Enhancing the crystallization and orientation of electrospinning poly (lactic acid) (PLLA) by combining with additives

PLLA is a thermoplastic biopolymer and can be used in industrial applications for medical and filtration applications. The brittleness of PLLA is attributed to slow crystallization rates and its glass transition temperature (Tg) is high (60 °C); for this reason, its applications are limited. The orientation, morphology, and crystal structure of the electrospun fibers was investigated by SEM, POM, DSC, FTIR, XRD, and SAXS. Combining with additives leads to a large decrease of fiber diameter, viscosity, and changes of fiber morphology and crystal structure compared to pure PLLA. DSC showed that the Tg of PLLA decreased about 15 °C and there was no change in relaxation enthalpy by the addition of plasticizer. FT-IR indicate a strong interaction between PLLA and additives; a new band appears in the PLLA blend at 1,756 cm−1 at room temperature as a crystalline band without any annealing. In addition, WAXD indicated that the intensities of the two peaks at (200/110) and (203) increased for the blend at room temperature without any annealing in comparison with PLLA; this means that PHB crystallizes in the amorphous region of PLLA. The POM experiments agree with the results from DSC, FTIR, and WAXS measurements, confirming that adding PHB results in an increase in the number of nuclei with much smaller spherulites and enhances the crystallization behavior of this material, thereby improving its potential for applications.

Poly(lactic acid-glycolic acid) nanoparticles markedly improve immunological protection provided by peptide P10 against murine paracoccidioidomycosis

Background and purpose: The present study reports on the preparation and testing of a sustained delivery system for the immunomodulatory peptide P10 aimed at reducing the in vivo degradation of the peptide and the amount required to elicit a protective immune response against paracoccidioidomycosis. Experimental approach: BALB/c mice were infected with the yeast Paracoccidioides brasiliensis to mimic the chronic form of paracoccidioidomycosis. The animals were treated daily with sulfamethoxazole/trimethoprim alone or combined with peptide P10, either emulsified in Freund`s adjuvant or entrapped in poly(lactic acid-glycolic acid) (PLGA) nanoparticles at different concentrations (1 mu g, 5 mu g, 10 mu g, 20 mu g or 40 mu g center dot 50 mu L-1). Therapeutic efficacy was assessed as fungal burden in tissues and the immune response by quantitative determination of cytokines. Key results: Animals given combined chemotherapy and P10 nanotherapy presented a marked reduction of fungal load in the lungs, compared with the non-treated animals. After 30 days of treatment, P10 entrapped within PLGA (1 mu g center dot 50 mu L-1) was more effective than `free` P10 emulsified in Freund`s adjuvant (20 mu g center dot 50 mu L-1), as an adjuvant to chemotherapy. After treatment for 90 days, the higher doses of P10 entrapped within PLGA (5 or 10 mu g center dot 50 mu L-1) were most effective. Treatment with P10 emulsified in Freund`s adjuvant (20 mu g center dot 50 mu L-1) or P10 entrapped within PLGA (1 mu g center dot 50 mu L-1) were accompanied by high levels of interferon-gamma in lung. Conclusions and implications: Combination of sulfamethoxazole/trimethoprim with the P10 peptide entrapped within PLGA demonstrated increased therapeutic efficacy against paracoccidioidomycosis. P10 incorporation into PLGA nanoparticles dramatically reduced the peptide amount necessary to elicit a protective effect.

Potential tuberculostatic agents: Micelle-forming copolymer poly(ethylene glycol)-poly(aspartic acid) prodrug with isoniazid

With the objective of obtaining slow-acting isoniazid derivatives, of potential use as chemoprophylactics or chemotherapeutics in tuberculosis, the micelle-forming copolymer of poly(ethylene glycol)-poly(aspartic acid) prodrug with isoniazid was synthesized. The derivative obtained was found to be active in Mycobacterium Il(tuberculosis culture, with a minimal inhibitory concentration (MIC) 5.6 times lower than that of the tuberculostatic drug.

Multifunctional antitumor magnetite/chitosan-l-glutamic acid (core/shell) nanocomposites

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Serum titres of anti-glutamic acid decarboxylase-65 and anti-IA-2 autoantibodies are associated with different immunoregulatory milieu in newly diagnosed type 1 diabetes patients

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Phytogenic additives and glutamine plus glutamic acid in broiler diets

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Study of Thermodegradation and Thermostabilization of Poly( lactide acid) Using Subsequent Extrusion Cycles

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

An Electrochemical Sensor for Reducing Sugars Based on a Glassy Carbon Electrode Modified with Electropolymerized Molecularly Imprinted Poly-o-phenylenediamine Film

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Effect of silica surface on luminescence properties of tb3+-glutamic acid.

We studied the effect of silica surface on luminescence properties of terbium complex by spectroscopy characterization, where microparticles of mesoporous silica type MSU-X was prepared. We used silica with different surface: calcined, washed, functionalized with 3- aminopropyl-triethoxysilane (APTES), and 3-glycidoxypropyl-trimethoxysilane (GPTMS); impregnated with Tb3+-glutamic acid complex. The obtained materials were characterized by scanning electron microscopy, porosity measurements, small-angle X-ray scattering, as structural characterization; Fourier transform infrared and luminescence spectroscopy, as spectroscopy characterization. Finally, we observed that functional groups at the silica surface lead to changes on luminescent properties of the final materials. The observed shift of the absorption and emission bands can be assigned to the effect of the functional groups of mesoporous silica.

Biodegradation of Thermoplastic and hermosetting Polyesters from Z-Protected Glutamic Acid

In a previous article,1 the development and molecular characterization of three polyesters from N-carbobenzyloxy-L-glutamic acid (ZGluOH) were reported. The polymers were a linear, heterochain polyester (ZGluOH and ethylene glycol), a crosslinked heterochain polyester (ZGluOH and diglycidyl ether of 1,4-butanediol), and a crosslinked, heterochain aromatic polyester (ZGluOH and diglycidyl ether of bisphenol A). In this manuscript, results of biodegradation studies are reported. The three polymers hydrolyzed to low molecular weight oligomers similar to the monomers with lipase. When exposed to a mixed culture of micro-organisms, the first two resins degraded to biomass and respiratory gases. The crosslinked heterochain aromatic polyester resisted microbial degradation.

Multi-Walled Carbon Nanotubes and Poly(lactic acid) Nanocomposite Fibrous Membranes Prepared by Solution Blow Spinning

Nanocomposite fibers based on multi-walled carbon nanotubes (MWCNT) and poly(lactic acid) (PLA) were prepared by solution blow spinning (SBS). Fiber morphology was characterized by scanning electron microscopy (SEM) and optical microscopy (OM). Electrical, thermal, surface and crystalline properties of the spun fibers were evaluated, respectively, by conductivity measurements (4-point probe), thermogravimetric analyses (TGA), differential scanning calorimetry (DSC), contact angle and X-ray diffraction (XRD). OM analysis of the spun mats showed a poor dispersion of MWCNT in the matrix, however dispersion in solution was increased during spinning where droplets of PLA in solution loaded with MWCNT were pulled by the pressure drop at the nozzle, producing PLA fibers filled with MWCNT. Good electrical conductivity and hydrophobicity can be achieved at low carbon nanotube contents. When only 1 wt% MWCNT was added to low-crystalline PLA, surface conductivity of the composites increased from 5 x 10(-8) to 0.46 S/cm. Addition of MWCNT can slightly influence the degree of crystallinity of PLA fibers as studied by XRD and DSC. Thermogravimetric analyses showed that MWCNT loading can decrease the onset degradation temperature of the composites which was attributed to the catalytic effect of metallic residues in MWCNT. Moreover, it was demonstrated that hydrophilicity slightly increased with an increase in MWCNT content. These results show that solution blow spinning can also be used to produce nanocomposite fibers with many potential applications such as in sensors and biosensors.

Synthesis and characterization of Poly(vinylphosphonic acid) for proton exchange membranes in fuel cells

Vinylphosphonic acid (VPA) was polymerized at 80 ºC by free radical polymerization to give polymers (PVPA) of different molecular weight depending on the initiator concentration. The highest molecular weight, Mw, achieved was 6.2 x 104 g/mol as determined by static light scattering. High resolution nuclear magnetic resonance (NMR) spectroscopy was used to gain microstructure information about the polymer chain. Information based on tetrad probabilities was utilized to deduce an almost atactic configuration. In addition, 13C-NMR gave evidence for the presence of head-head and tail-tail links. Refined analysis of the 1H NMR spectra allowed for the quantitative determination of the fraction of these links (23.5 percent of all links). Experimental evidence suggested that the polymerization proceeded via cyclopolymerization of the vinylphosphonic acid anhydride as an intermediate. Titration curves indicated that high molecular weight poly(vinylphosphonic acid) PVPA behaved as a monoprotic acid. Proton conductors with phosphonic acid moieties as protogenic groups are promising due to their high charge carrier concentration, thermal stability, and oxidation resistivity. Blends and copolymers of PVPA have already been reported, but PVPA has not been characterized sufficiently with respect to its polymer properties. Therefore, we also studied the proton conductivity behaviour of a well-characterized PVPA. PVPA is a conductor; however, the conductivity depends strongly on the water content of the material. The phosphonic acid functionality in the resulting polymer, PVPA, undergoes condensation leading to the formation of phosphonic anhydride groups at elevated temperature. Anhydride formation was found to be temperature dependent by solid state NMR. Anhydride formation affects the proton conductivity to a large extent because not only the number of charge carriers but also the mobility of the charge carriers seems to change.

Effect Of Confined Impinging Jet Mixing Processing Parameters On Poly (Lactic Acid) Nanoparticle Morphology

Biodegradable nanoparticles are at the forefront of drug delivery research as they provide numerous advantages over traditional drug delivery methods. An important factor affecting the ability of nanoparticles to circulate within the blood stream and interact with cells is their morphology. In this study a novel processing method, confined impinging jet mixing, was used to form poly (lactic acid) nanoparticles through a solvent-diffusion process with Pluronic F-127 being used as a stabilizing agent. This study focused on the effects of Reynolds number (flow rate), surfactant presence in mixing, and polymer concentration on the morphology of poly (lactic acid) nanoparticles. In addition to looking at the parameters affecting poly (lactic acid) morphology, this study attempted to improve nanoparticle isolation and purification methods to increase nanoparticle yield and ensure specific morphologies were not being excluded during isolation and purification. The isolation and purification methods used in this study were centrifugation and a stir cell. This study successfully produced particles having pyramidal and cubic morphologies. Despite successful production of these morphologies the yield of non-spherical particles was very low, additionally great variability existed between redundant trails. Surfactant was determined to be very important for the stabilization of nanoparticles in solution but appears to be unnecessary for the formation of nanoparticles. Isolation and purification methods that produce a high yield of surfactant free particles have still not been perfected and additional testing will be necessary for improvement.¿

Investigation Of Leucine And Glutamic Acid Properties From The Nanoscale To The Macroscale

Aerosols are known to have important effects on climate, the atmosphere, and human health. The extent of those effects is unknown and largely depend on the interaction of aerosols with water in the atmosphere. Ambient aerosols are complex mixtures of both inorganic and organic compounds. The cloud condensation nuclei (CCN) activities, hygroscopic behavior and particle morphology of a monocarboxylic amino acid (leucine) and a dicarboxylic amino acid (glutamic acid) were investigated. Activation diameters at various supersaturation conditions were experimentally determined and compared with Köhler theoretical values. The theory accounts for both surface tension and the limited solubility of organic compounds. It was discovered that glutamic acid aerosols readily took on water both when relative humidity was less than 100% and when the supersaturation condition was reached, while leucine did not show any water activation at those conditions. Moreover, the study also suggests that Köhler theory describes CCN activity of organic compounds well when only surface tension of the compound is taken into account and complete solubility is assumed. Single parameter ¿ was also computed using both CCN data and hygroscopic growth factor (GF). The results of ¿ range from 0.17 to 0.53 using CCN data and 0.09 to 0.2 using GFs. Finally, the study suggests that during the water-evaporation/particle-nucleation process, crystallization from solution droplets takes place at different locations: for glutamic acid at the particles¿ center and leucine at the particles¿ boundary.

Glutamic acid inducing kidney stone biomimicry by a brushite/gelatin composite

Brushite is a well known precursor of calcium oxalate monohydrate, the main mineral found in kidney stones having a monoclinic crystal structure. Here, we present a new method for biomimicking brushite using a single tube diffusion technique for gel growth. Brushite crystals were grown by precipitation of calcium hydrogen phosphate hydrate in a gelatin/glutamic acid network. They are compared with those produced in gel in the presence of urea. The aggregates were analyzed by scanning electron microscopy (SEM), X-ray diffraction (XRD), infrared spectroscopy (IR) and thermal gravimetric analysis (TGA). SEM revealed a change of morphology by glutamic acid from spherulitic growth to plate-shaped and mushroom-like forms consisting of crystal plates and highly ordered prismatic needles, respectively. Furthermore, brushite crystals grown in a gelatin/glutamic acid/urea network showed needle-shaped morphology being different from other brushite growth forms. The XRD method showed that cell parameters for brushite specimens were slightly larger than those of the American Mineral Society reference structure. The mushroom-like biomimetic composite bears a strong resemblance to the brushite kidney stones which may open up new future treatment options for crystal deposition diseases. Hence, suitable diets from glutamic acid rich foods could be recommended to inhibit and control brushite kidney stones.