The effect of the degree of hydrolysis of the PVA and the plasticizer concentration on the color, opacity, and thermal and mechanical properties of films based on PVA and gelatin blends

The objective of this work was to study the color, opacity, crystallinity, and the thermal and mechanical properties of films based on blends of gelatin and five different types of PVA [poly(vinyl alcohol)], with and without a plasticizer. The effect of the degree of hydrolysis of the PVA and the glycerol concentration on these properties was studied using colorimetry, differential scanning calorimetry (DSC), X-ray diffraction (XRD) and tensile mechanical tests. All films were essentially colorless (Delta E* < 5) and with low opacity ( Y <= 2.1). The DSC results were typical of partially crystalline materials, showing some phase separation characterized by a glass transition (T(g) = 40-55 degrees C), related to the amorphous part of the material, followed by two endothermic peaks related to the melting (T(m) = 100-160 and 170-210 degrees C) of the crystallites. The XRD results confirmed the crystallinity of the films. The film produced with PVA Celvol((R)) 418 (DH = 91.8%) showed the highest tensile resistance (tensile strength = 38 MPa), for films without plasticizer. However, with glycerol, the above-mentioned PVA and the PVA Celvol((R)) 504 produced the least resistant films of all the PVA types. But, although the mechanical properties of the blended films depended on the type of PVA used, there was no direct relationship between these properties and the degree of hydrolysis of the PVA. The properties studied were more closely dependent on the glycerol concentration. Finally, the mechanical resistance of the films presented a linear relationship with the glass transition temperature of the films. (c) 2007 Elsevier Ltd. All rights reserved.

Synthesis of biodegradable polyhydroxyalcanoate copolymer from a renewable source by alternate feeding

Polyhydroxyalcanoates copolymers with 3-hydroxybutirate (3HB) and 3-hydroxyvalerate (3HV) co-monomers, P3(HB-co-x%HV), were produced in fed-batch culture by Ralstonia eutropha DSM428 using fructose as a single carbon source in the first step and adding propionic acid in the second step by alternating feeding. Polymer yield was 0.18 g/L with a content of 24 mol% of the 3HV fraction determined by H-1 NMR. NMR measurements indicated that the polymer obtained is isotactic. The copolymer attained 35% of crystallinity according to X-ray diffraction measurements, and two (020) planes were observed. Thermal behavior presented melting temperature at 154 degrees C and the crystallization temperature was 65 degrees C. A glass transition temperature was observed at -10 degrees C. Average molecular weight measured by GPC was 4.9 x 10(5) Dalton. Isothermal radial growth rates of spherulites of P3(HB-co-24%HV) were studied. All experimental facts and the analysis of the sequence distribution of diads and triads of 3HB and 3HV units led to the conclusion that it is not a completely statistical random copolymer once it contains different types of segments. POLYM.

Biosynthesis and characterization of biodegradable Poly(3-hydroxybutyrate) from renewable sources

Poly(3-hydroxybutyrate) was produced in fed-batch cultures of Ralstonia eutropha DSM 428 and Alcaligenes latus ATCC 29712 on a mineral medium with different carbon sources such as sucrose, sodium lactate, lactic acid, soybean oil and fatty acid. The bacteria converted the different carbon sources supplied into P3HB. The best results were obtained when lactate or soybean oil were supplied as the sole carbon source. The range of number average molar mass (Mn) for the polymers, analyzed by Gel Permeation Chromatography was 1.65 to 0.79 x 10(5) g mol(-1). FTIR spectroscopy revealed a characteristic absorbance associated with polyester structures. The crystallinity degree, determinate from X-ray diffractograms, was about 69% in all synthesized polymers. The thermal properties associated to semicrystalline polymers indicated a glass transition at 0.1 degrees C and a melting point at about 175 degrees C and enthalpy of 63-89 J g(-1). The (1)H-NMR and (13)C-NMR spectra of the polymers were in agreement with the calculated chemical shifts associated with P3HB structures.

Numerical simulation of the liquid phase in SnO(2) thin film deposition by sol-gel-dip-coating

The fluid flow of the liquid phase in the sol-gel-dip-coating process for SnO(2) thin film deposition is numerically simulated. This calculation yields useful information on the velocity distribution close to the substrate, where the film is deposited. The fluid modeling is done by assuming Newtonian behavior, since the linear relation between shear stress and velocity gradient is observed. Besides, very low viscosities are used. The fluid governing equations are the Navier-Stokes in the two dimensional form, discretized by the finite difference technique. Results of optical transmittance and X-ray diffraction on films obtained from colloidal suspensions with regular viscosity, confirm the substrate base as the thickest part of the film, as inferred from the numerical simulation. In addition, as the viscosity increases, the fluid acquires more uniform velocity distribution close to the substrate, leading to more homogenous and uniform films.

Nanostructured copper thin film used for catalysis

Catalytic properties of copper thin films deposited in small channels and cavities were tested using Raman microscopy and mass spectroscopy (MS) techniques, mainly. The catalytic surface conditions were addressed visually and chemically by optical microscopy and X-ray photoelectron spectroscopy (XPS), respectively. The experimental conditions of present work induced copper oxidation; eventually a number of carbon species and graphite remained on the catalytic surface. Quartz crystal microbalance and mass spectroscopy data support both adsorption and catalysis phenomena. MS showed CO2 formation during n-hexane heating process but not to 2-propanol, probably due to redox reactions. XPS of copper surface present in the cavity after catalysis tests detected Cu2O and a range of possible carbon species. The adsorption and catalytic performance of copper films deposited in cavities and microchannels were quite similar. A simple miniaturized device for microanalysis was proposed. (C) 2007 Elsevier B.V. All rights reserved.

Highly Stable, Edible Cellulose Films Incorporating Chitosan Nanoparticles

The need for biodegradable polymers for packaging has fostered the development of novel, biodegradable polymeric materials from natural sources, as an alternative to reduce amount of waste and environmental impacts. The present investigation involves the synthesis of chitosan nanoparticles-carboxymethylcellulose films, in view of their increasing areas of application in packaging industry. The entire process consists of 2-steps including chitosan nanoparticles preparation and their incorporation in carboxymethylcellulose films. Uniform and stable particles were obtained with 3 different chitosan concentrations. The morphology of chitosan nanoparticles was tested by transmission electron microscopy, revealing the nanoparticles size in the range of 80 to 110 nm. The developed film chitosan nanoparticles-carboxymethylcellulose films were characterized by Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis, solubility tests, and mechanical analysis. Improvement of thermal and mechanical properties were observed in films containing nanoparticles, with the best results occurring upon addition of nanoparticles with 110 nm size in carboxymethylcellulose films. Practical Application Carboxymethylcellulose films containing chitosan nanoparticles synthesized and characterized in this article could be a potential material for food and beverage packaging applications products due to the increase mechanical properties and high stability. The potential application of the nanocomposites prepared would be in packaging industry to extend the shelf life of products.

Chemical modification of a nanocrystalline TiO(2) film for efficient electric connection of glucose oxidase

A novel biosensor for glucose was prepared by adsorption of 1,1`-bis(4-carboxybenzyl)-4,4`-bipyridinium di-bromide compound (H(2)BpybcBr(2)) onto the surface of a nanocrystalline TiO(2) film deposited onto FTO glasses, which was used as a platform to assemble the enzyme glucose oxidase to the electrode surface. The H(2)BpybcBr(2)/TiO(2)/FTO modified electrode was characterized by scanning electron microscopy, X-ray fluorescence image, cyclic voltammograms and spectroelectrochemical measurements. The immobilization of GOD on functionalized TiO(2) film led to stable amperometric biosensing for glucose with a linear range from 153 mu mol L(-1) to 1.30 mmol L(-1) and a detection limit of 51 mu mol L(-1). The apparent Michaelis-Menten constant (K(m)) was estimated to be 3.76 mmol L(-1), which suggested a high enzyme-substrate affinity. The maximum electrode sensitivity was 1.25 mu A mmol L(-1). The study proved that the combination of viologen mediators with TiO(2) film retains the electrocatalytic activity of the enzyme, and also enhances the electron transfer process, and hence regenerating the enzyme in the reaction with glucose. (C) 2010 Elsevier Inc. All rights reserved.

Thermal behavior and stability of biodegradable spray-dried microparticles containing triamcinolone

Thermal analysis has been widely used for obtaining information about drug-polymer interactions and for pre-formulation studies of pharmaceutical dosage forms. In this work, biodegradable microparticles Of Poly (D,L-lactide-co-glycolide) (PLGA) containing triamcinolone (TR) in various drug:polymer ratios were produced by spray drying. The main purpose of this study was to study the effect of the spray-drying process not only on the drug-polymer interactions but also on the stability of microparticles using differential scanning calorimetry (DSC), thermogravimetry (TG) and derivative thermogravimetry (DTG), X-ray analysis (XRD), and infrared spectroscopy (IR). The evaluation of drug-polymer interactions and the pre-formulation studies were assessed using the DSC, TG and DTG, and IR. The quantitative analysis of drugs entrapped in PLGA microparticles was performed by the HPLC method. The results showed high levels of drug-loading efficiency for all used drug: polymer ratio, and the polymorph used for preparing the microparticles was the form B. The DSC and TG/DTG profiles for drug-loaded microparticles were very similar to those for the physical mixtures of the components. Therefore, a correlation between drug content and the structural and thermal properties of drug-loaded PLGA microparticles was established. These data indicate that the spray-drying technique does not affect the physico-chemical stability of the microparticle components. These results are in agreement with the IR analysis demonstrating that no significant chemical interaction occurs between TR and PLGA in both physical mixtures and microparticles. The results of the X-ray analysis are in agreement with the thermal analysis data showing that the amorphous form of TR prevails over a small fraction of crystalline phase of the drug also present in the TR-loaded microparticles. From the pre-formulation studies, we have found that the spray-drying methodology is an efficient process for obtaining TR-loaded PLGA microparticles. (C) 2008 Elsevier B.V. All rights reserved.

Flow injection analysis using carbon film resistor electrodes for amperometric determination of ambroxol

Flow injection analysis (FIA) using a carbon film sensor for amperometric detection was explored for ambroxol analysis in pharmaceutical formulations. The specially designed flow cell designed in the lab generated sharp and reproducible current peaks, with a wide linear dynamic range from 5 x 10(-7) to 3.5 x 10(-4) mol L-1, in 0.1 mol L-1 sulfuric acid electrolyte, as well as high sensitivity, 0.110 A mol(-1) L cm(-2) at the optimized flow rate. A detection limit of 7.6 x 10(-8) mol L-1 and a sampling frequency of 50 determinations per hour were achieved, employing injected volumes of 100 mu L and a flow rate of 2.0 mL min(-1). The repeatability, expressed as R.S.D. for successive and alternated injections of 6.0 x 10(-6) and 6.0 x 10(-5) mol L-1 ambroxol solutions, was 3.0 and 1.5%, respectively, without any noticeable memory effect between injections. The proposed method was applied to the analysis of ambroxol in pharmaceutical samples and the results obtained were compared with UV spectrophotometric and acid-base titrimetric methods. Good agreement between the results utilizing the three methods and the labeled values was achieved, corroborating the good performance of the proposed electrochemical methodology for ambroxol analysis. (C) 2008 Elsevier B.V. All rights reserved.

The characterisation of the protective film formed by benzotriazole on the 90/10 copper-nickel alloy surface in H2SO4 media

The nature of the protective film formed by benzotriazole (BTAH) on the surface of the 90/10 CuNi alloy in deaerated 0.5 mol L-1 H2SO4 solution containing Fe(III) ions as oxidant was investigated by weight-loss, calorimetric measurements, and by surface-enhanced Raman spectroscopy (SERS). The SERS measurements show that the protective film is composed by the [Cu(I)BTA](n), polymeric complex and that the BTAH molecules are also adsorbed on the electrode surface. A modification of the BET isotherm for adsorption of gases ill solids is proposed to describe the experimental results obtained from weight-loss experiments that suggest an adsorption in multilayers. Electrochemical studies of copper and nickel in 0.5 mol L-1 H2SO4 in presence and absence of BTAH have also been made as an aid to interpret the results. The calculated adsorption free energy of the cuprous benzotriazolate on the surface of the alloy is in accordance with the value for pure copper. (C) 2007 Elsevier Ltd. All rights reserved.

Thermal analysis of biodegradable microparticles containing ciprofloxacin hydrochloride obtained by spray drying technique

Thermal analysis has been extensively used to obtain information about drug-polymer interactions and to perform pre-formulation studies of pharmaceutical dosage forms. In this work, biodegradable microparticles of poly(D,L-lactide-co-glycolide) (PLGA) containing ciprofloxacin hydrochloride (CP) in various drug:polymer ratios were obtained by spray drying. The main purpose of this study was to investigate the effect of the spray drying process on the drug-polymer interactions and on the stability of microparticles using differential scanning calorimetry (DSC), thermogravimetry (TG) and derivative thermogravimetry (DTG) and infrared spectroscopy (IR). The results showed that the high levels of encapsulation efficiency were dependant on drug:polymer ratio. DSC and TG/DTG analyses showed that for physical mixtures of the microparticles components the thermal profiles were different from those signals obtained with the pure substances. Thermal analysis data disclosed that physical interaction between CP and PLGA in high temperatures had occurred. The DSC and TG profiles for drug-loaded microparticles were very similar to the physical mixtures of components and it was possible to characterize the thermal properties of microparticles according to drug content. These data indicated that the spray dryer technique does not affect the physicochemical properties of the microparticles. In addition, the results are in agreement with IR data analysis demonstrating that no significant chemical interaction occurs between CP and PLGA in both physical mixtures and microparticles. In conclusion, we have found that the spray drying procedure used in this work can be a secure methodology to produce CP-loaded microparticles. (C) 2007 Elsevier B.V. All rights reserved.

Ex Situ Scanning Electrochemical Microscopy (SECM) Investigation of Bismuth- and Bismuth/Lead Alloy Film-Modified Gold Electrodes in Alkaline Medium

Scanning electrochemical microscopy (SECM) in feedback mode was employed to characterise the reactivity and microscopic peculiarities of bismuth and bismuth/lead alloys plated onto gold disk substrates in 0.1 molL(-1) NaOH solutions. Methyl viologen was used as redox mediator, while a platinum microelectrode was employed as the SECM tip. The metal films were electrodeposited ex situ from NaOH solutions containing either bismuth ions only or both bismuth and lead ions. Approach curves and SECM images indicated that the metal films were conductive and locally reactive with oxygen to provide Bi(3+) and Pb(2+) ions. The occurrence of the latter chemical reactions was verified by local anodic stripping voltammetry (ASV) at the substrate solution interface by using a mercury-coated platinum SECM tip. The latter types of measurements allowed also verifying that lead was not uniformly distributed onto the bismuth film electrode substrate. These findings were confirmed by scanning electron microscopy images. The surface heterogeneity produced during the metal deposition process, however, did not affect the analytical performance of the bismuth coated gold electrode in anodic stripping voltammetry for the determination of lead in alkaline media, even in aerated aqueous solutions. Under the latter conditions, stripping peak currents proportional to lead concentration with a satisfactory reproducibility (within 5% RSD) were obtained.

Pt film electrodes prepared by the Pechini method for electrochemical decolourisation of Reactive Orange 16

Electrochemical decolourisation of Reactive Orange 16 was carried out in an electrochemical flow-cell, using as working electrodes a Pt thin film deposited on a Ti substrate (Pt/Ti) prepared by the Pechini method and a pure platinum (Pt) foil. Using the Pt/Ti electrodes better results for dye decolourisation were obtained under milder conditions than those used for pure Pt. For the Pt electrode, colour removal of 93 % (lambda = 493 nm) was obtained after 60 min, at 2.2 V vs. RHE, using 0.017 mol L(-1) NaCl + 0.5 mol L(-1) H(2)SO(4) solution. For the Pt/Ti electrode there was better colour removal, 98%, than for the Pt electrode. Moreover, we used 0.017 mol L(-1) NaCl solution and the applied potential was 1.8 V. Under this condition after 15 min of electrolysis, more than 80% of colour was removed. The rate reaction constant, assuming a first order reaction, was 0.024 min(-1) and 0.069 min(-1), for Pt and Pt/Ti electrodes, respectively.

Physical Vapor Deposited Thin Films of Lignins Extracted from Sugar Cane Bagasse: Morphology, Electrical Properties, and Sensing Applications

The concern related to the environmental degradation and to the exhaustion of natural resources has induced the research on biodegradable materials obtained from renewable sources, which involves fundamental properties and general application. In this context, we have fabricated thin films of lignins, which were extracted from sugar cane bagasse via modified organosolv process using ethanol as organic solvent. The films were made using the vacuum thermal evaporation technique (PVD, physical vapor deposition) grown up to 120 nm. The main objective was to explore basic properties such as electrical and surface morphology and the sensing performance of these lignins as transducers. The PVD film growth was monitored via ultraviolet-visible (UV-vis) absorption spectroscopy and quartz crystal microbalance, revealing a linear relationship between absorbance and film thickness. The 120 nm lignin PVD film morphology presented small aggregates spread all over the film surface on the nanometer scale (atomic force microscopy, AFM) and homogeneous on the micrometer scale (optical microscopy). The PVD films were deposited onto Au interdigitated electrode (IDE) for both electrical characterization and sensing experiments. In the case of electrical characterization, current versus voltage (I vs V) dc measurements were carried out for the Au IDE coated with 120 nm lignin PVD film, leading to a conductivity of 3.6 x 10(-10) S/m. Using impedance spectroscopy, also for the Au IDE coated with the 120 nm lignin PVD film, dielectric constant of 8.0, tan delta of 3.9 x 10(-3)) and conductivity of 1.75 x 10(-9) S/m were calculated at 1 kHz. As a proof-of-principle, the application of these lignins as transducers in sensing devices was monitored by both impedance spectroscopy (capacitance vs frequency) and I versus time dc measurements toward aniline vapor (saturated atmosphere). The electrical responses showed that the sensing units are sensible to aniline vapor with the process being reversible. AFM images conducted directly onto the sensing units (Au IDE coated with 120 nm lignin PVD film) before and after the sensing experiments showed a decrease in the PVD film roughness from 5.8 to 3.2 nm after exposing to aniline.

Direct Electrochemical Determination of Glyphosate at Copper Phthalocyanine/Multiwalled Carbon Nanotube Film Electrodes

A copper phthalocyanine/multiwalled carbon nanotube film-modified glassy carbon electrode has been used for the determination of the herbicide glyphosate (Gly) at -50 mV vs. SCE by electrochemical oxidation using differential pulse voltamtnetry (DPV). Cyclic voltammetry and electrochemical impedance spectroscopy showed that Gly is adsorbed on the metallic centre of the copper phthalocyanine molecule, with formation of Gly-copper ion complexes. An analytical method was developed using DPV in pH 7.4 phosphate buffer solution, without any pretreatment steps: Gly was determined in the concentration range of 0.83-9.90 mu mol L(-1), with detection limit 12.2 nmol L(-1) (2.02 mu g L(-1))