An indirect conductimetric screening method for the detection of antibiotic residues in bovine kidneys

An indirect conductimetric screening method using three test bacterium-medium combinations was developed for rapid detection of antibiotic residues in bovine carcasses. The detection time (DT), i.e. the point when the growth of the test bacterium was detected, was determined by observing the rate of change in the conductance plotted against time. This detection time averaged half of the reference time recorded by the instrument software. Total change in conductance (TC) was used as a further measure of growth. Threshold values for DT and TC were determined with inhibitor-free kidney samples. The presence of a residue was indicated if the DT exceeded the respective threshold value and was confirmed if the TC remained below the TC threshold value. The limits of detection (LODs) determined with fortified samples were at about or below the MRLs for cephalexin, chlortetracycline, ciprofloxacin, dihydrostreptomycin, enrofloxacin, oxytetracycline and penicillin G. The LODs for penicillin G, oxytetracycline and the sum of enrofloxacin and ciprofloxacin were also estimated with incurred samples; these samples were also analysed using liquid chromatography. The LODs determined with fortified and incurred samples were in close agreement. Given its rapid detection, good sensitivity to a wide range of antibiotics and ease of performance, the indirect conductimetric method developed here would seem to offer an appealing alternative to agar diffusion tests.     

Proteomic analysis of protein oxidation in Alzheimer's disease brain

There is a growing body of evidence that oxidative stress plays a major role in Alzheimer's disease (AD) pathogenesis. Identification of oxidatively altered proteins in AD is important for understanding the relationship between protein oxidation, protein aggregation and neurodegeneration. In this communication, we report a method that can be applied to study oxidative changes of individual proteins in brain. In order to analyze protein oxidation by detection of protein-bound carbonyls, cytosolic protein extracts were derivatized with 2,4-dinitrophenylhydrazine (DNPH) and then separated by two-dimensional (2-D) gel electrophoresis. After electrotransfer to polyvinylidene difluoride (PVDF) membranes, proteins were first stained with Sypro Ruby protein stain, and then the oxidized proteins were detected with anti-dinitrophenyl (DNP) antibody. About 150 proteins and more than 100 oxidized proteins were detected and quantified in both AD and control cases by 2-D image analysis. The amount of protein-bound carbonyls was decreased for six and increased for one protein in AD. The amount of protein was increased for three proteins in AD. Furthermore, the degree of oxidation was calculated as the ratio of protein-bound carbonyls to the total amount of an individual protein. Two proteins showed a significant decrease in the degree of oxidation in AD. Our results suggest that the balance of protein oxidation and degradation is altered in AD.     

Re-evaluation of the First and Second Stoichiometric Dissociation Constants of Oxalic Acid at Temperatures from 0 to 60 °C in Aqueous Oxalate Buffer Solutions with or without Sodium or Potassium Chloride

Equations were developed for the calculation of the first stoichiometric (molality scale) dissociation constant (K _m1) of oxalic acid in buffer solutions containing oxalic acid, potassium hydrogen oxalate, and potassium chloride from the determined thermodynamic values of this dissociation constant (K _a1) and the molalities of the components in the solutions. Similar equations were also developed for the second stoichiometric dissociation constant (K _m2) of this acid in buffer solutions containing sodium or potassium hydrogen oxalate, oxalate and chloride. These equations apply at temperatures from 0 to 60 °C up to ionic strengths of 1.0 mol⋅kg⁻¹ and they have been based on single-ion activity coefficient equations of the Hückel type. For the equations for K _m1, the activity parameters of oxalate species and the K _a1 values were determined at various temperatures from the Harned cell data of a recent tetroxalate buffer paper (Juusola et al., J. Chem. Eng. Data 52:973–976, 2007). By using the resulting equations for K _m1, the activity parameters of oxalate species for K _m2 and the K _a2 values were then determined from the new Harned cell data and from those of Pinching and Bates (J. Res. Natl. Bur. Stand. (U.S.) 40:405–416, 1948) for solutions of sodium or potassium oxalates with NaCl or KCl. The resulting simple equations for calculation of K _m1 and K _m2 for oxalic acid were tested with all important thermodynamic data available in the literature for this purpose. The equations for ln (K _a1) and ln (K _a2) are of the form ln (K _a)=a+b(t/°C)+c(t/°C)². The coefficients for ln (K _a1) are the following: a=−2.8737, b=0.000159, and c=−0.00009. The corresponding coefficients for ln (K _a2) are −9.6563, −0.003059, and −0.000125, respectively. The new activity coefficient equations were used to evaluate the pH values of the tetroxalate buffer solution (i.e., of the 0.05 mol⋅kg⁻¹ KH₃C₄O₈ solution) for comparison with the pH values recommended by IUPAC at temperatures from 0 to 60 °C and to develop a new two-component oxalate pH buffer of 0.01 mol⋅kg⁻¹ KHC₂O₄+0.05 mol⋅kg⁻¹ Na₂C₂O₄ for which pH values are given from 0 to 60  °C. Values of p(m _H) calculated from these equations are tabulated for these buffers as well as for buffer solutions with KCl and KH₃C₄O₈ as the major component and minor component, respectively. Tables of p(m _H) are also presented for 0.001 mol⋅kg⁻¹ KHC₂O₄+0.005 mol⋅kg⁻¹ Na₂C₂O₄ solutions in which KCl is the supporting electrolyte.     

Preparation of new modified catalyst carriers

Novel modified catalyst carriers have been prepared. First, aminopropyltriethoxysilane (APTES) was immobilized on the silica surface by using the saturated gas–solid reactions. Secondly, two different (tetramethylcyclopentadienyl)chlorosilanes, (Me₂Si(C₅Me₄H)Cl and MeHSi(C₅Me₄H)Cl), were synthesized and anchored on the amine surface using liquid-phase reactions. Characterization of these stepwise prepared surfaces was carried out by ¹H, ¹³C and ²⁹Si solid state NMR and FTIR spectroscopy.     

Re-evaluation of the Activity Coefficients of Aqueous Hydrochloric Acid Solutions up to a Molality of 16.0 mol·kg<Superscript>−1</Superscript> Using the Hückel and Pitzer Equations at Temperatures from 0 to 50 °C

The simple three-parameter Pitzer and extended Hückel equations were used for calculation of activity coefficients of aqueous hydrochloric acid at various temperatures from 0 to 50 °C up to a molality of 5.0 mol·kg^?1. A more complex Hückel equation was also used at these temperatures up to a HCl molality of 16 mol·kg^?1. The literature data measured by Harned and Ehlers J. Am. Chem. Soc. 54, 1350–1357 (1932) and 55, 2179–2193 (1933) and by Åkerlöf and Teare [J. Am. Chem. Soc. 59, 1855–1868 (1937)] on galvanic cells without a liquid junction were used in the parameter estimations for these equations. The latter data consist of sets of measurements in the temperature range 0 to 50 °C at intervals of 10 °C, and data at these temperatures were used in all of these estimations. It was observed that the estimated parameters follow very simple equations with respect to temperature. They are either constant or depend linearly on the temperature. The values for the activity coefficient parameters calculated by using these simple equations are recommended here. The suggested new parameter values were tested with all reliable cell potential and vapor pressure data available in literature for concentrated HCl solutions. New Harned cell data at 5, 15, 25, 35, and 45 °C up to a molality of 6.5 mol·kg^?1 are reported and were also used in the tests. The activity coefficients obtained from the new equations were compared to those calculated by using the Pitzer equations of Holmes et al. [J. Chem. Thermodyn. 19, 863–890 (1987)] and of Saluja et al. [Can. J. Chem. 64, 1328–1335 (1986)] at various temperatures, and by using the extended Hückel equation of Hamer and Wu [J. Phys. Chem. Ref. Data 1, 1047–1099 (1972)] at 25 °C.     

Photocatalytic degradation of methylene blue in water solution by multilayer TiO2 coating on HDPE

A multilayer photocatalytic TiO₂ coating on a high-density polyethylene (HDPE) disk was found to degrade aqueous methylene blue in a batch reactor study. The TiO₂ coating was fabricated by a low-temperature method using polyurethane resin (PU) as a barrier layer for HDPE and as a binding agent for two TiO₂ layers. Adequate adhesion between the HDPE substrate and PU barrier in aqueous environment was ensured with an oxygen plasma treatment.The photocatalytic effect of immersed TiO₂ coating on the degradation of methylene blue in aqueous solution was monitored by UV–vis spectrometry as a function of UV-illumination time. Samples were allowed to adsorb methylene blue in the dark for 1 h before the UV-degradation experiments were started. The percentages of methylene blue degraded during 6 h UV illumination (λ = 365 nm) varied from 80% to 92%. The degradation followed pseudo-first order reaction kinetics, and the observed rate constants (k_obs) were between 0.27 and 0.43 h⁻¹.     

Re-evaluation of Activity Coefficients in Dilute Aqueous Hydrobromic and Hydriodic Acid Solutions at Temperatures from 0 to 60 °C

Simple two-parameter Hückel equations can be used for the calculation of the activity coefficients in aqueous hydrobromic and hydriodic acid solutions at temperatures from 0 to 60 °C and from 0 to 50 °C, respectively, at least up to a molality of 0.5 mol·kg^?1. The data measured by Macaskill and Bates (J. Solution Chem. 12:607–619, 1983) at 25 °C and those measured by Hetzer et al. (J. Phys. Chem. 68:1929–1933, 1964) at various temperatures on galvanic cells without a liquid junction were used in the parameter estimations for the hydrogen bromide (HBr) and hydrogen iodide (HI) solutions, respectively. The latter data consist of sets from 0 to 50 °C at intervals of 5 °C. The parameter values for HBr solutions were also tested using the numerous galvanic cell points from the other three data sets existing in the literature for hydrobromic acid solutions and covering wide range of temperatures from 0 to 60 °C. It was observed in the parameter estimations and tests that all of the estimated parameters are independent of the temperature. The recommended parameter values were additionally tested using the isopiestic data of Macaskill and Bates (see the citation above) and those of Harned and Robinson (Trans. Faraday Soc. 37:302–307, 1941) for dilute HBr and HI solutions at 25 °C, respectively. In more concentrated solutions up to a HBr molality of 4.5 mol·kg^?1 and up to a HI molality of 3.0 mol·kg^?1, an extended Hückel equation was used, which contains an additional quadratic term with respect to the molality. The parameters for the extended Hückel equations were determined from these isopiestic data and tested using these data and the existing galvanic cell data. The activity and osmotic coefficients calculated from the resulting equations are recommended in the present study for the more concentrated solutions. The recommended values are compared to the activity values reported in several previous tabulations.     

Synthesis,characterization and polymerization of the novel carbazole‐based monomer 9‐(bicyclo[2.2.1]hept‐5‐en‐2‐ylmethyl)‐9H‐carbazole

Synthesis and characterization of a novel carbazole‐based monomer, 9‐(bicyclo[2.2.1]hept‐5‐en‐2‐ylmethyl)‐9H‐carbazole (BHMCZ) and its copolymerization with ethylene by using two metallocene/MAO catalyst systems are presented. The monomer was characterized by means of NMR spectroscopy, MS and elementary analysis. Copolymerization studies were conducted using [Ph₂C(Ind)(Cp)ZrCl₂] and [Ph₂C(Flu)(Cp)ZrCl₂] catalysts. The [Ph₂C(Ind)(Cp)ZrCl₂] catalyst gave a copolymer containing as much as 4.6 mol‐% of BHMCZ. Polymers were characterized using NMR spectroscopy, gel permeation chromatography (GPC) and differential scanning calorimetry (DSC).     

Effects of N-substitution on the fragmentations of some cyclohexene-fused 2-N-phenyliminoperhydro-3,1-oxazines and related thiazines

Six cyclohexene-fused 2-N-phenyliminoperhydro-3,1-oxazines and four related thiazines were prepared and their mass spectrometric behavior was studied by means of metastable ion analysis and exact mass measurement. In most of the fragmentations, extensive rearrangements took place. The decompositions through the retro-Diels-Alder reaction initiated by the double bond dominated in the case of the unsubstituted compounds. The effect of the double bond, however, was greatly outweighed by the effect of the substituent on the ring nitrogen atom. In comparison with the unsubstituted compounds, both electron-releasing (methyl) and electron-withdrawing (benzyl) substituents increased the contribution of the ring cleavage reactions in the heterocyclic part of the molecule; in the case of the benzyl group the loss of the substituent also became important. For isomeric compounds, the relative peak intensities were so different that such compounds were easy to differentiate.