ESR study of free radicals in UHMW-PE fiber irradiated by gamma rays

ESR spectra of the trapped radicals in an ultra-high molecular weight polyethylene (UHMW-PE) fiber irradiated by gamma rays showed well-resolved hyperfine splitting at room temperature since the c-axis of the crystallites is aligned with the fiber direction and the radicals are trapped in crystallites. The alkyl radical (?CH₂?^?CH?CH₂?) was the major product after irradiation in vacuum and in air at room temperature. Some of the alkyl radicals converted to allyl radicals (?CH₂?^?CH?CH=CH?) and polyenyl radicals (?CH₂?^?CH?(CH=CH)_n?CH₂?) during storage in vacuum. Upon storage in air atmosphere, the alkyl radicals decayed by reaction with oxygen. Of particular interest is the very slow decay rate of the alkyl radical trapped in UHMW-PE fiber, the half-life is 26 days in vacuum, and 13 days in air at room temperature, which is about 1/30 and 1/100 of that reported for high density polyethylene (HDPE), respectively. The extremely long lifetime of the alkyl radical is supposed to be caused by the large size of crystallites in UHMW-PE fiber. The rate of radical decay was accelerated by annealing at elevated temperature.     

Micellization in solutions of anionic surfactants with two ionogenic groups

Conductometry is employed to measure the critical micellization concentrations of homologous sodium monoalkyl sulfosuccinates with double-charged surface-active anions and alkyl radicals R containing 10–14 carbon atoms (ROOCCH₂CH(SO₃Na)COONa). The degrees of counterion binding with micelles and the Gibbs energy ΔG ^m of micellization are calculated. The incorporation of an additional ionogenic group into a surfactant molecule somewhat decreases ΔG ^m. For the examined series of surfactants, the increment of ΔG ^m due to one methylene group is ?4.44 kJ/mol.     

LC�CMS�CMS Quantitative Determination of Brivudine in Human Plasma and Its Application to Pharmacokinetic Studies

A sensitive and specific liquid chromatography?Celectrospray ionization?Ctandem mass spectrometry method has been developed and validated for the identification and quantification of brivudine in human plasma using diclofenac as an internal standard. The method involves extraction with ethyl acetate. The analyte was separated on a C₁₈ column and analyzed in multiple reaction monitoring mode with a negative electrospray ionization interface using the [M?CH]^? ions, m/z 332.8??m/z 80.9 for brivudine, m/z 293.6??m/z 249.5 for diclofenac. The method was validated over the concentration range of 5.54?C2,836 ??g L^?1 for brivudine. The intra-and inter-day precisions were less than 8.91% in terms of relative standard deviation (RSD), and the accuracy was within ?4.22% in terms of relative error (RE). The lower limit of quantification (LLOQ) was 5.54 ??g L^?1 with acceptable precision and accuracy. There were almost no matrix effects. Recovery of brivudine spiked in drug-free plasma was higher than 77.17%. The method was used to study the pharmacokinetic profile of brivudine in human plasma after oral administration of brivudine tablets.     

Effect of Low Temperature Air Plasma Treatment on Wetting and Flow Properties of Kaolinite Powders

It was found in this study that the air plasma treatment of particular kaolinite has led to the change of its wettability, which was reflected in the decreased values of water contact angles of wetting from 88.7° for virgin kaolinite to 86.3° for 30?min air plasma treated one. Plasma treated samples show higher average surface energies in the wide range of coverage regimes in comparison to the virgin samples as determined by inverse gas chromatography. Results of these measurements confirmed our assumption, that air plasma treatment activates surface energy of the crystal planes of the kaolinite as reflected in the broadened dispersive surface energy distribution after 10?min treatment time. However with prolonged 30?min treatment time the dispersive surface energy distribution profile was decreased. We assume, that the latter decrease reflects the distorsion of the crystal lattice of the kaolinite as confirmed by FTIR analysis as reflected in changes of Si?CO?CSi and Al₂O?CH characteristic absorption bands. Calculated dispersive surface free energy for 24?% surface coverage was increased from original 35?mJ/m² to 40.3 and 40.8?mJ/m² for 10 and 30?min treatment times. There were determined yield locus and flow function dependencies at different stress levels for virgin and different time plasma treated samples (flow index??ff _c , effective angle of internal friction???? _e , unconfined yield strength???? _c ). It was found that by plasma treatment the character of the flow was shifting from region of very cohesive (ff _c ?=?2.39) to the cohesive (ff _c ?=?3.19). For untreated samples effective angle of internal friction was decreased with increasing applied consolidation stress, while for plasma treated kaolinite it was increased.     

Lignin-type, α,β-unsaturated aldehydes of lignin-type in organic solvents

A 1:1 reaction of [HO(CH₂)₃]₃P with 4-hydroxy-3-methoxy-cinnamaldehyde (coniferaldehyde) or 3,5-dimethoxy-4-hydroxycinnamaldehyde (sinapaldehyde) in acetone at room temperature affords phosphonium zwitterions of the type R₃P⁺CH(4-O^?-Ar)CH₂CHO; other phosphines [R = Et, n-Bu, (CH₂)₂CN, and p-Tol] do not react under the same conditions. In alcohols R??OH(D) [R?? = CD₃, Et, (CD₃)₂CD, s-Bu, HOCH₂CH₂], the above phosphines (except the cyano-derivative) and those where R = i-Pr, Cy, Me₂Ph, MePh₂ do react within an equilibrium established between the reactants and the zwitterion-hemiacetal products R₃P⁺CH(4-O^?-Ar)CH₂CH(OH)(OR??) that are formed as a mixture of two diastereomers. The nature of the phosphine and the alcohol affects the equilibrium and the diastereomeric ratio.     

Effect of plastic deformation on the character of micro-brownian motions in glassy poly(methyl methacrylate)

Glassy PMMA samples are plastically deformed at room temperature in the uniaxial compression regime to residual strains of e _res = 25%. Dielectric spectra of the initial and deformed samples are recorded via the method of broadband dielectric spectroscopy in the frequency range f = (5 × 10^?4) ? 10⁷ Hz. The results are compared with the dynamic mechanical spectra of samples deformed under the same conditions. Dielectric and mechanical spectra are noticeably distorted by deformation. As a result, dielectric permittivity ??? increases, shear modulus G?? decreases, and the intensity of dielectric ?? losses slightly increases, while dielectric and mechanical ?? losses increase appreciably. In addition, the ??anomaly?? of total dielectric ???_tot and total mechanical ??G _tot dispersions (???_tot = ?₀ ? ?_?? ?? ???_?? + ???_?? and ??G _tot = G ₀ ? G _?? ?? ??G _?? + ??G _??) occurs, that is, the polymer is transformed from the state with ???_?? ? ???_?? and ??G _?? < ??G _?? into the state with ???_?? > ???_?? and ??G _?? > ??G _??. The described phenomenon is related to a strong gain in ?? dielectric and mechanical losses in the deformed material. It is found that ?? losses increase owing to an anelastic deformation component arising during glass loading. This component is responsible for an increase in the internal energy of the glass during its anelastic deformation. Possible causes of the observed effects are discussed.     

Electrotransfer in nonstoichiometric lanthanum scandate LaSc1 ? x O3 ? �� (x = 0?0.1)

The phase composition and the total and partial conductivities of ceramic samples LaSc_{1 ? x} O_{3 ? ??} (x = 0?0.1) are studied as a function of the air humidity (pH₂O = 0.04?2.35 kPa) and the oxygen partial pressure (?15 ?? logpO₂ ?? ?0.68) in a wide temperature range from 100 to 900??C as well as their thermal expansion.     

Production, Purification, and Characterization of a β-Glucosidase of Penicillium funiculosum NCL1

Penicillium funiculosum NCL1, a filamentous fungus, produced significantly higher levels of ??-glucosidase. The effect of initial pH, incubation temperature, and different carbon sources on extracellular ??-glucosidase production was studied in submerged fermentation. At 30?°C with initial pH 5.0, enzyme production was increased by 48-fold upon induction with paper mill waste, as compared to commercial cellulose powder. In zymogram analysis, four isoforms of ??-glucosidases were observed with wheat bran whereas a minimum of one isoform was observed with other carbon sources. A major ??-glucosidase (Bgl3A) with the apparent molecular weight of ~120?kDa, induced by paper mill waste, was purified 19-fold to homogeneity, with a specific activity of 1,796 U/mg. Bgl3A was a monomeric glycoprotein with 29% of neutral carbohydrate content. It showed optimum activity at pH 4.0 and 5.0, optimum temperature at 60?°C, and exhibited a half-life of 1?h at 60?°C. K _m of Bgl3A was found to be 0.057?mM with p-nitrophenyl ??-d-glucoside and V _max was 1,920 U/mg. The purified enzyme exhibited glucose tolerance with a K _i of 1.5?mM. Bgl3A readily hydrolyzed glucosides with ??-linkage. Bgl3A activity was enhanced (156%) by Zn²⁺ and was not affected by other metal cations and reagents. The supplementation of Bgl3A (5 U/mg) with Trichoderma reesei cellulase complex (5 FPU/mg) resulted in about 70% of enhanced glucose production, which emphasizes the industrial importance of Bgl3A.     

High-precision analysis of ethanol in bioethanol by gas chromatography with flame ionization detector

This paper describes the establishment and validation of gas chromatography-flame ionization detector (GC-FID) method for the determination of ethanol amount fraction in bioethanol samples. A general view of the development and optimization of the method is presented. The main aim of this study is the calculation of validation parameters. Selectivity of the method was determined. Linearity (R ²?>?0.999) was obtained in the range from 9.0 to 3040???g of ethanol per sample (because the mass of the test sample used was around 200?mg, this corresponds to 45?C2200???g?g^?1). The method showed good recoveries (average 99.0?%), and the relative standard deviation for repeatability and intermediate precision was 4.5 and 5.5?%, respectively. The limit of detection (LOD) and limit of quantification (LOQ) were calculated as 10 and 30???g?g^?1, respectively. The uncertainty budget was finally done according to the ??Guide to the Expression of Uncertainty in Measurement?? (GUM), and the relative expanded uncertainty was 4.8?% at coverage of k?=?2.     

Kinetics of CH(X2Π) radical reactions with propane,isobutane and neopentane

Rate constants over the temperature range 298–689 K are reported for the reaction of CH(X²Π) radicals with C₃H₈, i-C₄H₁₀ and neo-C₅H₁₂. The CH radical was generated by multiphoton laser photolysis of CHBr₃ and its disappearance monitored by laser-induced fluorescence (LIF) at 429.8 nm. Absolute rate constants were determined as a function of temperature and total pressure. The following Arrhenius parameters were derived: k = (1.85 ± 0.13) × 10⁻¹⁰ exp[(240±30)/T] cm³/s for CH+propane; k = (2.03±0.19)×10⁻¹⁰ exp[(240±40)/T] cm³/s for CH+isobutane; k = (1.61±0.10)×10⁻¹⁰ exp[(340±30)/T] cm³/s for CH+neopentane, all independent of total pressure. The negative temperature dependences along with the energetics and lack of pressure effects lead to the conclusion that the reactions proceed by CH insertion into the alkane. The activated adduct thus formed rapidly decomposes via many energetically accessible channels. An analysis of CH reactions with C₁ to C₅ alkanes shows an increase in the room temperature rate constants in going from C₁ to C₄ irrespective of the nature of CH bonds. The rate constant then begins to level off near ≈ 5 × 10⁻¹⁰ cm/s for C₄ and C₅ alkanes.     

Studies on the production feasibility of 64Cu by (n, p) reactions on Zn targets in Dhruva research reactor

⁶⁴Cu is an useful radionuclide for both PET imaging and targeted therapy, as it decays by three different modes, namely, electron capture (41%), ??^? (40%) and positron emission (19%). ⁶⁴Cu is generally produced by ⁶⁴Ni (p, n) reaction in a cyclotron for medical use. High specific activity ??no carrier added?? grade ⁶⁴Cu by ⁶⁴Zn (n, p) route is an alternative for research studies and was hence explored. 10?mg zinc foil target (48.63% in ⁶⁴Zn) was irradiated in the medium flux reactor Dhruva at a thermal neutron flux of ~5.6?×?10¹³ n?cm^?2?s^?1 for 3?days. The irradiated Zn foil was dissolved in 5?mL 10?M HCl and ⁶⁴Cu was separated by anion exchange chromatography (Dowex 1?×?8; 100?C200 mesh) at 3?M HCl conditions. ⁶⁴Cu radioactivity content and its radionuclide purity were ascertained by ??-ray spectrometry using HPGe detector coupled to a 4?K multichannel analyser system. Radiochemical separation yielded a radionuclidic purity of 99.9% ⁶⁴Cu.     

Purification and Properties of a Thermostable Xylanase GH 11 from Penicillium occitanis Pol6

An extracellular, endo-??-1,4-xylanase was purified to homogeneity from the culture filtrate of the filamentous fungus Penicillium occitanis Pol6, grown on oat spelt xylan. The purified enzyme (PoXyn2) showed a single band on SDS?CPAGE with an apparent molecular weight of 30?kDa. The xylanase activity was optimal at pH?3.0 and 65?°C. The specific activity measured for oat spelt xylan was 2,368?U?mg^?1. The apparent K _m and V _max values were 8.33?mg?ml^?1 and 58.82???mol?min^?1?ml^?1, respectively, as measured on oat spelt xylan. Thin-layer chromatography experiments revealed that purified PoXyn2 degrades xylan in an endo-fashion releasing xylobiose as main end product. The genomic DNA and cDNA encoding this protein were cloned and sequenced. This PoXyn2 presents an open reading frame of 962?bp, not interrupted by any introns and encoding for a mature protein of 320 amino acids and 29.88?kDa.     

On the influence of the milling time in the Curie temperature of Fe56Co7Ni7Zr10B20 investigated by magnetic thermogravimetric analysis

Magnetic thermogravimetric analysis (TGM) was used to investigate the influence of the milling time (t _mill) in the Curie temperature (T _C) of nanocrystalline powders and of a melt-spun amorphous ribbon with composition Fe₅₆Co₇Ni₇Zr₁₀B₂₀. The TGM analysis was carried in a continuous flow of 99.99% pure argon from room temperature up to 1250?K. A magnetic field of 100?Oe was applied throughout the measurements. Nanopowders of Fe₅₆Co₇Ni₇Zr₁₀B₂₀ were produced by mechanical alloying the samples in an argon atmosphere for milling times ranging from 1 to 100?h. The samples were characterized by X-ray diffraction and by scanning electron microscopy. The average particle size decreased from 45.4?nm for a powder milled for 1?h to 5?nm after being milled for 100?h. Moreover, T _C (=1126.4?±?4.4?K) was found to be nearly independent of t _mill while for the melt-spun amorphous ribbon it was found to be substantially smaller (T _C?=?482?K). This is a clear indication that T _C is quite sensitive to the degree of amorphosity present in the sample. The activation energy associated to the crystallization process was estimated from DSC data by using the Kissinger??s method to be 193?kJ/mol.     

LC Determination of Trace Biogenic Amines in Foods Samples with Fluorescence Detection and MS Identification

A pre-column derivatization method for the simple, sensitive determination of biogenic amines using 10-ethyl-acridine-3-sulfonyl chloride (EASC) as labeling reagent with fluorescence detection and mass spectrometry (MS) identification has been developed. After pre-column derivatization, the labeled biogenic amines were separated on a Hypersil BDS-C18 column by gradient elution. The derivatives showed an intense protonated molecular ion corresponding m/z [M + H]⁺ in positive-ion mode. The collision-induced dissociation of protonated molecular ion formed specific fragment ions at m/z 196.5, m/z 222.7, m/z 224.4 and m/z 272.5, m/z 286.2. Satisfactory linear responses were observed at the concentration range of 0.02?C10 ??mol L^?1 with coefficients of >0.9993. Detection limits obtained by the analysis of a derivatized standard containing 0.2 pmol of each biogenic amine, were from 20.22 to 109.2 fmol (at a signal-to-noise ratio of 3). The relative standard deviations of retention times and peak areas for each biogenic amine were <0.96 and 3.22%, respectively. Recoveries except for PUT were in the range of 96.7?C103.6% for chicken sausage and 95.8?C104.6% for pork sausage The established method for the determination of biogenic amines except for PUT from real samples was satisfactory.     

LC Tissue Distribution Study of Paeonol in Rats after Oral Administration

Paeonol, an important constituent of the traditional Chinese medicine Cortex Moutan, has a variety of bioactivity. A simple and sensitive HPLC?CUV method has been developed for analysis of paeonol in different rat tissue (heart, liver, spleen, lung, kidney, and brain). Bio-samples were prepared by simple protein precipitation, and separation of paeonol was achieved on a C₁₈ column with methanol?C2% glacial acetic acid solution 70:30 (v/v) as mobile phase at a flow rate of 1.0 mL min^?1. UV detection was at 274 nm and the column temperature was 30 °C. Linearity was good between 0.025 and 5.0 ??g mL^?1 (r ² ?? 0.9990) for tissue samples. Inter-day and intra-day accuracy (as relative error, RE) and precision (as relative standard deviation, RSD) were <5.94 and 6.05%, respectively. The limit of detection was 0.025 ??g mL^?1 and extraction recovery for all samples was ??85.86%. The method was successfully applied to a tissue-distribution study after oral administration of 40 mg kg^?1 paeonol to healthy Sprague?CDawley rats. The study showed that paeonol was quickly distributed and eliminated after oral administration; liver and kidney were the major distribution tissues of paeonol in rats, and paeonol quickly passed through the blood?Cbrain barrier. It was also found there was no long-term accumulation of paeonol in rat tissues.     

Adsorption of uranium from aqueous solution using HDTMA+-pillared bentonite: isotherm, kinetic and thermodynamic aspects

The ability of hexadecyltrimethylammonium cation pillared bentonite (HDTMA⁺-bentonite) has been explored for the removal and recovery of uranium from aqueous solutions. The adsorbent was characterized using small-angle X-ray diffraction, high resolution transmission electron microscopy, and Fourier transform infrared spectroscopy. The influences of different experimental parameters such as solution pH, initial uranium concentration, contact time, dosage and temperature on adsorption were investigated. The HDTMA⁺-bentonite exhibited the highest uranium sorption capacity at initial pH of 6.0 and at 80?min. Adsorption kinetics was better described by the pseudo-second-order model and adsorption process could be well defined by the Langmuir isotherm. The thermodynamic parameters, ??G° (308?K), ??H°, and ??S° were determined to be ?31.64, ?83.84?kJ/mol, and ?169.49?J/mol/K, respectively, which demonstrated the sorption process of HDTMA⁺-bentonite towards U(VI) was feasible, spontaneous, and exothermic in nature. The adsorption on HDTMA⁺-bentonite was more favor than Na-bentonite, in addition the saturated monolayer sorption capacity increased from 65.02 to 106.38?mg/g at 298?K after HDTMA⁺ pillaring. Complete removal (??100%) of U(VI) from 1.0?L simulated nuclear industry wastewater containing 10.0?mg U(VI) ions was possible with 1.5?g HDTMA⁺-bentonite.     

Effects of Ionic Liquids on the Growth of Arthrobacter simplex and Improved Biodehydrogenation in an Ionic Liquid-Containing System with Immobilized Cells

Dehydrogenated derivatives of corticosteroids are usually more effective than their precursors in treating diseases. In this study, the toxicity of seven water-miscible ionic liquid and three organic solvents to the biocatalyst Arthrobacter simplex UR016 was tested to evaluate the possibility of biodehydrogenation from 17??-hydroxy-16??-methyl-pregna-4,9(11)-diene-3,20-dione (HMPDD) to 17??-hydroxy-16??-methyl-pregna-1,4,9(11)-triene-3,20-dione (HMPTD) in an ionic liquid-containing system. Although most tested room temperature ionic liquids (RTILs) showed higher toxicities to A. simplex UR016 than organic solvents, bacterial growth was promoted in the presence of [EMIM](l)-Lac or [BMIM](l)-Lac at concentrations below 2.5?mmol/l, especially [EMIM](l)-Lac, presented the lowest toxicity to A. simplex. Following immobilization investigations, a conversion ratio of 89.9?% was achieved with a cell biomass of 10?g/l (dry cell weight/reaction mixture volume) in the polyethylene glycol (PEG)-modified calcium alginate gel bead, a suitable matrix for cell immobilization. Further studies indicated that the conversion ratio can be improved by increasing cell loading to 60 beads per flask (containing 30?ml reaction mixture). Under optimal conditions with a [EMIM](l)-Lac content of 0.3?%, the conversion ratio reached 93.4?%, the highest value ever reported.     

Edge-shared [M2Cl10]2? complexes of reaction between oxophilic group 4 metal and phosphorus ylides

The reactions between oxophilic group 4 metal chlorides, ??-keto ylides in THF, led to the formation of titanium, zirconium and hafnium edge-shared [M₂Cl₁₀]^2? complexes (1a?C3f). We describe that the reaction between MCl₄ (M = Ti, Zr and Hf) with phosphorus ylides produce edge-shared [M₂X₁₀]^2? complexes instead of O-coordination previously reported complexes. Adding dimethyl sulfoxide (DMSO) to these complexes in room temperature crystalline solid [M(DMSO)₈] · 4Cl · mH₂O · DMSO] (M = Ti (1g), Zr (2g) and Hf (3g); m = 0?C3) together with phosphonium salts in mother liquid were formed. The compounds were characterized by elemental analysis, IR and ¹H, ¹³C and ³¹P NMR spectroscopy.     

Submerged Arc Breakdown of Methylene Blue in Aqueous Solutions

Low voltage, low energy submerged pulsed arcs between a pair of carbon or iron electrodes with a pulse repetition rate of 100?Hz, energies of 2.6?C192?mJ and durations of 20, 50 and 100???s were used to remove methylene blue (MB) contamination from 30?ml aqueous solutions. The MB concentration decreased exponentially with rates of 0.0006?C0.0143?s^?1 during processing with the carbon electrode pair. With the iron electrodes, the MB concentration initially decreased faster (0.030?s^?1) than with the carbon electrodes, but later saturated. However when microparticles produced with the iron electrodes were periodically filtered, the high removal rate was maintained. Under these conditions, the volume of water which can be treated per unit energy expenditure was much higher with the submerged arc than with other plasma processes. A kinetic model based on MB degradation by OH· radicals formed by the discharge was formulated. The higher initial MB removal rate with iron electrodes is explained by additional OH· production from Fenton??s reaction between Fe⁺⁺ and H₂O₂ produced by the discharge. This rate is maintained if the eroded iron particles are filtered, but if eroded iron particles accumulate, degradation slows down and stops, possibly because the iron particles catalytically decompose H₂O₂ and hence stops Fenton??s reaction, and either directly or via increased Fe⁺⁺ dissolved from the particles, scavenge the OH· radicals.     

Electron spin resonance study of γ-irradiated poly(acrylic acid)

Electron spin resonance (ESR) spectra of poly(acrylic acid) (PAA) γ-irradiated in air at room temperature and recorded at room temperature and at liquid-nitrogen temperature have been studied to identify the radiation products. The ESR spectra are composed of eight lines with hyperfine splittings of 23 ± 1 G and 11 ± 1 G. The method of least-squares total curve fitting, employing the Lorentzian line shape function, to the observed spectra enabled the assignment of the spectra. Computed spectra obtained by the superposition of a singlet and the spectra due to chain radicals are considered to give the best fits to the observed ESR spectra. The singlet is assigned to the radicals COOH, and the component 10-line spectra are assigned to the chain radicals CH₃? CH? CH₂ ～ and/or ～ CH₂? CH? CH₂ ～. The observed change in line shape with temperature of the ESR spectra is attributed to the hindered oscillations of the methyl groups about the C_α? C_β bond axis of the chain radicals. The existence of the methyl groups is confirmed by the measurement of infrared absorption.