Synthesis, spectral and thermal studies on dicarboxylate-bridged palladium(II) coordination polymers. Part I

This work describes the synthesis, IR and (13)C CPMAS NMR spectroscopic as well the thermal characterization of the new dicarboxylate complexes [Pd(2)(ox)(2)(4,4'-bipy)]n (1), [Pd(2)(ox)(2)(bpe)](n) (2) and [Pd(2)(ox)(2)(pz)](n) (3) {ox = oxalate, bipy = 4,4'-bipyridine, bpe = 1,2-bis(4-pyridyl)ethane, pz = pyrazine}. TG experiments reveal that compounds 1-3 undergo thermal decomposition in three steps. Metal palladium was the final product of the thermal decompositions, which was identified by X-ray powder diffraction.

Synthesis, spectral and thermal studies on dicarboxylate-bridged palladium(II) coordination polymers. Part II

The synthesis and thermal behavior of the new [Pd(fum)(bipy)] (n) center dot 2nH(2)O (1), [Pd(fum)(bpe)] (n) center dot nH(2)O (2) and [Pd(fum)(pz)] (n) center dot 3nH(2)O (3) {bipy = 4,4'-bipyridine, bpe = 1,2-bis(4-pyridyl)ethene and pz = pyrazine} fumarate complexes are described in this work as well their characterization by IR and (13)C CPMAS NMR spectroscopies. TG curves showed that the compounds released organic ligands and lattice water molecules in the temperature range of 46-491 A degrees C. In all the cases, metallic palladium was identified as the final residue.

Synthesis, spectral and thermal studies on pyrazolate-bridged palladium(II) coordination polymers

Synthesis, spectroscopic characterization and thermal behavior of pyrazolate-bridged palladium complexes [Pd(mu-Pz)(2)](n) (1), [Pd(mu-mPz)(2)](n) (2), [Pd(mu-dmPz)(2)](n) (3), [Pd(mu-IPz)(2)](n) (4) {pyrazolate (Pz(-)), 4-methylpyrazolate (mPz(-)), 3,5-dimethylpyrazolate (dmPz(-)), 4-iodopyrazolate (IPz(-))} have been described in this work. The exobidentate coordination mode of pyrazolato ligands in 1-4 was inferred on basis of IR spectroscopic evidences. TG investigations indicated that the introduction of substituents at the 4 position in the pyrazolyl moiety into coordination polymers do not affect significantly their thermal stability, whereas at the 3 and 5 position reduced the stability of the main chain. Metal palladium was the final product of the thermal decompositions, which was identified by X-ray powder diffraction.

Self-assembly of Pd(II) pyrazolyl complexes to 1-D hydrogen-bonded coordination polymers

This work describes the synthesis and characterization of two novel Pd(II) pyrazolyl complexes of the type [PdX2(HdmPz)(2)](n) {X=SCN- (1), N-3(-) (2); HdmPz=3,5-dimethylpyrazole} that self-assemble through N-H...NCS or N-H...NNN hydrogen bonds to yield infinite one-dimensional chains, as confirmed by single crystal X-ray study on 1. The expected solid state polymeric structure for 2 is slowly broken up in CHCl3 Solution, leading to an equilibrium mixture of cis and trans-[Pd(N-3)(2)(HdmPz)(2)] monomers, as demonstrated by time-dependent IR and NMR studies. (C) 2003 Elsevier B.V. B.V. All rights reserved.

Natural gum-assisted phthalocyanine immobilization in electroactive nanocomposites: Physicochemical characterization and sensing applications

Natural gums have been traditionally applied in cosmetics and the food industry, mainly as emulsification agents. Due to their biodegradability and excellent mechanical properties, new technological applications have been proposed involving their use with conventional polymers forming blends and composites. In this study, we take advantage of the polyelectrolyte character exhibited by the natural gum Chicha (Sterculia striata), extracted in the Northeastern region of Brazil, to produce electroactive nanocomposites. The nanocomposites were fabricated in the form of ultrathin films by combining a metallic phthalocyanine (nickel tetrasulfonated phthalocyanine, NiTsPc) and the Chicha gum in a tetralayer architecture, in conjunction with conventional polyelectrolytes. The presence of the gum led to an efficient adsorption of the phthalocyanine and enhanced the electrochemical response of the films. Upon combining the electrochemical and UV-vis absorption data, energy diagrams of the Chicha/NiTsPc-based system were obtained. Furthermore, modified electrodes based on gum/phthalocyanine films were able to detect dopamine at concentrations as low as 10(-5) M.

Synthesis and characterization of cellulose acetate produced from recycled newspaper

In this work, the viability of recycling newspaper for producing cellulose acetate was tested. Newspaper recycling is extremely important not only for the environment preservation, but also from the economical point of view of aggregating value to this residue. Cellulose acetate was produced from a homogeneous acetylation, and then characterized by FTIR, DSC and TGA. Acetylation times were 48 h for as received newspaper (CA48) and 24 h for delignified newspaper (CA24), resulting in cellulose diacetate (DS = 1.98 +/- 0.22) for CA48 and cellulose triacetate (DS = 2.79 +/- 0.02) for CA24, respectively. Membranes of these materials were produced and characterized according to the previously mentioned techniques and by measurements of water vapor flux, which were compared to membranes of nanofiltration SG from Osmonix (R). Results showed that independently of a purification step, it is possible to produce cellulose acetate membranes through the chemical recycling of newspaper and that membrane CA24 presents thermal stability comparable to membranes produced of commercial cellulose acetate. (C) 2007 Elsevier Ltd. All rights reserved.

Characterization of Si : O : C : H films fabricated using electron emission enhanced chemical vapour deposition

Silicon-based polymers and oxides may be formed when vapours of oxygen-containing organosilicone compounds are exposed to energetic electrons drawn from a hot filament by a bias potential applied to a second electrode in a controlled atmosphere in a vacuum chamber. As little deposition occurs in the absence of the bias potential, electron impact fragmentation is the key mechanism in film fabrication using electron-emission enhanced chemical vapour deposition (EEECVD). The feasibility of depositing amorphous hydrogenated carbon films also containing silicon from plasmas of tetramethylsilane or hexamethyldisiloxane has already been shown. In this work, we report the deposition of diverse films from plasmas of tetraethoxysilane (TEOS)-argon mixtures and the characterization of the materials obtained. The effects of changes in the substrate holder bias (Vs) and of the proportion of TEOS in the mixture (XT) on the chemical structure of the films are examined by infrared-reflection absorption spectroscopy (IRRAS) at near-normal and oblique incidence using unpolarised and p-polarised, light, respectively. The latter is particularly useful in detecting vibrational modes not observed when using conventional near-normal incidence. Elemental analyses of the film were carried out by X-ray photoelectron spectroscopy (XPS), which was also useful in complementary structural investigations. In addition, the dependencies of the deposition rate on Vs and XT are presented. (c) 2007 Elsevier B.V. All rights reserved.

Surface characterization of absorbing polymer films deposited on transparent glasses

PANI films were deposited on glass substrates by in-situ polymerization and characterized by UV-VIS spectroscopy and atomic force microscopy. A method is developed to accurately analyze ellipsometric data obtained for transparent glass substrates before and after modification with absorbing polymer films. Surface modification was made with an overlayer such as polyaniline ( PANI), which exhibits different optical properties by varying its oxidation state. First, the issue of using transparent substrates for ellipsometry studies was examined and then, spectroscopic ellipsometry was used to characterize absorbing overlayers on transparent glasses. The same methodologies of data analysis can be also applied to other absorbing films on transparent substrates, and deposited by different techniques.

Synthesis and characterization of ruthenium complexes immobilized on poly(4-vinylpyridine)

The [Ru(NH3)5(H2O)]2+ and trans-[Ru(NH3)4SO2(H2O)]2+ complexes ions were immobilized on poly(4-vinylpyridine) (4-PVP) through reactions in aqueous solutions. The stability of the imobilized complexes was checked in aqueous solution in the pH 2.0-8.0 range. The number of pyridinic nitrogens in the polymer 4-PVP is 2.80±0.05 mmol/g according to nitrogen elemental analysis. Potentiometric titration experiments showed that the accessible nitrogen, in aqueous medium, was 0.94±0.02 mmol/g with a p Ka value of 7.4±0.2. In addition, ruthenium and sulfate analysis has demonstrated that about 15% of the accessible nitrogen sites are able to coordinate to the metal centers. The characterization of the immobilized complexes was made through diffuse electronic and infrared spectroscopies and differential pulse and cyclic voltammetries. © 1993 Plenum Publishing Corporation.

Preparation and characterization of SrBi2Nb2O9 thin films made by polymeric precursors

A polymeric precursor solution was employed in preparing SrBi2Nb2O9 (SBN) powder and thin films dip coated onto Si(100) substrate. XRD results show that the SBN perovskite phase forms at temperatures as low as 600°C through an intermediate fluorite phase. This fluorite phase is observed for samples heat-treated at temperatures of 400 and 500°C. After heat treatment at temperatures ranging from 300 to 800°C, thin films were shown to be crack free. Grazing incident angle XRD characterization shows the occurrence of the fluorite intermediate phase for films also. The thickness of films, measured by MEV, was in the order of 80-100 nm.

Synthesis and spectroscopic characterization of a novel coordination polymer of palladium(II) with pyrazole and azido ligands

The one-dimensional coordination polymer of palladium(II) with pyrazolato (Pz -) and azide (N 3 -) as bridging ligands, of formula [Pd 3(μ-N 3)(μ-Pz) 5] n, has been prepared. From IR and Raman studies it was evidenced the exobidentate nature of pyrazole ligands as well the μ-1,1-bridging coordination of azido groups. NMR experiments showed two sets of broadened signals with different intensities indicating the presence of pyrazolato groups in distinct chemical environments. The proposed structure of [Pd 3(μ-N 3)(μ-Pz) 5] n consists of a zigzag ribbon in which each (Pz) 2Pd(Pz) 2 entity is bound to two stacked planar units [Pd(μ-Pz)(μ-N 3)Pd core] with very weak Pd-Pd interaction, based on UV-Vis spectroscopy.

Structural control of photoluminescence of four poly(urethane-urea-co-1,3,5-triazine)s: Synthesis and characterization

A series of segmented poly(urethane-urea)s containing 1,3,5 triazine in the hard block and hexamethylene spacers in the soft block was prepared. The hard to soft segment ratio was varied systematically, to afford a series of polymers in which the chromophore concentration varied from 4.2% to 18.1%. Although triazine emission is located in the UV region, the films with higher content of the chromophore emitted a visible blue light (425 nm) when excited at the very red-edge of the absorption band. The photophysical properties of the materials were strongly dependent on the relative amount of triazine moieties along the main chain. Isolated moieties emit in copolymers with small amount of triazine groups, indicating that even though in solid state, these moieties tend to be apart. Two photophysical consequences were observed when the amount of triazine increases: there is some energy transfer process involving isolated moieties with consequent decrease of the lifetime and an additional red-edge emission attributed to aggregated lumophores. The mono-exponential decay observed for the isolated form is substituted by a bi-exponential decay of the aggregated species. The materials were not strong emitters, but since the N-containing triazine moieties are good electron transport groups, the polymers have potential application as electron transport enhancers in various applications. © 2006 Elsevier B.V. All rights reserved.

Structural characterization of a new dextran with a low degree of branching produced by Leuconostoc mesenteroides FT045B dextransucrase

This paper offers the physical and chemical characterization of a new dextran produced by Leuconostoc mesenteroides FT045B. The chemical structure was determined by Fourier Transform Infrared spectroscopy and 1H Nuclear Magnetic Resonance spectroscopy. The dextran was hydrolyzed by endodextranase; the products were analyzed using thin layer chromatography and compared with those of commercial B-512F dextran. The number-average molecular weight and degree of polymerization of the FT045B dextran were determined by the measurement of the reducing value using the copper bicinchoninate method and the measurement of total carbohydrate using the phenol-sulfuric acid method. The data revealed that the structure of the dextran synthesized by FT045B dextran sucrase is composed of d-glucose residues, containing 97.9% α-(1,6) linkages in the main chains and 2.1% α-(1,3) branch linkages compared with the commercial B-512F dextran, which has 95% α-(1,6) linkages in the main chains and 5% α-(1,3) branch linkages. © 2012 Elsevier Ltd. All rights reserved.

Soft-chemical synthesis, characterization and humidity sensing behavior of WO3/TiO2 nanopowders

Tungsten oxide/titania (WO3/TiO2) nanopowders were synthesized by the polymeric precursor method which varied the WO3 content between 0 and 10 mol%. The powders were thermally treated in a conventional furnace and their structural, microstructural and electric properties were evaluated by X-ray diffraction (XRD), Raman spectrometry, N 2 physisorption, NH3 chemisorption, temperature-programmed reduction (TPR), X-ray absorption near-edge spectroscopy (XANES) in situ XANES and extended X-ray absorption fine structure spectroscopy (EXAFS) and transmission electron microscopy (TEM). XRD and Raman spectrometry confirmed the homogeneous distribution of an amorphous WO3 phase in the TiO 2 matrix which stabilized the anatase phase through the generation of [TiO5·V0] or [TiO5·V 0] complex sites. Conventional TPR-H2 (temperature programmed reduction) along with XANES TPR-H2 and XANES TPR-EtOH showed that WO3/TiO2 sample reduction occurs through the formation of these complex clusters. Moreover, the addition of WO3 promoted an increase in the surface acidity of doped samples as revealed by NH3 chemisorption. The WO3/TiO2 bulk-ceramic samples were further used to estimate their potential application in a humidity sensor in the range of 15-85% relative humidity. Probable reasons that lead to the different humidity sensor responses of samples were given based on the structural and surface characterizations. Correlation between the sensing performance of the sensor and its structural features are also discussed. Although all samples responded as a humidity sensor, the W2T sample (2 mol% added WO3) excelled for sensitivity due to the increase in acid sites, optimum mean pore size and pore size distribution. © 2013 Elsevier B.V.

Synthesis and characterization of cross-linked molecularly imprinted polyacrylamide for the extraction/preconcentration of glyphosate and aminomethylphosphonic acid from water samples

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