Optimal composition of a new polymer gel dosimeter-DEMBIG

Polymeric gel dosimeters are used to verify three-dimensional (3D) dose distributions of various types of radiotherapy treatments, particularly radiosurgery. The present paper investigates the low toxicity and high dose response of a new acrylate gel. The optimal recipe with the best linearity (R ² = 0.998) is 7% gelatin, 5% 2-(dimethylamino) ethyl acrylate monomer, and 4% N′N′-methylene-bisacrylamide crosslinker. The dose range is 0–30 Gy, and the temporal stability time is 12 h after irradiation. No significant energy dependency has been observed. The results show that the 2-(dimethylamino) ethyl acrylate N′N′-methylene-bisacrylamide gelatin gel is a potential 3D dosimeter.     

Effect of cellulose nanofiber dimensions on sheet forming through filtration

Four different cellulose nanofibers samples were prepared from northern bleached softwood kraft fibers. Fiber diameter distributions were measured from SEM images. Fiber aspect ratios ranging from 84 to 146 were estimated from fiber suspension sedimentation measurements. Three samples had heterogeneous distributions of fiber diameters, while one sample was more homogeneous. Sheet forming experiments using filters with pores ranging from 150 to 5 μm showed that the samples with a heterogeneous distribution of fiber dimensions could be easily formed into sheets at 0.2% initial solids concentration with all filter openings. On the other hand, sheets could only be formed from the homogenous sample by using 0.5% or more initial solids content and a lower applied vacuum and smaller filter openings. The forming data and estimated aspect ratios show reasonable agreement with the predictions of the crowding number and percolation theories for the connectivity and rigidity thresholds for fiber suspensions.     

Percolation, phase separation, and gelation in fluids and mixtures of spheres and rods

The relationship between kinetic arrest, connectivity percolation, structure and phase separation in protein, nanoparticle, and colloidal suspensions is a rich and complex problem. Using a combination of integral equation theory, connectivity percolation methods, nai?ve mode coupling theory, and the activated dynamics nonlinear Langevin equation approach, we study this problem for isotropic one-component fluids of spheres and variable aspect ratio rigid rods, and also percolation in rod-sphere mixtures. The key control parameters are interparticle attraction strength and its (short) spatial range, total packing fraction, and mixture composition. For spherical particles, formation of a homogeneous one-phase kinetically stable and percolated physical gel is predicted to be possible, but depends on non-universal factors. On the other hand, the dynamic crossover to activated dynamics and physical bond formation, which signals discrete cluster formation below the percolation threshold, almost always occurs in the one phase region. Rods more easily gel in the homogeneous isotropic regime, but whether a percolation or kinetic arrest boundary is reached first upon increasing interparticle attraction depends sensitively on packing fraction, rod aspect ratio and attraction range. Overall, the connectivity percolation threshold is much more sensitive to attraction range than either the kinetic arrest or phase separation boundaries. Our results appear to be qualitatively consistent with recent experiments on polymer-colloid depletion systems and brush mediated attractive nanoparticle suspensions.     

Kinetic investigation on thermal decomposition of organophosphorous compounds

In this paper, the thermal behaviours of two organophosphorous compounds, N,N-dimethyl-N′,N′-diphenylphosphorodihydrazidic (NDD) and diphenyl amidophosphate (DPA), were studied by thermogravimetery (TG), differential thermal analysis (DTA) and differential scanning calorimetery (DSC) techniques under non-isothermal conditions. The results showed that NDD melts about 185 °C before it decomposes. NDD decomposition occurs in two continuous steps, in the 190–410 °C temperature range. First thermal degradation stage for NDD results a broad exothermic peak in the DTA curve that is continued with a small exothermic peak at the end of decomposition process. On the other hand, applying TG-DTA techniques indicates that DPA melts about 150 °C before it decomposes. This compound decomposes in the temperature range of 230 to 330 °C in two steps. These steps are endothermic and exothermic, respectively. Activation energy and pre-exponential factor for the first step of decomposition of each compound were found by means of Kissinger method and were verified by Ozawa–Flynn–Wall method. Activation energy obtained by Kissinger method for the first stage of NDD and DPA decompositions are 138 and 170 KJ mol⁻¹, respectively. Finally, the thermodynamic parameters (ΔG ^#, ΔH ^# and ΔS ^#) for first step decomposition of investigated organophosphorous were determined.     

Thermoanalytical behaviour of carbaryl and its copper(II) and zinc(II) complexes

Non-isothermal techniques, i.e. thermogravimetry (TG) and differential scanning calorimetry (DSC), have been applied to investigate the thermal behaviour of carbaryl (1-naphthyl-N-methylcarbamate = 1-Naph-N-Mecbm) and its complexes, M(1-Naph-N-Mecbm)₄X₂, where M = Cu, X = Cl, NO₃ and CH₃COO and M = Zn, X = Cl. Carbaryl and Zn(1-Naph-N-Mecbm)₄Cl₂ complex exhibit two-stage thermal decomposition while the copper(II) complexes exhibit three and four-stage decomposition in their TG curves. The nature of the metal ion has been found to play highly influential role on the nature of thermal decomposition products as well as energy of activation ‘E*’. The presence of different anions does not seem to alter the thermal decomposition patterns. The complexes display weak to medium intensity exothermic and endothermic DSC curves, while the free ligand exhibits two endothermic peaks. The kinetic and thermodynamic parameters namely, the energy of activation ‘E*’, the frequency factor ‘A’ and the entropy of activation ‘S*’ etc. have been rationalized in relation to the bonding aspect of the carbaryl ligand. The nature and chemical composition of the residues of the decomposition steps have been studied by elemental analysis and FTIR data.     

Conductivity,proton percolation,and gelation during the network growth in a flexible chain diepoxide and diamine mixture

The conductivity of a stoichiometric mixture of diglycidyl ether of 1,4‐butanediol and 1,6‐hexamethylene diamine has been studied during its polymerization at several temperatures where the ultimate product is a crosslinked gel. The decrease in the dc conductivity, σ₀, with the polymerization time, t, fits an equation for bond percolation, σ₀ ∼ [(t_gel‐t)/t_gel]^p, and yields a gelation time, t_gel which agrees with the t_gel determined from the viscosity and shear modulus measurements. It is proposed that as one covalent bond forms on chemical reaction, an indeterminable number of intermolecular H‐bonds in the structure vanish, and protonic conduction is disrupted. Thus, as the original H‐bond network gives way to a covalently bonded network, the mechanical rigidity increases, and protonic conductivity decreases. The gel point is reached when the increase in the number of covalent bonds brings the liquid's state up to its rigidity percolation threshold, and the decrease in the number of H‐bonds brings it down to its electrical percolation threshold. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 122–126, 2000     

Modeling force-induced bio-polymer unfolding

We study the conformations of polymer chains in a poor solvent, with and without bending rigidity, by means of a simple statistical mechanics model. This model can be exactly solved for chains of length up to N = 55 using exact enumeration techniques. We analyze in detail the differences between the constant force and constant distance ensembles for large but finite N. At low temperatures, and in the constant force ensemble, the force–extension curve shows multiple plateaus (intermediate states), in contrast with the abrupt transition to an extended state prevailing in the N → ∞ limit. In the constant distance ensemble, the same curve provides a unified response to pulling and compressing forces, and agrees qualitatively with recent experimental results. We identify a cross-over length, proportional to N, below which the critical force of unfolding decreases with temperature, while above, it increases with temperature. Finally, the force–extension curve for stiff chains exhibits “saw-tooth” like behavior, as observed in protein unfolding experiments.     

Rate constant distribution for the target problem on lattice clusters above the percolation threshold

A diffusion-controlled reaction A+B (N _A ≫N _B (0)) has been studied by computer simulation of random walk of particles A on a simple cubic lattice with randomly closed sites above the percolation threshold. It is shown that at low concentrations of walkers the nonexponential decay of particles B derives mainly from rate constant distribution.     

Density functional theory study on (F2AlN3) n (n = 1–4) clusters

Possible geometrical structures and relative stabilities of (F₂AlN₃) _n (n = 1–4) clusters were studied using density functional theory at the B3LYP/6-311+G* level. The optimized clusters (F₂AlN₃) _n (n = 2–4) possess cyclic structure containing Al–N_α–Al linkages, and azido in azides has linear structure. The IR spectra of the optimized (F₂AlN₃) _n (n = 1–4) clusters have three vibrational sections, the whole strongest vibrational peaks lie in 2218–2246 cm⁻¹, and the vibrational modes are N₃ asymmetric stretching vibrations. Trends in thermodynamic properties with temperature and oligomerization degree n are discussed, respectively. A study of their thermodynamic properties suggests that monomer 1A forms the most stable clusters (2A, 3A, and 4B) can occur spontaneously in the gas phase at temperatures up to 800 K.     

Thermal study of mononuclear Pd(II) complexes of the type [Pd(X)<Subscript>2</Subscript>(Rtu)(PPh<Subscript>3</Subscript>)] (X = Cl,SCN; Rtu = <Emphasis Type="Italic">N</Emphasis>-methylthiourea, <Emphasis Type="Italic">N</Emphasis>-phenylthiourea)

The synthesis, spectroscopic characterization, and thermal analysis of the compounds [Pd(X)₂(mtu)(PPh₃)] (X = Cl⁻ (1), SCN⁻ (2); mtu = N-methylthiourea; PPh₃ = triphenylphosphine) and [Pd(X)₂(phtu)(PPh₃)] (X = Cl⁻ (3), SCN⁻ (4); phtu = N-phenylthiourea) are described. The thermal decomposition of the compounds occurs in two, three, or four stages and the final decomposition products were identified as Pd⁰ by X-ray powder diffraction. The thermal stability order of the complexes is 4 > 3>2 > 1.     

Solid state electrochemical of the erbium hexacyanoferrate-modified carbon ceramic electrode and its electrocatalytic oxidation of <Emphasis Type="SmallCaps">l</Emphasis>-cysteine

A kind of erbium hexacyanoferrate (ErHCF)-modified carbon ceramic electrodes (CCEs) fabricated by mechanically attaching ErHCF samples to the surface of CCEs derived from sol–gel technique was proposed. The resulting modified electrodes exhibit well-defined redox responses with the formal potential of +0.215 V [vs saturated calomel electrode (SCE)] at a scan rate of 20 mV s⁻¹ in 0.5 M KCl (pH 7) solution. The voltammetric characteristics of the ErHCF-modified CCEs were investigated by voltammetry. Attractively, the ErHCF-modified CCEs presented good electrocatalytic activity with a marked decrease in the overvoltage about 400 mV for l-cysteine oxidation. The calibration plot for l-cysteine determination was linear at 5.0 × 10⁻⁶–1.3 × 10⁻⁴ M with a linear regression equation of I(A) = 0.558 + 0.148c (μM) (R ² = 0.9989, n = 20), and the detection limit was 2 × 10⁻⁶ M (S/N = 3). At last, the ErHCF-modified CCEs were used for amperometric detection of l-cysteine in real samples.     

Orientation of cellulose crystallites in regenerated cellulose fibres under tensile and bending loads

The degree of orientation in regenerated cellulose fibres with a diameter of 36μm was determined using position-resolved synchrotron X-ray microbeam diffraction. The fibres were characterized in unstrained condition, under tensile strain, and in bending. A homogeneous distribution of the degree of crystalline orientation (Herman’s orientation factor f _c = 0.85) across the fibre thickness was found in the unstrained fibre. The degree of orientation of cellulose crystallites increased in a linear manner with increasing tensile strain applied to the fibre. Also in bending, a linear relationship between applied strain and the degree of crystalline orientation was found, where f _c increased in tension and decreased in compression. This linear relationship was found to be valid for both the tensile and the compressive zone of the bent fibre.     

Preparation and thermal behaviour of divalent transition metal complexes of pyromellitic acid with hydrazine

Hydrazine forms two different types of complexes with divalent metal ions and pyromellitic acid (H₄pml) in aqueous medium: (i) hydrazinium complexes of formulae, (N₂H₅)₂M(pml)·xH₂O, where x = 3 for M=Ni and x = 4 for M=Co or Zn, and (N₂H₅)₂Mn(H₂pml)₂, at pH 4.5, (ii) neutral hydrazine complexes with formulae, M₂(pml)(N₂H₄) _n ·xH₂O where M=Co or Ni when n = 4 and x = 5 or 4 and M=Zn or Cd when n = 2, and x = 4 or 3 at pH 7, and M(H₂pml)(N₂H₄)·xH₂O where x = 4; M=Cu and x = 0; M=Hg, at pH 3, 7.5, respectively. All the complexes are insoluble in water, alcohol and ether. The N–N stretching frequency (990–1,007 cm⁻¹ for coordinated hydrazinium ion and 956–985 cm⁻¹ for bridged neutral hydrazine) indicates the nature of hydrazine present in the complexes. Simultaneously TG-DTA analysis indicates that hydrazinium complexes undergo dehydration and dehydrazination in a single step endothermally in the range of 289–300 °C whereas neutral hydrazine complexes undergo endothermic dehydration (~100 °C) followed by exothermic dehydrazination in the temperature range, 253–332 °C. The anhydrous metal carboxylates further decompose exothermally to leave the respective metal oxides or metal carbonates except zinc, which gives its oxalate as the end product. X-ray powder patterns indicate that even the complexes with the same formulation possess no isomorphism.     

Extraction behavior of cerium by tetraoctyldiglycolamide from nitric acid solutions

The diamide N,N,N′,N′-tetraoctyldiglycolamide (TODGA) was synthesized and characterized. The prepared TODGA was applied for extraction of Ce(III) from nitric acid solutions. The equilibrium studies included the dependencies of cerium distribution ratio on nitric acid, TODGA, nitrate ion, hydrogen ion and cerous ion concentrations. Analysis of the results indicates that the main extracted species is Ce(TODGA)₂(NO₃)₃HNO₃. The capacity of Ce loading is approximately 45 mmol/L for 0.1 M solution of TODGA in n-hexane. Finally, the thermodynamic parameters were calculated: K (25 °C) = 3.8 × 10³, ΔH = −36.7 ± 1.0 kJ/mol, ΔS = −54.6 ± 3.0 J/K mol, and ΔG = −20.4 ± 0.1 kJ/mol.     

Influence of temperature on the reactivity of phosphorus acid esters in reverse micellar systems based on sodium bis(2-ethylhexyl)sulfosuccinate

A change in the reactivity of ethyl p-nitrophenyl chloromethylphosphonate in the sodium bis(2-ethylhexyl)sulfosuccinate-n-nonane-water system around the percolation threshold was found. Study of location sites of the reactants by NMR self-diffusion and optical spectroscopy and modeling of the kinetic data in terms of the pseudophase approach demonstrated that below the percolation threshold, the reaction occurs in the surface layer. The observed rate constant for substrate hydrolysis in a microemulsion below the percolation threshold is described by the Arrhenius equation, like that in aqueous solutions. Above the percolation threshold, the slope of the Arrhenius plot sharply changes, which is apparently due to a change in the reactant location pattern and, hence, the microscopic properties of the medium in the region of their solubilization. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1407–1414, June, 2005.     

Purification and Characterization of a Low Molecular Weight Endo-xylanase from Mushroom <Emphasis Type="Italic">Termitomyces clypeatus</Emphasis>

A low molecular weight endo-xylanase (EC 3.2.1.8) was purified from an edible mushroom Termitomyces clypeatus grown in submerged medium with oat spelt xylan. Xylanase was purified to apparent homogeneity by ammonium sulfate fractionation and gel filtration chromatography. Its molecular weight was determined by gel filtration chromatography and sodium dodecyl sulfate-polyacrylamide gel electrophoresis to be 12 kDa. The enzyme was found to be most active at 50°C and pH 5.0, being most stable at pH 6.5. The K_m for oat spelt xylan was determined to be 10.4 mg/ml. The specificities of the enzyme was observed to be highly specific towards oat spelt xylan and was inhibited by mercuric chloride (HgCl₂), N-bromosuccinimide, and trans-1,2-diaminocyclohexane-N′,N′,N′,N′-tetraacetic acid strongly. The inhibitory action of N-bromosuccinimide on enzyme confirmed the presence of one tryptophan residue in its substrate-binding site. Amino acid analysis for xylanase showed the presence of high amount of hydrophobic serine, glycine, threonine, and alanine residues. The N-terminal sequencing study for the previously purified and characterized 56 kDa xylanolytic amyloglucosidase reveal the presence of 33.30% identity with glucoamylase chain A from Aspergillus awamori. The N-terminal sequence analysis of the present 12 kDa enzyme showed highest similarity (72.22% identity) towards xylanase from Neurospora crassa.     

Molecular energetics of alkyl substituted pyridine <Emphasis Type="Italic">N</Emphasis>-oxides

The standard (p° = 0.1 MPa) energies of combustion in oxygen, at T = 298.15 K, for the solid compounds 2-methylpyridine-N-oxide (2-MePyNO), 3-methylpyridine-N-oxide (3-MePyNO) and 3,5-dimethylpyridine-N-oxide (3,5-DMePyNO) were measured by static-bomb calorimetry, from which the respective standard molar enthalpies of formation in the condensed phase were derived. The standard molar enthalpies of sublimation, at the same temperature, were measured by Calvet microcalorimetry. From the standard molar enthalpy of formation in gaseous phase, the molar dissociation enthalpies of the N–O bonds were derived, and compared with values of the dissociation enthalpies of other N–O bonds available for other pyridine-N-oxide derivatives.     

Novel syndiotactic polystyrene/BaTiO3-graphite nanosheets three-phase composites with high dielectric permittivity

Novel three-phase composites were prepared by embedding graphite nanosheets (GNs) and BaTiO₃ nanoparticles into syndiotactic polystyrene (sPS) matrix via a solution blending and flocculation method. The dependences of electric and dielectric properties of the resultant sPS/BaTiO₃-GNs composites on volume fractions of GNs (f_GNs) and frequency were investigated. The percolation theory was employed to explain the electric and dielectric behavior of sPS/BaTiO₃-GNs composite. It was found that the sPS/BaTiO₃-GNs composite showed an obvious insulator-conductor transition with a much low percolation threshold of f_GNs = 1.44 vol%. The dielectric permittivity of sPS/BaTiO₃-GNs composite reached as high as 51.8 at 100 Hz at percolation threshold, which was about 18 and 7 times higher than that of pure sPS and sPS/BaTiO₃ composite, respectively.     

Heat capacities of antiferromagnetic dimer-Mott insulators in organic charge-transfer complexes

Heat capacity measurements of quasi-two-dimensional Mott insulating compounds consisting of BEDT-TTF (bisethylendithiotetrathiafulubalene) donor molecules and counter anions were performed by the thermal relaxation calorimetry technique for single crystal samples. No distinct thermal anomalies at the predicted antiferromagnetic transition temperatures in κ-(BEDT-TTF)₂Cu[N(CN)₂]Cl (T _N = 27 K) and β′-(BEDT-TTF)₂ICl₂ (T _N = 22 K) were observed. These results demonstrate that the Mott insulating state of the organic salts which are dominated by the strong two-dimensional intra-layer antiferromagnetic interactions between neighboring S = 1/2 spins shows somewhat different features from the simple quasi-two-dimensional Heisenberg model with S = 1/2. The strong quantum fluctuations produced by the electron correlations suppress the long-range character of the spin correlations, which seems to be an important aspect of this kind of Mott insulating materials.     

Determination of butoxyacetic acid (biomarker of ethylene glycol monobutyl ether exposure) in human urine candidate reference material

Ethylene glycol monobutyl ether (EGBE), an industrial solvent, is absorbed by the body not only by inhalation but also by dermal absorption (liquid or vapour). EGBE is metabolized to butoxyacetic acid (BAA). Pooled freeze-dried urine candidate reference material (RM) was prepared from urine obtained from persons occupationally exposed to EGBE. This material has the advantage of containing butoxyacetic acid in both the free and conjugated (glutamine and glycine) forms, as found in native urine. In all GC method modifications used, acid hydrolysis was used to release BAA from its conjugated form. The amount of butoxyacetic acid in homogeneity and stability testing was measured by GC after derivatisation with N-tert-butyldimethylsilyl-N-methyltrifluoroacetamide. Detection was by MS in EI mode, in the authors’ laboratory. For interlaboratory comparison of the reference material GC methods with MS, FID, and ECD were used. Different extraction solvents (dichloromethane–isopropanol 2:1, ethyl acetate, or dichloromethane) and derivatisation reagents (trimethylsilyldiazomethane, N-tert-butyldimethylsilyl-N-methyltrifluoroacetamide) were used. Using ANOVA (at the statistical level α = 0.05) no changes were found in the concentration of butoxyacetic acid during fifteen month isochronous stability testing, or in homogeneity testing. The uncertainty contributions were u _h = 8.8 mg L⁻¹ and u _s = 6.5 mg L⁻¹. The concentration of butoxyacetic acid in freeze-dried urine RM was evaluated from the results of eight laboratory data sets within an interlaboratory comparison by use of the interactive statistical software IPECA. The contribution to total uncertainty derived from interlaboratory comparison was u _i = 12.7 mg L⁻¹. The reference value (c = 273 ± 33 mg L⁻¹) is an unweighted arithmetic average of accepted results. The value is traceable to the pure butoxyacetic acid (98% w/w; Acros Organic #257760010) used as calibrant. The uncertainty given is combined expanded uncertainty derived from the results from interlaboratory comparison, and from homogeneity and stability tests (k = 2). The reference material will be used to verify method performance in the biological monitoring of occupational exposure to EGBE.