Solvent‐free fabrication of proton‐conducting membranes based on commercial elastomers

Five different types of elastomers were examined as the matrix materials in the preparation of non‐fluorinated proton exchange membranes utilizing a solvent‐free route via the in situ reaction of sodium 4‐styrenesulfonate (NaSS). The morphology of the elastomer/NaSS vulcanizates was studied to evaluate the effect of polarity, viscosity and saturation degree of the elastomer matrixes. Much better dispersion of NaSS was found in chlorosulfonated polyethylene rubber (CSM) and hydrogenated nitrile butadiene rubber (HNBR) matrixes than in the other three types of elastomer matrixes. For CSM/NaSS and HNBR/NaSS proton exchange membranes, distinctive membrane properties were observed and correlated with their different structure and morphologies. The CSM/NaSS membranes exhibited the proton conductivity as high as ~0.03 S cm^?1 and the selectivity (the ratio of proton conductivity to methanol permeability) higher than that of Nafion. Copyright © 2015 John Wiley & Sons, Ltd.     

Stereoselective determination of dufulin in watermelon under field conditions using chiral ultra high performance liquid chromatography with high‐resolution mass spectrometry

An effective and sensitive chiral analytical method was established to investigate the stereoselective dissipation of rac‐dufulin in watermelon using ultra high performance liquid chromatography with a superchiral S‐OD chiral column (4.6 × 150 mm i.d., 5 μm) coupled with high‐resolution mass spectrometry. To optimize the pretreatment method for detecting rac‐dufulin in the three matrixes, different extraction solvents, extractant volumes, extraction times, and absorbents were investigated to improve extraction efficiency. Moreover, analysis of variance was used to perform method validation for determination of the two dufulin enantiomers in the three matrixes. Using the optimized method, good linearity was obtained (determination coefficient > 0.999). The limits of detection and quantification of the two dufulin enantiomers in soil, watermelon, and pulp were 0.15 and 0.5 μg/kg, respectively. The average recoveries of the two enantiomers in the three matrixes at four spiked levels ranged from 75.0 to 107.8%, with intra‐ and inter‐day relative standard deviations of 0.4–10.4%. In field trials, the R enantiomer was preferentially dissipated in watermelon. These method validation results confirmed that the developed method was convenient and reliable for the stereoselective determination of enantiomers of rac‐dufulin in watermelon.     

Flammability, microhardness and transparency of nanocomposites based on functionalized polyethylenes

The flammability, microhardness and transparency of nanocomposites based on poly(ethylene-co-acrylic acid) copolymers having different concentration of acrylic acid and different molar mass, their Zn ionomer and ethylene-glycidylmethacrylate copolymer as matrixes and on organically modified montmorillonite as a nanofiller have been investigated. The presence and the increase in the content of the clay lead to the increase in the limiting oxygen index and to significant reduction of the burning rate of all materials. The results from the Vickers microhardness measurements have shown that the addition of the clay to matrixes of polar functionalized polyethylenes leads to a significant increase in the microhardness of the materials, while the creep constant does not decrease significantly. The UV spectra show that the light transmittance of the materials does not change significantly in the presence of the clay, i.e., the nanocomposite films preserve the polymer transparency. The results have been interpreted by the intercalated structures of the nanocomposites investigated.     

Ion-selective potentiometric sensors with silicone sensing membranes: A review

Ion-selective electrodes (ISEs) are used widely in mainframe analyzers for clinical chemistry, but there is also an increasing interest in the development of paper-based devices, wearable and implantable sensors, and other miniaturized ISEs. This trend is spurring much research in developing solid contact materials that enable miniaturization. The development of suitable polymeric matrixes for such sensors has only received less attention. In particular, in spite of lifetime limitations and toxicity concerns, polymeric matrixes comprising plasticizers are still commonly used. To that end, we note the benefits of silicone materials as alternative polymeric matrixes and, in particular, their promise for enhanced biocompatibility. While there has been steady progress in the development of ISEs with silicone membranes, this topic has not been reviewed for many years. This review critically discusses key fundamental characteristics of ISEs with silicone sensing and reference membranes, including their biocompatibility, adhesion to device substrates, water uptake, polarity, common impurities, and commercial availabilities. This is followed by a discussion of specific types of silicones and their use in ISEs, with the goal to inform and stimulate future research efforts into such devices.     

Study on Influence of Gelatin-Alginate Matrixes on the Coagulation System and Morphotic Blood Elements

Summary: The paper presents evaluation hemolytic and hemostatic activity of gelatin-alginate matrixes in contact with human blood in vitro studies. The percentage of hemolysis and free hemoglobin concentration were normal. The blood recalcyfication time (CT) was shortened and activated partial thromboplastin time (APTT) was prolonged. That sugested that coagulation processes were activated. Discrabed changes were depended an component composition of sponge.     

UV-induced oxo --> hydroxy unimolecular proton-transfer reactions in hypoxanthine

Monomers of hypoxanthine isolated in low-temperature Ar matrixes were studied using Fourier transform infrared spectroscopy. Two most stable tautomeric forms of hypoxanthine: oxo-N(9)-H and oxo-N(7)-H as well as a very small amount of the minor hydroxy-N(9)-H tautomer were observed in Ar matrixes directly after their deposition. UV irradiation of the matrixes induced conversion of the oxo-N(9)-H and oxo-N(7)-H tautomers of the compound into the hydroxy-N(9)-H and hydroxy-N(7)-H forms, respectively. Upon exposure of the matrixes to the UV (lambda > 270 nm) light, the oxo-N(9)-H --> hydroxy-N(9)-H phototautomeric reaction dominated strongly over the oxo-N(7)-H --> hydroxy-N(7)-H phototransformation. The latter phototautomeric reaction occurred effectively when matrix-isolated hypoxanthine was irradiated with shorter-wavelength (lambda > 230 nm) UV light. Thanks to this wavelength dependency, it was possible to clearly distinguish the oxo --> hydroxy photoreaction within the N(9)-H tautomers from the analogous phototautomeric process within the N(7)-H tautomers. All of the observed isomers of hypoxanthine (substrates and products of the photoreactions) were identified by comparison of their IR spectra with the spectra calculated at the DFT(B3LYP)/6-31++G(d,p) level of theory.     

Molecular Weight Development in Free‐Radical Polymerization with Polyfunctional Chain‐Transfer Agents, 2. Substitution Effects

The analytic expression for the weight‐average molecular weight development proposed in the first part of this series^[1] is extended to account for the substitution effects of the functional groups in a polyfunctional chain‐transfer agent. The obtained functional form of the matrix formula, P_w = W { D _w + ( I + T ) SPE ( I – TSPE )^–1 D _f } is essentially the same as for equal reactivity model, but the NxN square matrixes, S and P in the equal reactivity model is now expanded to NxfN and fNxfN matrixes, respectively, to account for the different reactivities of f functional groups. The number of chain types, N is extrapolated to infinity to obtain the P_w‐value for free‐radical polymerization. Practically, such extrapolation can be conducted with calculated P_w‐values for only three different N‐values. Illustrative calculations show that the obtained results agree with those from the Monte Carlo method. The present approach provides newer insight into the branched structure formation during complex polymerization reactions.     

Recent advances in the bioanalytical methods of polyethylene glycols and PEGylated pharmaceuticals

Polyethylene glycols are synthetic polymers composed of repeating oxyethylene subunits, which have been known for non‐toxic, non‐immunogenic, non‐antigenic, good solubility in water and therefore approved for pharmaceutical applications. Recently, attachment or amalgamation of polyethylene glycols to therapeutic small molecules, peptides, proteins, or nanoparticles has become a mature technology for the sake of improving their pharmacokinetic and pharmacological profiles, also referred to as PEGylation. By comparison, there are only a few PEGylated pharmaceuticals have been registered for further clinical trials and even less was approved for marketing. High failure rate of PEGylated pharmaceuticals in pre‐clinical and clinical trials could be majorly attributed to their unclear pharmacokinetic behaviors. Therefore, the in vivo fate of the PEGylated pharmaceuticals for the various routes of administration needs to be thoroughly investigated An accurate in vivo pharmacological study thereof highly depends on the precise detection of polyethylene glycols as well as their fragments in biological matrixes. The goal of this review is to highlight the analytical methods that were developed and applied to evaluate the polyethylene glycols in pharmaceutical ingredients and excipients, which bring us closer to bridging the gap between the development of polyethylene glycol‐based drug delivery systems and their clinical application.     

新型表面辅助激光解吸附/离子化质谱基质及其在生物检测中的应用

表面辅助激光解吸附/离子化质谱(Surface-assisted laser desorption/ionization mass spectrometry,SALDI-MS)是一种利用无机纳米粒子或纳米结构表面作为基质,辅助待测分子的解吸附和离子化的质谱技术。由于其具有灵敏度高、耐盐性好、操作简便、重现性好、检测通量高等优势,已经被广泛应用于食品安全、环境监测、生命科学等诸多领域。该文总结了近5年来,SALDI基质材料(金属及金属氧化物材料、碳材料、硅材料、金属有机骨架化合物材料等)的最新研究进展及其在生物检测领域中的应用,并对SALDI-MS基质材料的发展及应用进行了展望。     

Promoting organic room temperature phosphorescence through in situ polymerization

Organic room temperature phosphorescence materials (RTP) have attracted much attention for their wide application in organic light-emitting diodes, anti-counterfeiting, and sensors. In this work, a series of organic luminogens containing carbonyl and aromatics were fixed in a three-dimensional polymethyl methacrylate (PMMA) network by in situ polymerization. All organic luminogens-doped in situ PMMA (s-PMMA) columns achieved longer RTP lifetimes than those of doped commercial PMMA (c-PMMA) films, especially, the RTP lifetime of NMP2O in these PMMA matrixes increased from 1.82 ms to 156.34 ms by about 86 times. It is mainly due to the restriction of molecular motions by highly entangled polymer chains and rigid environments to efficiently inhibit the non-radiative transitions. Also, the excellent shielding effect toward oxygen by the in situ polymerization process can avoid possible quenching effects on triplet excited states, beneficial to RTP emission. Thus, it affords an efficient approach to achieving persistent RTP for three-dimensional displaying applications.     

Micro‐rheology and relaxation phenomena in Tg vicinity

The present paper describes possible forms of relaxation phenomena in T_g vicinity. The individual types of relaxation in amorphous matrix are described in the areas of Vogel's temperature, T_g and crossover temperature. Special emphasis is laid on the difference between Flory's relaxation mechanism and the approach by Di Marzio, Adams and Gibbs. These authors used the common formula of Flory, however, their interpretations of the so‐called “configurational phenomena” reflect completely different realities. The theoretical justification of heat capacity as a complex number (recently introduced by Hutchinson, Monserrat and Schawe in T_g vicinity) is provided in detail and compared with the existing experimental evidence quoted by the authors of these contributions as well as with data published in literature. The relation between complex heat capacity and relaxation of internal stress in amorphous matrixes or the effects of ageing are discussed.     

Intra- and intermolecular hydrogen bonding in formohydroxamic acid complexes with water and ammonia: infrared matrix isolation and theoretical study

The complexes of formohydroxamic acid with water and ammonia have been studied using FTIR matrix isolation spectroscopy and MP2 calculations with a 6-311++G(2d,2p) basis set. The analysis of the experimental spectra of the HCONHOH/H₂O(NH₃)/Ar matrixes indicates formation of strongly hydrogen-bonded complexes in which the NH group of formohydroxamic acid acts as a proton donor toward the oxygen atom of water or the nitrogen atom of ammonia. The NH stretching vibration of formohydroxamic acid exhibits 150 cm⁻¹ red shift in the complex with water and 443 cm⁻¹ red shift in the complex with ammonia as compared to the NH stretch of the HCONHOH monomer. The theoretical calculations indicate stability of five isomers for the water complex and three isomers for the ammonia complex. The most stable are the cyclic structures in which the water or ammonia molecules are inserted within the intramolecular hydrogen bond of the formohydroxamic acid molecule and act as proton donors for the CO group and proton acceptors for the OH group of the formohydroxamic acid molecule. In spite of their stability the cyclic structures have not been observed in the matrixes which indicates high energy barrier for their formation, the reaction of complex formation is under kinetic and not thermodynamic control.     

Preparation, properties and cytotoxicity evaluation of a biodegradable polyester elastomer composite

Multi-walled carbon nanotube (MWCNT)/poly(glycerol–sebacate–citrate) (PGSC) elastomer composite were prepared and their morphologies, compositions, glass transition temperatures, mechanical properties, water absorption, biodegradation and cytotoxicity were investigated. Results showed that the chemical structures of PGSC elastomers were hardly influenced by the MWCNT loadings, and physical adsorption was thought as the main interaction between the MWCNTs and PGSC matrixes. When the MWCNT loading was 3 wt%, MWCNTs displayed a homogenous dispersion in the matrixes, and the composite's strength and modulus respectively reached 4.4 MPa and 9.2 MPa, increasing by 62.96% and 33.33% than that of pure PGSC matrixes. The degradation rates of the composites tended to decrease with the increase of MWCNT loadings in simulated body fluid (SBF) solution. The composites presented no cytotoxicity especially when the MWCNT loadings were above 1 wt%. We expect the composites can be used as degradable bio-coatings and tissue engineering scaffolds in future.     

The chemical states of tellurium produced by spontaneous fission of252Cf

The distribution of the chemical states of tellurium isotopes produced by²⁵²Cf spontaneous fission, collected separately in the matrixes of NaCl, Kl, NaF, CH₃COONa·3H₂O, Na₂SO₄ and NaNO₃ crystals have been investigated. Two chemical states of tellurium isotopes maintained in these matrixes are Te(IV) and Te(VI). The relationships between the distribution of the chemical states of tellurium isotopes and the produced mode of tellurium, the chemical properties of collection matrixes, the time for collecting fission fragments are studied and the possible mechanism of the interactions of the fission products and the matrixes is discussed. The results show that the distribution of chemical states of tellurium isotopes depends on the chemical properties of the collection matrixes mainly.     

Lipidic Matrixes Containing Clove Essential Oil: Biological Activity,Microstructural and Textural Studies

Clove essential oil (CEO) is known for having excellent antioxidant and antimicrobial properties, but the poor stability of its components to light and temperature compromise this activity. The aim of this study is to evaluate the textural, antioxidant, antimicrobial and microstructural properties of matrixes produced with representative natural waxes and CEO. Thus, waxy emulsifiers, such as beeswax, candelilla wax, carnauba wax, and ozokerite wax, were employed to create such matrixes. The thermal, microstructural, textural, wetting, antioxidant, antimicrobial and infrared characteristics of the matrixes were then studied. The diverse chemical composition (long-chain wax esters in carnauba wax and short-chain fatty acids and hydrocarbons in beeswax and ozokerite wax, respectively) explained the differences in wetting, texture, melting, and crystallization characteristics. Crystal forms of these matrix systems varied from grainy, oval, to needle-like shape, but keeping an orthorhombic allomorph. The alignment and reorganization of beeswax and ozokerite wax into needle-like crystals increased the matrix strength and adhesion force compared to those of carnauba and candelilla matrixes, which showed weak strength and grainy morphology. The former two waxes and their matrixes also showed the largest plasticity. These lipidic matrixes show potential use for topical applications having acceptable antioxidant and textural properties.     

Photodissociation of formyl fluoride in rare gas matrixes

Photodissociation of formyl fluoride (HCOF) is studied in Ar, Kr, and Xe matrixes at 248 and 193 nm excitation by following spectral changes in the infrared absorption spectra. In all matrixes, the main photodissociation products are CO/HF species, including CO-HF and OC-HF complexes and thermally unstable CO/HF species (a distorted CO/HF complex or a reaction intermediate), which indicate negligible cage exit of atoms produced via the C-F and C-H bond cleavage channels. However, the observation of traces of H, F, CO, CO(2), F(2)CO, FCO, and HRg(2)(+) (Rg = Kr or Xe) in Kr and Xe matrixes would imply some importance of other reaction channels too. The analysis of the decay curves of the precursor shows that dissociation efficiency of HCOF increases as Ar < Kr < Xe, the difference being the factor of 10 between Ar and Xe. Moreover, HCOF dissociates 20-50 times faster at 193 nm compared to 248 nm. Interestingly, whereas the CO/HF species are stable with respect to photolysis in Ar, they photobleach in Kr and Xe matrixes at 248 and 193 nm, even though the first excited states of CO and HF are not energetically accessible with 193 and 248 nm photons. In krypton matrix, the photodissociation of CO/HF species at 248 nm is observed to be a single photon process. Quantum chemical calculations of electronic excitation energies of CO-HF and OC-HF complexes show that the electronic states of HF and CO mostly retain their diatomic nature in the pair. This clearly demonstrates that photodissociation of CO/HF complexes is promoted by the surrounding rare gas lattice.     

Molecular composite films from polybenzoxazole and crosslinked polymer matrixes

Films consisting of a rigid-rod polymer and thermoset resin matrixes were prepared. Poly{(benzo[1,2-d : 5,4-d′]bis(oxazole-2,6-diyl))-1,4-phenylene} (PBO) in polyphosphoric acid (PPA) was blended with 2,6-bis(4-benzocyclobutene) benzo[1,2- d : 5,4-d′]bis(oxazole) ( 1 ), and films were extruded from these solutions. The coagulated films were soluble in methanesulfonic acid (MSA). After heat treatment at 300°C, the films became insoluble in MSA. Crosslinked films were homogeneous and did not show phase segregation between the two components. These were composite films at the molecular level. Transmission electron microscopy (TEM) showed enhanced interlayer integrity and reduced microfibril separation for the molecular composite films as compared to normal PBO film. These films had significantly better torsion and tension delamination resistance. The incorporation of a second component did not sacrifice the tensile properties of PBO film. Thermal stability of these composite films was only slightly lower than that of normal PBO film. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2157–2165, 1997     

Geographic Characterization of Leccinum rugosiceps by Ultraviolet and Infrared Spectral Fusion

Leccinum rugosiceps is an edible mushroom belonging to genus Leccinum of Boletaceae. Its fruiting bodies are richer in nutrients than many vegetables and fruit. The model of support vector machine was established for the discrimination of L. rugosiceps from regions based on rapid and low-cost ultraviolet and infrared spectroscopies. The mid-level data fusion was performed by support vector machine. Compared to a single spectroscopic technique, mid-level data fusion provided higher accuracy by selecting the most significant variance from data matrixes based on partial least squares discriminant analysis. The accuracy of the classification of samples in the calibration and test sets were 85.00 and 94.74%, higher than separate measurements by ultraviolet or infrared spectroscopy. This approach has applications for authentication and quality assessment of L. rugosiceps.     

Radioecological Research on the Marine Environment Facing the Italian Base in Antarctica (1989–91)

Abstract

The results of the analysis of both natural (Th-232, U-238 and K-40) and artificial (Cs-137) radioactivity contained in samples collected during the 1989–90 and 1990–91 PNRA Scientific Campaigns in the Terra Nova Bay (Ross Sea) marine ecosystem, are presented in this paper. The data refers to samples of sea water, pack water, sediments and organisms belonging to demersal ichthyofauna (Pagothenia bernacchii, Chionodraco hamatus) and soft bottom macrofauna (Adamussium colbecki) collected in different coastal and off shore stations of the area investigated. Some sea water samples collected on the way to subAntarctic areas were also considered. The radiocontamination detected in sediments was correlated to the quantities of organic matter, organic carbon and nitrogen contained in the samples. Additionally, Cs-137 concentration factors were calculated for the different biological specimens and their anatomical components. Data values, with special consideration for anthropogenic Cs-137, are compared to results obtained from similar matrixes collected in the Northern Hemisphere in temperate waters before and after the accident at the Chernobyl nuclear plant.     

Validation of a Gas Chromatographic–Tandem Mass Spectrometric Method for Analysis of Pesticide Residues in Six Food Commodities. Selection of a Reference Matrix for Calibration

A gas chromatographic–tandem mass spectrometric (GC–MS–MS) method for analysis of 30 multi-class pesticide residues in four vegetables (cucumber, marrow, pepper, and eggplant) and two fruits (melon and watermelon) has been developed and validated. The performance characteristics linearity, detection limit (LOD), quantification limit (LOQ), precision, and recovery were studied. The effect of the matrix on the calibration step was studied by comparing calibration curves and recoveries for each food commodity. Two different food commodities, cucumber and watermelon, were selected as potential reference matrixes for the target vegetables and fruits, respectively.