetiva no ferimento, contra a intrusão de bactérias externas, embora permitam a passagem de oxigênio e de medicamentos, por serem permeáveis a eles. Pseudoboemitas obtidas pelo processo sol-gel são nanopartículas que apresentam uma alta área superficial, além de apresentar expressivas propriedades de absorção do exsudado, podem adsorver grande concentração de medicamentos e estes são liberados gradativamente em um meio contendo grande quantidade de água como é o caso das membranas de hidrogéis. As propriedades terapêuticas das membranas de hidrogel são altamente influenciadas pela concentração de água presente, que deve ser ao redor de 85 a 90%, a qual determina a vida útil e as propriedades mecânicas do produto. Os hidrogéis produzidos somente a base de PVP apresentam propriedades mecânicas pobres o que dificulta o manuseio de curativos com maiores dimensões. O interesse do estudo da obtenção de hidrogéis a base de PVP contendo alginato de sódio e nanocarga de pseudoboemita obtida pelo processo sol-gel consiste em obter membranas com melhores propriedades mecânicas e com a possibilidade de incorporação de fármacos adequados a cada tipo de lesão. Neste trabalho foram obtidas e caracterizadas membranas de hidrogéis a base de PVP (10%) contendo alginato de sódio e nanocarga de pseudoboemita nas concentrações de 1% e 3%, respectivamente. As membranas foram obtidas por radiação ionizante com dose de 25 kGy. A caracterização das membranas foi realizada por meio de ensaios mecânicos de tração e ensaios físico-químicos de fração gel/fração sol, intumescimento, desidratação isotérmica em função do tempo e análises térmicas. Os resultados mostraram que as membranas de PVP contendo alginato de sódio apresentaram maior grau de reticulação (maior fração gel), maior resistência mecânica, maior grau de desidratação em função do tempo fração gel e maior absorção de água em relação às membranas tradicionais, somente a base de PVP.

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M. Tech. (Department of Chemistry, Faculty of Applied and Computer Science): Vaal University of Technology / Here, we report the synthesis and characterization of silver (Ag) and silver selenide (Ag2Se) nanoparticles using the metal-organic route method. This method involves the reduction of selenium powder and silver nitrate in the presence of trioctylphosphine as a solvent. Tri-n-octylphosphine oxide (TOPO) and hexadecylamine (HDA) were used in the study as capping molecules. The optical properties of the as-prepared nanoparticles were studied using UV-Visible and photoluminescence spectroscopy (PL). Transmission electron microscopy (TEM) and X-ray powder diffraction (XRD) were used to study the structural properties. The effect of capping molecules and temperature were investigated on the growth of the nanoparticles. The prepared nanoparticles seem to depend on the reaction temperature were the increase in temperature led to an increase in particle sizes. The growth of the as-prepared TOPO-capped Ag2Se nanoparticles was influenced by temperature, this was evident when the temperature was increased, the nanoparticles evolved from sphere to hexagonal shape. TOPO-capped nanoparticles showed the tendency of agglomeration with increase in temperature compared to HDA-capped nanoparticles. The X-ray diffraction results showed peaks which were identified as due to α-Ag2Se body centered cubic compound for both TOPO/HDA-capped Ag2Se nanoparticles. Some evidence of impurities were observed in the XRD analysis and indexed to metallic silver. HDA-capped Ag nanoparticles were found to be affected by temperature variation. The prepared nanoparticles were characterized with UV-Vis spectroscopy and transmission electron microscopy. XRD analysis was not performed due to small yield obtained. The absorption spectra of HDA-capped Ag nanoparticles at different temperatures show a surface Plasmon resonance (SPR) band in the regions 418 - 428 nm. Uniform spherical shapes were obtained for both 130 and 190 °C and fewer particles were obtained at 160 °C. The synthesis of TOPO–capped Ag nanoparticles was unsuccessful since none of the particles were isolated from the solution due to its lower capping ability or it may be that TOPO is binding too strongly to Ag. The polymer nanofibres were electrospun using electrospinning technique. Parameters such as concentration and voltage were investigated. These parameters significantly affect the formation of fibre morphology. PVP and PMMA polymers were used for this study. The electrospun composite fibres were characterized using UV-Visible spectroscopy, scanning electron microscopy (SEM), Thermal gravimetric analysis (TGA), X-ray diffraction (XRD) and Fourier transformer infrared (FTIR) spectroscopy. The SEM results show that increasing the polymer concentration resulted in increased fibre diameters. Hence increasing the voltage decreases the fibre diameters. Ag2Se nanoparticles were incorporated into PVP and PMMA and electrospun using electrospinning to produce composite fibres. Their addition into PVP polymer fibres improved the fibre’s uniformity and further decreased their diameters. The SEM of composite fibres for PMMA is not shown. The absorption bands for PVP composites fibres show a blue shift from the pure Ag2Se nanoparticles, whereas the one for PMMA show a red shift from the pure Ag2Se nanoparticles. Both the composite fibres for PVP and PMMA show a blue shift from the bulk of Ag2Se. The XRD analysis of the composite fibres shows no significant effect upon addition of Ag2Se nanoparticles on the amorphous peak of the PVP polymer, whereas on the PMMA, it shows peaks which were due to the face centered cubic phase of Ag. The FTIR spectra of the composite fibres and pure polymers (PVP and PMMA) gave almost identical features. TGA curves show no significant effect on the thermal properties of the PVP polymer and its composites, however, on the PMMA composite fibres it show an increase in the thermal stability of the polymers upon addition of Ag2Se nanoparticles. The study was based on silver nanoparicles and its antibacterial activities. One of the synthetic challenges for silver nanoparticles is their solubility and yield. Selenide was introduced in the study to improve such shortcomings of silver nanoparticles and also for possible improved properties, chemical stability and increased activity against bacteria. The selenide group on the metal also provides stronger chemical interaction between the nanoparticles and the polymer. Therefore, the intension was to use these nanoparticles into polymer fibres for potential use in wound dressing.