Pyrazolyl coordination polymers of cadmium(II)

The coordination polymers [Cd(mu-Cl)(2)(HPz)(2)](n) (1) and [Cd(mu-1,3-SCN)(2)(HPz)(2)](n) (2) (HPz = pyrazole) have been prepared and characterized by elemental analysis, infrared spectroscopy, and single crystal X-ray diffraction. Both complexes exhibited chain structures made by linear arrays of Cd(II) bridged by chloro (1) or inversely related 1,3-SCN groups (2) and the pyrazole ligands at the apical. sites. Intermolecular hydrogen bonds and another non-covalent interactions are responsible for the self-assembly of linear chains into 2D networks. (c) 2005 Elsevier B.V. All rights reserved.

MEASURING HYSTERESIS LOOPS OF FERROELECTRIC POLYMERS USING THE CONSTANT CHARGING CURRENT CORONA TRIODE

A novel method is proposed for measuring the hysteresis loops of ferroelectric polymers. The samples need to have only one electrode and are poled by corona discharge in a constant current corona triode. It is shown how the sample surface potential and the charging current are related to the remanent polarization and coercive field, so that the hysteresis loops can be obtained. An illustrative example is given for samples of beta-PVDF for which the hysteresis cycles were remarkably close to those obtained with the traditional Sawyer-Tower circuit. Values of 80 MV/m and 70 mC/m2 were estimated for the coercive field and remanent polarization, respectively.

Low-weight coordination polymers derived from the self-assembly reactions of Pd(II) pyrazolyl compounds and azide ion

The low-weight Pd(II) coordination polymers [(N(3))(HL)Pd {Pd(3)(mu-N(3))(mu-L)(5)}10(mu-L)(2)Pd(L)(HL)]{L = Pz(-) (1); mPz(-) (2), IPz(-)(3)} and [(N(3))(HPz)Pd{Pd(6)(mu-N(3))(2)(mu-PZ)(5)(mu-L)(5)}(10)(mu-L)(2)Pd(Pz)(HPz)] {L = mPz(-) (4), dmPz(-) (5); IPz(-) (6)} {L = pyrazolate (Pz(-)), 4-methylpyrazolate(mPz(-)), 4-iodopyrazo late (IPz(-)), 3,5-dimethylpyrazolate (dmPz(-))} have been prepared in this work. IR spectra clearly indicated the exobidentate nature of pyrazolato ligands as well the end-on coordination mode of the azido group. The molecular weight determinations by osmometry indicated that the species have a low degree of polymerization (n = 10). NMR experiments showed two pyrazolate environments in a 2:1 ratio, being assigned to the six-membered ring Pd(mu-L)(2)Pd and the Pd(mu-N(3))(mu-L)Pd metallocycle, respectively. UV-visible spectroscopy gave further evidences for the oligomeric structures of 1-6. Some alternative structures for the isostructural polymers have been suggested. (c) 2005 Elsevier Ltd. All rights reserved.

Collapse and Color Changes in Grapefruit Juice Powder as Affected by Water Activity, Glass Transition, and Addition of Carbohydrate Polymers

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Effects of helium ion irradiation on fluorinated plasma polymers

The effects of ion irradiation on fluorinated plasma polymer films are investigated using profilometry, surface contact-angle measurements, infrared reflection absorption spectroscopy (IRRAS) and X-ray photoelectron spectroscopy (XPS). Remarkably, helium plasma immersion ion implantation (PIII) of several amorphous hydrogenated fluorinated plasma polymers deposited from C(2)H(2)-SF(6), C(6)H(6)-SF(6) or C(6)F(6) produces film compactions of up to 40%, and modifies the surface energy in the 35 to 65 dyn cm(-1) range. As revealed by IRRAS and XPS, the films contain C-H, C-C, C=C, C=O, O-H and C-F groups. XPS spectra confirm the presence of N (typically similar to 5%). The films produced from SF(6)-containing plasmas also contain S. For irradiation times of 80 min, the film carbon content is increased, and the fluorine content is greatly reduced, by factors of about 3 to 15, depending on the initial film composition. (C) 2010 Elsevier B.V. All rights reserved.

The ferromagnetic behaviour of conducting polymers revisited

The magnetic properties of doped pellets of poly(3-methylthiophene) showing room temperature ferromagnetic behaviour have been discussed in a previous article. The magnetic behaviour was attributed to a weak ferromagnetic phase, due to the superexchange interaction of polarons via the dopant anions. The Dzialoshinsky-Morya interaction among canted spins was proposed to explain the ferromagnetism. In this article the main conclusions of that work concerning the magnetic behaviour are revised. The basic assumption now is that the magnetic moments are spin 1/2 polarons that can interact antiferromagnetically and/or ferromagnetically. In the small crystalline regions of the polymer, which are identified with the polymer portion that remains ferromagnetic at room temperature, the interaction gives rise to S = 0 and 1 bipolarons and the S = 1 triplet state is lower in energy. In the disordered region, disorder will prevent the complete S = 1 and 0 coupling and bands of polarons ferromagnetically and antiferromagnetically coupled will appear. Using this approach, all the magnetization data can be qualitatively explained, as well as the electron spin resonance data.

Polarons, bipolarons, and crystallization in conducting polymers: An ESR study

Electron spin resonance (ESR) experiments give extremely important information concerning spin arrangements in conducting polymers. This is evidenced by the behavior of the ESR lines as a function of temperature and microwave power. Our ESR data of pressed pellets of ClO- 4 doped poly(3-methylthiophene) (P3MT) synthesized at 25 °C show the predominance of polarons. Instead, the sample prepared at 5 °C shows the predominance of bipolarons. Besides, for both types of samples, crystallization, observed from the ESR data, has shown a rearrangement of spin species.

Polaronic ferromagnetism in conducting polymers

Ferromagnetic behavior at room temperature is reported in metal-free-conducting polymer samples of poly(3-methylthiophene) doped with ClO 4 -. Magnetic moments associated with spin 1/2 positive polarons are possibly interacting through a Dzialoshinski-Moriya anisotropic superexchange via the dopant anions, giving rise to weak ferromagnetism. © 2001 Elsevier Science B.V. All rights reserved.

Studies on the interaction between humic substances and conducting polymers for sensor application

The interaction between humic substances and poly(o-ethoxyaniline) (POEA), a conducting polymer, was investigated for both solution and self-assembled films. The results have shown that the humic substances induce a doping of POEA by protonation, as indicated by UV-Vis and Raman spectroscopies. The atomic force microscopy (AFM) studies on the self-assembled films have shown that the average roughness of the polymer film has increased after exposing it to humic substances (fulvic and humic acids), consistent with the interaction between POEA and humic substances. However, this change in morphology is reversible by washing the films with water in agreement with the electrical data allowing using this system in sensor applications. Here, the sensor formed by an array of different sensing units was able to detect and distinguish humic substances in aqueous solution, as shown by multivariate analysis (principal component analysis). The motivation to detect humic substance comes due to its importance in terms of quality control of water or soil. ©2005 Sociedade Brasileira de Química.

Relationship between the dielectric and mechanical properties and the ratio of epoxy resin to hardener of the hybrid thermosetting polymers

The relationship between the dielectric properties (dielectric constant, ε′, and loss factor, ε; activation energy, E a) and the ratio of epoxy resin (OG) to hardener of the epoxy resin thermosetting polymers was investigated. The amplitude of the ε″ peak decreases with increasing OG content until about 73 wt.% and slightly increases at higher OG content. The temperature of the position of the ε″ peak increases with the increasing of OG content, reaching maximum values for compositions in the range of 67 and 73 wt.%, and then it decreases sharply at higher OG content. The activation energy obtained from dielectric relaxation increased with increasing wt.% OG up to around 70 wt.%. Further increase in concentration of OG up to 83 wt.% reduced E a. The curves of tensile modulus and fracture toughness mechanical properties as a function of OG content presented a similar behavior. ©2006 Sociedade Brasileira de Química.

Kinetic parameters for thermal decomposition of supramolecular polymers derived from diclofenac-meglumine supramolecular adducts

Meglumine is an aminocarbohydrate able to form supramolecular adducts with organic acids. The recognition is based on hydrogen bonds and the structures resulting from the complexation have high solubility in water. This property has been exploited by the pharmaceutical industry in the improvement of existing drugs, and the successful example of this approach involves the poorly soluble non-steroidal anti-inflammatory drugs (NSAIDs). Investigation of the thermal behavior of adduct obtained from meglumine and the NSAID diclofenac revealed that a polymer-like material is formed from the self-assembly of diclofenac-meglumine adducts in the melt. This polymer showed a high molecular weight around 2.0×105kDa. The kinetic parameters for the thermal decomposition step of the polymer were determined by the Capela-Ribeiro non-linear isoconversional method. From data for the TG curves in nitrogen atmosphere and heating rates of 5, 10, 15 and 20°Cmin-1, the Eα and Bα terms could be determined, and consequently the pre-exponential factor, Aα, as well as the kinetic model, g(α). © 2012 Elsevier B.V.

Modelling polymers with side chains: MEH-PPV and P3HT

Modelling polymers with side chains is always a challenge once the degrees of freedom are very high. In this study, we present a successful methodology to model poly[2-methoxy-5-(2′-ethyl-hexyloxy)-p-phenylenevinylene] (MEH-PPV) and poly[3-hexylthiophene] (P3HT) in solutions, taking into account the influence of side chains on the polymer conformation. Molecular dynamics and semi-empirical quantum mechanical methods were used for structure optimisation and evaluation of optical properties. The methodology allows to describe structural and optical characteristics of the polymers in a satisfactory way, as well as to evaluate some usual simplifications adopted for modelling these systems. Effective conjugation lengths of 8-14.6 and 21 monomers were obtained for MEH-PPV and P3HT, respectively, in accordance with experimental findings. In addition, anti/syn conformations of these polymers could be predicted based on intrinsic interactions of the lateral branches. © 2013 Copyright Taylor and Francis Group, LLC.

Thermal stability of ionene polymers

Two different cationic polymers of the same chemical type and with very similar chemical structures were reacted with a natural bentonite over a wide range of polymer/clay ratios. This study involved the synthesis of cationic aliphatic ammonium polyionenes, specifically 3,6-ionene and 3,6-dodecylionene. Ionenes are ion-containing polymers that contain quaternary nitrogen atoms in the main macromolecular chain as opposed to a pendant chain. The CHN content, basal spacing, and elemental composition of each of the polymer-clay complexes were analyzed by X-ray diffraction, X-ray fluorescence, and thermogravimetry. All the polycations reacted to form interlayer complexes with clay, which displaced more Na+ and little Ca2+. Sodium and calcium were both present as interlayer cations in the clay and its complexes. The TG/DTG curves show that both polymers underwent thermal degradation in more than one stage. Specifically, 3,6-ionene was found to undergo two stages of decomposition and 3,6-dodecylionene undergo three stages. The behavior of the TG/DTG curves and the activation energy values suggest that 3,6-dodecylionene (E = 174,85 kJ mol-1) complexes have greater thermal stability than 3,6-ionene (E = 115,52 kJ mol-1) complexes. The mechanism of degradation suggests a direct interaction with the dodecyl chain containing 12 carbons, which are present in 3,6-dodecylionene but not in 3,6-ionene. © 2012 Akadémiai Kiadó, Budapest, Hungary.

Subcutaneous tissue reaction and cytotoxicity of polyvinylidene fluoride and polyvinylidene fluoride-trifluoroethylene blends associated with natural polymers

Cytotoxicity and subcutaneous tissue reaction of innovative blends composed by polyvinylidene fluoride and polyvinylidene fluoride-trifluoroethylene associated with natural polymers (natural rubber and native starch) forming membranes were evaluated, aiming its applications associated with bone regeneration. Cytotoxicity was evaluated in mouse fibroblasts culture cells (NIH3T3) using trypan blue staining. Tissue response was in vivo evaluated by subcutaneous implantation of materials in rats, taking into account the presence of necrosis and connective tissue capsule around implanted materials after 7, 14, 21, 28, 35, 60, and 100 days of surgery. The pattern of inflammation was evaluated by histomorphometry of the inflammatory cells. Chemical and morphological changes of implanted materials after 60 and 100 days were evaluated by Fourier transform infrared (FTIR) absorption spectroscopy and scanning electron microscopy (SEM) images. Cytotoxicity tests indicated a good tolerance of the cells to the biomaterial. The in vivo tissue response of all studied materials showed normal inflammatory pattern, characterized by a reduction of polymorphonuclear leukocytes and an increase in mononuclear leukocytes over the time (p < 0.05 Kruskal-Wallis). On day 60, microscopic analysis showed regression of the chronic inflammatory process around all materials. FTIR showed no changes in chemical composition of materials due to implantation, whereas SEM demonstrated the delivery of starch in the medium. Therefore, the results of the tests performed in vitro and in vivo show that the innovative blends can further be used as biomaterials. © 2013 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater 101B: 1284-1293, 2013. Copyright © 2013 Wiley Periodicals, Inc.

Production and evaluation of recycled polymers from açaí fibers

The possibility of recycling and the favorable mechanical properties of the products have encouraged the study and production of thermoplastic composites from natural fibrous waste. Açaí (cabbage palm) fiber, which is removed from the seed, has been slightly investigated, as compared to what is already known about the fruit pulp. In this study, the influence of açaí fiber as an element of reinforcement in recycled everyday usage thermoplastics using simple, low cost methodology was evaluated. Recycled matrixes of high impact polystyrene and polypropylene were molded by hot compression from which the fiber composites were obtained. The FTIR technique showed that the process was efficient in preventing degradation of the açaí fibers. The influence of the fiber on the mechanical behavior of the recycled matrixes was investigated by microscopic images of compression and impact tests. The results showed better impact performance for the fiber combined with the polymeric matrixes.