Kinetic parameters from thermogravimetric study of used rubber granulates–polyurethane composites

From the TG data of rubber granulates, different polyurethane and composites it can be seen that the thermal decomposition for the rubber granulate and all of the composites start above 520 K. Two major mass losses for the rubber granulates and majority of the composites were observed and thermal decomposition is essentially complete by ~820 K. The changes of activation energies of lower and higher temperature decomposition, calculated according to the different equations were observed for a priori assumed first-order reaction for devolatilisation. Differences between determined and calculated results could suggest a possible reaction between polyurethane agents and rubber granulate during the composites formations.     

Beiträge zur Chemie der Alkylverbindungen von Übergangsmetallen. 58. Zur Kenntnis von 2-(Dimethylaminomethyl)ferrocenyl-Verbindungen des Vanadiums,Molybdäns,Wolframs, Thoriums und Urans

Contributions to the Chemistry of Transition Metal Alkyl Compounds. 58 On 2-(Dimethylaminomethyl)ferrocenyl Compounds of Vanadium, Molybdenum, Tungsten, Thorium, and Uranium Earlier results according to which dimethylaminomethylferrocenyl groups (FcN) are able to form stable organometallic chelate compounds were confirmed by synthesis of the heterobimetallic chelate compounds (FcN)₂VO · Li(acac) II , (FcN)MoO₂(acac) III , (FcN)WOCl₃ IV , (FcN)Th(acac)₃ V , and (FcN)UO₂(acac) VI from the corresponding metal acetylacetonates or oxidchlorides and (FcN)Li I . The new compounds were characterized by elemental analysis, the i.r., ¹H-n.m.r., and electron spectra and by their effective magnetic moments.     

Properties of monolayers of crown ethers bearing an azo and azoxy group in the macrocycle

Two methods are described for preparing monomolecular layers of crown ethers with an azo or azoxy group in the macrocycle. When the molecules used to build the monolayer are soluble in aqueous solutions, adsorptive preconcentration on mercury electrodes was used to prepare the monolayer coating. The monolayer was electroactive due to the presence of the azo or azoxy unit in the molecules. Monolayers of crown ethers bearing an azo group in the macrocycle were shown to recognize alkali metal cations present in the solution. Changes of the parameters of the voltammetric reduction peaks - peak potential and peak width, served as an indication of specific interactions of the monolayer of 13-membered and 16-membered azocrown ethers with Na⁺ and K⁺ cations, respectively.The monolayers capable of recognizing cations have also been prepared on the aqueous solution-air interface, using the Langmuir technique. In this approach, amphiphilic derivatives of the azocrowns were synthesized and the monolayer has been assembled on the subphase containing metal cations. Binding of the cation by the macrocycle has a stabilizing effect on the monolayer and higher collapse pressures are achieved than on the pure water subphase. The monolayer was transferred from the air-water interface on the solid substrate using the Langmuir-Blodgett technique. Thin mercury film electrodes on the Ag substrate, or An films evaporated on glass slides were employed as the electrode substrates. The former gave monolayer modified electrodes of higher stability.Presented at the Sixth International Seminar on Inclusion Compounds, Istanbul, Turkey, 27–31 August, 1995.     

Electrochemical vapor generation of selenium species after online photolysis and reduction by UV-irradiation under nano TiO<Subscript>2</Subscript> photocatalysis and its application to selenium speciation by HPLC coupled with atomic fluorescence spectrometry

An online UV photolysis and UV/TiO₂ photocatalysis reduction device (UV–UV/TiO₂ PCRD) and an electrochemical vapor generation (ECVG) cell have been used for the first time as an interface between high-performance liquid chromatography (HPLC) and atomic fluorescence spectrometry (AFS) for selenium speciation. The newly designed ECVG cell of approximately 115 L dead volume consists of a carbon fiber cathode and a platinum loop anode; the atomic hydrogen generated on the cathode was used to reduce selenium to vapor species for AFS determination. The noise was greatly reduced compared with that obtained by use of the UV–UV/TiO₂ PCRD–KBH₄–acid interface. The detection limits obtained for seleno-DL-cystine (SeCys), selenite (Se^IV), seleno-DL-methionine (SeMet), and selenate (Se^VI) were 2.1, 2.9, 4.3, and 3.5 ng mL^–1, respectively. The proposed method was successfully applied to the speciation of selenium in water-soluble extracts of garlic shoots cultured with different selenium species. The results obtained suggested that UV–UV/TiO₂ PCRD–ECVG should be an effective interface between HPLC and AFS for the speciation of elements amenable to vapor generation, and is superior to methods involving KBH₄.     

Multiple-injection affinity capillary electrophoresis to estimate binding constants of receptors to ligands

Multiple-injection affinity capillary electrophoresis (MIACE) is used to determine binding constants (K _b) between receptors and ligands using as model systems vancomycin and teicoplanin from Streptomyces orientalis and Actinoplanes teichomyceticus, respectively, and their binding to D-Ala-D-Ala peptides and carbonic anhydrase B (CAB. EC 4.2.1.1) and the binding of the latter to arylsulfonamides. A sample plug containing a non-interacting standard is first injected followed by multiple plugs of sample containing the receptor and then a final injection of sample containing a second standard. Between each injection of sample, a small plug of buffer is injected which contains an increasing concentration of ligand to effect separation between the multiple injections of sample. Electrophoresis is then carried out in an increasing concentration of ligand in the running buffer. Continued electrophoresis results in a shift in the migration time of the receptor in the sample plugs upon binding to their respective ligand. Analysis of the change in the relative migration time ratio (RMTR) or electrophoretic mobility (μ) of the resultant receptor–ligand complex relative to the non-interacting standards, as a function of the concentration of ligand yields a value for K _b. The MIACE technique is a modification in the ACE method that allows for the estimation of binding affinities between biological interactions on a timescale faster than that found for standard ACE. In addition sample volume requirements for the technique are reduced compared to traditional ACE assays. These findings demonstrate the advantage of using MIACE to estimate binding parameters between receptors and ligands.     

Computer simulation study of metastable ice VII and amorphous phases obtained by its melting

Molecular dynamics simulations of metastable ice VII and cubic ice Ic are carried out in order to examine (1) the ability of commonly used water interaction potentials to reproduce the properties of ices, and (2) the possibility of generating low-density amorphous (LDA) structures by heating ice VII, which is known to transform to LDA at approximately 135 K at normal pressure [S. Klotz, J. M. Besson, G. Hamel, R. J. Nelmes, J. S. Loveday, and W. G. Marshall, Nature (London) 398, 681 (1999)]. We test four simple empirical interaction potentials of water: TIP4P [W. L. Jorgensen, J. Chandrasekhar, J. D. Madura, R. W. Impey, and M. L. Klein, J. Chem. Phys. 79, 926 (1983)], SPC/E [H. J. C. Berendsen, J. R. Grigera, and T. P. Straatsma, J. Phys. Chem. B 91, 6269 (1987)], TIP5P [M. W. Mahoney and W. L. Jorgensen, J. Chem. Phys. 112, 8910 (2000)], and ST2 [F. H. Stillinger and A. Rahman, J. Chem. Phys. 60, 1545 (1974)]. We have found that TIP5P ice VII melts at 210 K, TIP4P at 90 K, and SPC/E at 70 K. Only TIP5P water after transition has a structure similar to that of LDA. TIP4P and SPC/E have almost identical structures, dissimilar to any known water or amorphous phases, but upon heating both slowly evolve towards LDA-like structure. ST2 ice VII is remarkably stable up to 430 K. TIP4P and SPC/E predict correctly the cubic ice collapse into a high-density amorphous ice (HDA) at approximately 1 GPa whereas TIP5P remains stable up to approximately 5 GPa. The densities of the simulated ice phases differ significantly, depending on the potential used, and are generally higher than experimental values. The importance of proper treatment of long-range electrostatic interactions is also discussed.     

Estimating measurement uncertainty in an afternoon. A case study in the practical application of measurement uncertainty

The ISO/IEC 17025:1999 standard requires chemical testing laboratories to have an estimate of the uncertainty of their measurements. This is a new requirement for many laboratories and there is confusion as to how to estimate uncertainty. Concerns have been raised about the time and effort required to obtain uncertainty estimates.Uncertainty budgets were prepared for the measurement of benzene, toluene, ethyl benzene and xylenes (BTEX) in water using purge and trap coupled with GC/MS. A time limit of one working afternoon (2 pm–5.30 pm) was imposed for preparing the uncertainty estimate. Details of the uncertainty estimate for toluene are described.The method in question had been in routine use for several years and the laboratory held third party (NATA) accreditation for the test. Consequently a considerable amount of performance data was readily available. Relevant information was extracted from the documented test method, validation data, instrument calibration and from routine quality control. This data was combined according to the principles of the ISO Guide to the Expression of Uncertainty, as promulgated in the Eurachem document "Quantifying Uncertainty in Analytical Measurement."The uncertainty estimates were compared to estimates obtained from generalised empirical models (the Horwitz and Lowthian equations), and from interlaboratory studies of this analysis.A traceability chain from routine measurements to the SI units of metre, kilogram and mole is described.Realistic and useful uncertainty estimates were obtained with a few hours work using data extant in the laboratory.     

Progress in the realisation of an autonomous environmental monitoring device for ammonia

Progress in the development of a micro-fluidic system for colorimetric monitoring of ammonia in drinking and wastewater is described. The ultimate goal is to have a miniaturised instrument that can produce accurate, reliable measurements, is easy to operate, has minimal power consumption, and can operate autonomously for a year. In this study, the indophenol reaction is incorporated into a simple, reliable analytical micro-fluidic system. Absorbance measurements for the blue ammonia-indophenol complex formed in the micro-fluidic system are shown. A key issue is the limiting stability of hypochlorite, a reagent used in the assay. The effects of hypochlorite concentration and impurities on the stability of hypochlorite are investigated and discussed. Decomposition is shown to be very dependent on the presence of heavy-metal impurities. With low levels of these catalytic metals and careful storage, hypochlorite has been shown to be stable for over a year.     

Surface patterns of block copolymers in thin layers after vapor treatment

A systematic study of formation of surface patterns in block copolymer thin layers after their exposure to solvent vapors was performed. The studied effect involves layers of thickness approximately equal to the ordering size of polymers - about 45 nm. Experiments were performed on three styrene - methacrylate derivative block copolymers, synthesized by living anionic polymerization: poly(4-octylstyrene)-block-poly(butyl methacrylate), poly(4-fluorostyrene)-block-poly(butyl methacrylate) and poly(p-octylstyrene)-block-poly(methyl methacrylate). The polymers were exposed to vapors of chloroform, 1,4-dioxane, hexane, acetone and tetrahydrofuran.     

Alkyl (C<Subscript>10</Subscript>, C<Subscript>12</Subscript>, C<Subscript>14</Subscript> and C<Subscript>16</Subscript>) triphenyl phosphonium bromide influenced cloud points of nonionic surfactants (Triton X 100, Brij 56 and Brij 97) and the polymer (Polyvinyl methyl ether)

The clouding points (CP) of the nonionic surfactants p-tert-octyl phenyl polyoxyethylene ether (Triton X 100), Brij-56 and Brij-97, and the water soluble polymer polyvinylmethylether (PVME) have been measured in the presence of the ionic surfactants alkyl (C₁₀, C₁₂, C₁₄ and C₁₆) triphenyl phosphonium bromides (ATPBs). The threshold additive concentrations required for efficient CP enhancement of the systems that were studied have been determined. Considering CP as the threshold state of phase separation, the energetics of the process at different additive concentrations has been evaluated. The spontaneity of free energy of the clouding process (G _c ⁰ ) at the transition concentrations followed the order PVME > TX 100  Bj 56 > Bj 97. The clouding process has been found to be energetically endothermic with fairly large enthalpy and entropy changes that nicely compensate each other. The compensation temperature has been evaluated and compared with different types of the clouding agents.This revised version was published online in January 2005 with corrections to the names of the authors.