Approach on the Electrochemical Reactivity of Poly-L-Glutamic Acid Against Doxorubicin and Its Application in the Development of a Voltammetric Sensor

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

Cathodic stripping voltammetric determination of ceftazidime with reactive accumulation at a poly-L-lysine modified hanging mercury drop electrode

Ceftazidime is hydrolysed only slowly at pH 10 at room temperature. This is indicated by a small cathodic stripping voltammetric peak obtained at pH 10 at a hanging mercury drop electrode at about -0.6 V which corresponds to the reduction of the hydrolysis product. This peak is enhanced more than tenfold by the addition of poly-L-lysine (PLL) to the electrolyte solution. The optimum accumulation potential is between 0 and -0.1 V: the size of the peak decreases steadily, however, as the accumulation potential is moved to more negative potentials and is about one-sixth the size for accumulation at -0.4 V. Existing knowledge of the organic chemistry of cephalosporins indicates that the accumulation must involve an aminolysis reaction of the unprotonated PLL with the beta-lactam ring of the ceftazidime. The limit of detection (3 sigma) in standard solutions was calculated to be 1 x 10(-10) mol l(-1). The detection limit in buffer solution containing 1% of urine was calculated to be 5 x 10(-9) mol l(-1), i.e. 5 x 10(-6) mol l(-1) in the urine. (C) 1999 Elsevier B.V. B.V. AU rights reserved.

STUDY OF POLING BEHAVIOR OF BIAXIALLY STRETCHED POLY(VINYLIDENE FLUORIDE) FILMS USING THE CONSTANT-CURRENT CORONA TRIODE

This article reports systematic results of corona poling measurements obtained on biaxially stretched polyvinylidene fluoride films charged in dry air. Charging was performed using the constant current corona triode. The dependence of the poling process on the sample thickness, charging current, and successive charging processes was investigated. Phase transitions from alpha to delta and to beta phases were observed when virgin samples were corona charged. The thermal pulse technique showed that the polarization profiles during charging can be made consistently almost uniform and that the ferroelectric reorientation can be associated with the rising plateau region displayed on potential buildup curves. (C) 1995 American Institute of Physics.

Regeneration of poly-L-lysine modified carbon electrodes in the accumulation and cathodic stripping voltammetric determination of the cromoglycate anion

Cromoglycate is accumulated on a poly-L-lysine (PLL) modified carbon electrode best from pH 4 solution, where it is anionic and the PLL is cationic, and at which pH the cromoglycate gives a good reduction peak at -0.82 V. The PLL film can be regenerated readily by washing the electrode with 3 M sodium hydroxide solution, in which the PLL is deprotonated. Regeneration of the film is not required as frequently when larger amounts of PLL are incorporated into it. This allows standard addition procedures to be carried out without regenerating the electrode. Linear calibration graphs have been obtained typically in the range 0.1 - 1.5 mug ml(-1). Detection limits have been calculated to be 10 ng ml(-1). The standard addition method has been applied satisfactorily to diluted urine solutions. (C) 2003 Elsevier B.V. B.V. All rights reserved.

Modification of glassy carbon electrodes with a poly-L-lysine/glutaraldehyde film

A film of poly-L-lysine (PLL) adheres better to the surface of a glassy carbon electrode when the PLL is partially cross-linked by means of glutaraldehyde. A film composition of 97.5% PLL/2.5% glutaraldehyde gives good adhesion and retains the anionic exchange capability of the PLL. The performance of the film was tested with hexacyanoferrate(III) using electrochemical and nonelectrochemical accumulation.

Determination of iodide and idoxuridine at a glutaraldehyde-cross-linked poly-L-lysine modified glassy carbon electrode

The detection limit (about 0.017 mu g mL(-1)) for voltammetric determination of iodide (peak at +0.87 V vs. Ag/AgCl at pH 2) at a glutaraldehyde-cross-linked poly-L-lysine modified glassy carbon electrode involving oxidation to iodine was found to be several orders of magnitude lower than that for the voltammetric determination on a bare glassy carbon electrode. This method was applied successfully to the determination of iodide in two medicinal formulations. Idoxuridine was determined indirectly at the same electrode by accumulating it first at -0.8 V vs. Ag/AgCl. At this potential the C-I bond in the adsorbed idoxuridine is reduced giving iodide, which is then determined at the modified electrode. The method was successfully applied to the determination of idoxuridine in a urine sample.

Increasing the dielectric breakdown strength of poly(ethylene terephthalate) films using a coated polyaniline layer

The dielectric strength of films made from poly(ethylene terephthalate) (PET) coated with a thin layer of polyaniline (PANI) was studied. The PANI layer was deposited on the PET films by the 'in situ' chemical polymerization method. The PANI layer of the PANI/PET films was undoped in NH4OH 0.1 M solution and re-doped with aqueous HCl solution under different pH values varying from 1 to 10. Electric breakdown measurements were performed by applying a voltage ramp and the results showed a dependence of the dielectric strength on the pH of the doping solution due to the changes in the electrical conductivity of the PANI layer. The dielectric strength of PET/PANI films treated under higher pH conditions showed an electric strength about 30% larger than the PET films, since it leads to a non-conductive PANI layer.

Osteointegration of poly(L-lactic acid)PLLA and poly(L-lactic acid)PLLA/poly(ethylene oxide)PEO implants in rat tibiae

Natural or synthetic materials may be used to aid tissue repair of fracture or pathologies where there has been a loss of bone mass. Polymeric materials have been widely studied, aiming at their use in orthopaedics and aesthetic plastic surgery. Polymeric biodegradable blends formed from two or more kinds of polymers could present faster degradation rate than homopolymers. The purpose of this work was to compare the biological response of two biomaterials: poly(L-lactic acid)PLLA and poly(L-lactic acid)PLLA/poly(ethylene oxide)PEO blend. Forty four-week-old rats were divided into two groups of 20 animals, of which one group received PLLA and the other PLLA/PEO implants. In each of the animals, one of the biomaterials was implanted in the proximal epiphysis of the right tibia. Each group was divided into subgroups of 5 animals, and sacrificed 2, 4, 8 and 16 weeks after surgery, respectively. Samples were then processed for analysis by light microscopy. Newly formed bone was found around both PLLA and PLLA/PEO implants. PLLA/PEO blends had a porous morphology after immersion in a buffer solution and in vivo implantation. The proportion 50/50 PLLA/PEO blend was adequate to promote this porous morphology, which resulted in gradual bone tissue growth into the implant.

Desenvolvimento e caracterização de nanocápsulas de poli(l-lactídeo) contendo benzocaína

In this paper we describe the preparation poly (L-lactide) (PLA) nanocapsules as a drug delivery system for the local anesthetic benzocaine. The characterization and in vitro release properties of the system were investigated. The characterization results showed a polydispersity index of 0.14, an average diameter of 190.1± 3 nm, zeta potential of –38.5 mV and an entrapment efficiency of 73%. The release profile of Benzocaine loaded in PLA nanocapsules showed a significant different behavior than that of the pure anesthetic in solution. This study is important to characterize a drug release system using benzocaine for application in pain treatment.

Zidovudine-poly (L-lactic acid) solid dispersions with improved intestinal permeability prepared by supercritical antisolvent process

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

Comparison of crystalline thin poly(vinylidene (70%)–trifluoroethylene (30%)) copolymer films with short chain poly(vinylidene fluoride) films

We compare the photoemission and electron energy loss spectra of crystalline poly(vinylidene-fluoride with trifluoroethylene: 70%: 30%), P(VDF–TrFE), films, fabricated by the Langmuir–Blodgett technique and annealed in vacuum, with in situ thermally evaporated films of poly(vinylidene-fluoride) (PVDF) in vacuum. The electronic structure and vibrational modes of the short chain PVDF films compare well with the crystalline P(VDF–TrFE) films indicating that vacuum annealed films prepared ex situ are free of significant surface contamination once vacuum annealed. The electronic structure for the short chain PVDF films exhibits, however, different temperature dependence than the crystalline P(VDF–TrFE) films. PACS: 68.47.Mn; 71.20.Rv; 63.22.+m; 73.22.-f

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.

Bionanocomposites based on Plla, Pcl and montmorillonite: synthesis, characterization and crystallization

Poly(lactide) is one of the best candidate to replace conventional petroleum-based polymers, since it is biobased, biocompatible and biodegradable. However, commercial PLA materials typically have low crystallization rate resulting in long processing time and low production efficiency. In this work the effects of two nanofillers MMT30B and MMT30B-g-P(LA-co-CL) on the crystallization rate of neat PLA and PLA/PCL blend were investigated. MMT30B-g-P(LA-co-CL) was synthetized by in situ grafting reaction. The synthesis was carried in xylene at 140°C, upon the results of a screening. The grafted copolymers were evaluated by 1H-NMR ,ATR–IR and TGA. Solvent casted films were obtained by mixing MMT30B-g-P(LA-co-CL) at 5% (w/w) with neat PLA and PLA/PCL blend, comparing the properties with the corresponding blends with and without a 5% of (w/w) unmodified clay. SEM images on PLA based blends shows that MMT30B is aggregated into larger particles compared to MMT30B-g-P(LLA-co-CL). This behavior is correlated to the better exfoliation of MMT30B-g-P(LA-co-CL) clay layers. SEM images on PLA/PCL based blends exhibit the typical sea-island morphology, characteristic of immiscible blends. PLA is the matrix while PCL is finely dispersed in droplets. MMT30B does not reduce PCL droplets size, while MMT30B-g-P(LA-co-CL) reduces the size of PCL droplets. This means that MMT30B-g-P(LA-co-CL) can migrate to the PLA-PCL interface, acting as a compatibilizer. Non-isothermal DSC cooling scans show a fractionated crystallization of the PCL phase in PLA/PCL/MMT30B-g-P(LA-co-CL), confirming the compatibilizer effect of MMT30B-g-P(LA-co-CL). At the same timeMMT30B-g-P(LA-co-CL) can better nucleate the PLA phase, both in neat PLA and PLA/PCL blend, promoting the crystallization during the heating scans. In isothermal condition, both the nanofillers increase the crystallization rate of PLA phase in neat PLA, while in PLA/PCL blends the effect is covered by the nucleating effect of PCL.

Development of novel melt-processable biopolymer nanocomposites based on poly(L-lactic acid) and WS2 inorganic nanotubes.

The use of tungsten disulphide inorganic nanotubes (INT-WS2) offers the opportunity to produce novel and advanced biopolymer-based nanocomposite materials with excellent nanoparticle dispersion without the need for modifiers or surfactants via conventional melt blending. The study of the non-isothermal melt-crystallization kinetics provides a clear picture of the transformation of poly(L-lactic acid) (PLLA) molecules from the non-ordered to the ordered state. The overall crystallization rate, final crystallinity and subsequent melting behaviour of PLLA were controlled by both the incorporation of INT-WS2 and the variation of the cooling rate. In particular, it was shown that INT-WS2 exhibits much more prominent nucleation activity on the crystallization of PLLA than other specific nucleating agents or nano-sized fillers. These features may be advantageous for the enhancement of mechanical properties and process-ability of PLLA-based materials. PLLA/INT-WS2 nanocomposites can be employed as low cost biodegradable materials for many eco-friendly and medical applications, and the exceptional crystallization behaviour observed opens new perspectives for scale-up and broader applications.

Treatment of Mycobacterium tuberculosis with antisense oligonucleotides to glutamine synthetase mRNA inhibits glutamine synthetase activity, formation of the poly-l-glutamate/glutamine cell wall structure, and bacterial replication

New antibiotics to combat the emerging pandemic of drug-resistant strains of Mycobacterium tuberculosis are urgently needed. We have investigated the effects on M. tuberculosis of phosphorothioate-modified antisense oligodeoxyribonucleotides (PS-ODNs) against the mRNA of glutamine synthetase, an enzyme whose export is associated with pathogenicity and with the formation of a poly-l-glutamate/glutamine cell wall structure. Treatment of virulent M. tuberculosis with 10 μM antisense PS-ODNs reduced glutamine synthetase activity and expression by 25–50% depending on whether one, two, or three different PS-ODNs were used and the PS-ODNs' specific target sites on the mRNA. Treatment with PS-ODNs of a recombinant strain of Mycobacterium smegmatis expressing M. tuberculosis glutamine synthetase selectively inhibited the recombinant enzyme but not the endogenous enzyme for which the mRNA transcript was mismatched by 2–4 nt. Treatment of M. tuberculosis with the antisense PS-ODNs also reduced the amount of poly-l-glutamate/glutamine in the cell wall by 24%. Finally, treatment with antisense PS-ODNs reduced M. tuberculosis growth by 0.7 logs (1 PS-ODN) to 1.25 logs (3 PS-ODNs) but had no effect on the growth of M. smegmatis, which does not export glutamine synthetase nor possess the poly-l-glutamate/glutamine (P-l-glx) cell wall structure. The experiments indicate that the antisense PS-ODNs enter the cytoplasm of M. tuberculosis and bind to their cognate targets. Although more potent ODN technology is needed, this study demonstrates the feasibility of using antisense ODNs in the antibiotic armamentarium against M. tuberculosis.