Synthesis of an ammonium ionophore and its application in a planar ion-selective electrode

A modular technique was used to synthesize an ammonium-selective ionophore based on a cyclic depsipeptide structure. The ionophore was incorporated into a planar ion-selective electrode sensor format and the selectivity tested versus a range of metal cations in a commercial clinical diagnostic "point-of-care" instrument. Four sensor membrane formulations were tested, all of which consisted of plasticized PVC. Formulations differed as to the type of plasticizer used and whether an ionic additive was present. It was found that the membrane containing the polar plasticizer nitrophenyl octyl ether in the absence of ionic additive exhibited near-Nernstian behavior (slope, 60.1 mV/decade at 37 degrees C) and possessed high selectivity for ammonium ion over lithium and the divalent cations, calcium and magnesium (log K(POT)NH4+(j) = -7.3, -4.4, and -7.1 for lithium, calcium, and magnesium ions, respectively). The same membrane also exhibited sodium and potassium selectivity that was comparable to that reported for nonactin (log K(POT)NH4+(j) = -2.1 and -0.6 for sodium and potassium, respectively, compared to -2.4 and -0.9 in the case of nonactin). Membranes containing the less polar plasticizer, dioctyl phthalate, showed sub-Nernstian behavior (slope, <50 mV/decade at 37 degrees C). In all cases, the presence of the ionic additive potassium tetrakis(4-chlorophenyl)borate substantially reduced the selectivity observed. The flexible modular synthetic technique developed and reported here will allow the cyclic depsipeptide structure to be tuned for optimum selectivity.     

Fast cross-validation of high-breakdown resampling methods for PCA

Cross-validation (CV) is a very popular technique for model selection and model validation. The general procedure of leave-one-out CV (LOO-CV) is to exclude one observation from the data set, to construct the fit of the remaining observations and to evaluate that fit on the item that was left out. In classical procedures such as least-squares regression or kernel density estimation, easy formulas can be derived to compute this CV fit or the residuals of the removed observations. However, when high-breakdown resampling algorithms are used, it is no longer possible to derive such closed-form expressions. High-breakdown methods are developed to obtain estimates that can withstand the effects of outlying observations. Fast algorithms are presented for LOO-CV when using a high-breakdown method based on resampling, in the context of robust covariance estimation by means of the MCD estimator and robust principal component analysis. A robust PRESS curve is introduced as an exploratory tool to select the number of principal components. Simulation results and applications on real data show the accuracy and the gain in computation time of these fast CV algorithms.     

Thermodynamic and experimental study of chemical bath deposition of Zn(S,O,OH) buffer layers in basic aqueous ammonia solutions. Cell results with electrodeposited CuIn(S,Se)2 absorbers

This paper presents a thermodynamic study of Chemical Bath Deposition (CBD) of zinc sulphide based films in aqueous ammonia solutions. The aim is a better understanding of ammonia and temperature effects on the deposition conditions and films composition. The formation of solid phases has been predicted by means of the precipitation conditions of ZnO, Zn(OH)₂ and ZnS as a function of temperature between 298 and 333 K. Films have been deposited according to calculated diagrams and preliminary results on solar cells based on electrodeposited CuIn(S,Se)₂ layers have been demonstrated. Composition and thickness of the films have been extracted to link the theoretical study with experiments.     

El Sur Global: Future Resilient City

Shifting the focus from futuristic visions, Alfredo Brillembourg and Hubert Klumpner with Alexis Kalagas of interdisciplinary design practice Urban-Think Tank urge us to ‘forget about utopia’, for in the most part the urban environment of 2050 is already built. Architects’ sights need to be set on the sometimes grim and unfolding reality of favelas and the world's informal cities.     

Amino‐functionalised mesoporous silica microspheres for immobilisation of Candida antarctica lipase B – application towards greener production of 2,5‐furandicarboxylic acid

In the present study, amino‐functionalised mesoporous silica microspheres were utilised as support for the covalent immobilisation of Candida antarctica lipase B (CaLB) for the subsequent production of 2,5‐furandicarboxylic acid (FDCA) from 2,5‐diformylfuran (DFF). Under the optimised operating conditions of pH 6.5, particle/enzyme ratio of 1.25:1.0 and glutaraldehyde concentration of 4 mM, a maximum CaLB immobilisation yield of 82.4% on silica microspheres was obtained in 12.25 h. The immobilised CaLB was used for the synthesis of alkyl esters, which were utilised along with hydrogen peroxide for FDCA synthesis. The biocatalytic conversion of 30 mM DFF dictated a 77–79% FDCA in 48 h at 30°C; where the turnover number and turnover frequency of immobilised CaLB were 6220.73 mol mol⁻¹ and 129.59 h⁻¹, respectively, for ethyl acetate, against 6297.65 mol mol⁻¹ and 131.2 h⁻¹, respectively, for ethyl butyrate. Upon examining the operational stability, the immobilised CaLB exhibited high stability till five cycles of FDCA production.Inspec keywords: mesoporous materials, organic compounds, biotechnology, silicon compounds, renewable materials, catalysis, catalysts, enzymes, thermal stability, biofuelOther keywords: FDCA production, amino‐functionalised mesoporous silica microspheres, greener production, 2,5‐furandicarboxylic acid, covalent immobilisation, 2,5‐diformylfuran, CaLB immobilisation, Candida antarctica lipase B immobilisation, ethyl butyrate, time 48.0 hour, temperature 30.0 degC, time 12.25 hour     

Factors responsible for rapid dissipation of acidic herbicides in the coastal lagoons of the Camargue (Rhône River Delta, France)

This study was aimed at investigating which processes cause acidic herbicides (e.g., bentazone, MCPA and dichlorprop) to rapidly disappear in the lagoons of the Rhône delta, which are peculiar brackish and shallow aquatic environments. The use of the model MASAS (Modeling of Anthropogenic Substances in Aquatic Systems) revealed that sorption, sedimentation, volatilization, flushing and abiotic hydrolysis had a minor role in the attenuation of the investigated herbicides. Laboratory scale biodegradation and photodegradation studies were conducted to better assess the significance of these two processes in the natural attenuation of herbicides in brackish (lagoons) waters with respect to fresh waters (canals draining paddy fields). Herbicide biodegradation rates were significantly lower in lagoon water than in canal water. Consequently, photodegradation was the main dissipation route of all investigated herbicides. The contribution of indirect photolysis was relevant for MCPA and dichlorprop while direct photolysis dominated for bentazone removal. There is a need to further investigate the identity of phototransformation products of herbicides in lagoons.     

Functional and molecular properties of calcium precipitated soy glycinin and the effect of glycation with κ-carrageenan

This study describes an extraction process for the preparation of highly purified calcium precipitated glycinin (11S). Initial extraction of soy proteins using isoelectric precipitation at pH 6.8 followed by cryo-precipitation yielded 4.2% product (11S) recovery with 98% protein purity for the control extracted with NaOH. Addition of calcium chloride (CaCl₂) doubled the extraction yield (9%) compared to the control and when two other salts were used (i.e., sodium (Na₂SO₄) and ammonium (NH₄)₂SO₄ sulfate, average yields of 4.4% and 5.17%, respectively). Thermal and molecular stability under varying conditions (pH, salts, SDS as a protein structure perturbing agent), and effect of glycation on functional and structural properties were investigated. Size exclusion chromatography and electrophoresis confirmed the predominance of a major band with MW of ～342 kDa with 98.4% purity. Differential scanning calorimetry (DSC) yielded one endothermic transition peak at 95.5 °C. Denaturation temperatures were >100 °C for all salt concentrations studied. The pH had a dominant influence on the structural properties of glycinin. In the presence of NaCl and CaCl₂ (0.2–1 M), the protein structure showed very little denaturation and no aggregation bands were observed even on heating to 95 °C. Lower SDS concentrations (0.5–1%) resulted in denaturation and aggregation, while at 2% SDS only denaturation was observed. Glycation did not alter the conformational structure of protein. Improvements in surface properties were observed with moderate degree of glycation (6–24 h).     

Dye–fiber interactions in PET fibers: Hydrogen bonding studied by IR‐spectroscopy

Dye–fiber interactions are studied in poly (ethylene terephthalate) fibers by FT‐IR spectroscopy. It is shown for the first time that DRIFTS (diffuse reflectance infrared Fourier transform spectroscopy) serves as an easy applicable and accurate technique for the study of fibrous structures. This article focuses on the possible hydrogen bond interactions in the dye–fiber system, where the PET fibers are dyed with anthraquinone‐based disperse dyes. The dyes and related anthraquinone structures are studied in both the dilute solution state, the solid state, and as present in the PET fibers. It is proven that 1‐amino anthraquinones show strong “chelate‐type” intramolecular hydrogen bonding in all three states. In the fibers an important supplementary intermolecular hydrogen bonding with the C?O groups in the PET fiber is observed. The extend of hydrogen bonding seems to be prone to dye concentration variations. Further analysis by modulated differential scanning calorimetry links the hydrogen bonding to an intrinsic plasticizing effect of the dyes affecting the dye diffusion process. This thus offers a tool for the fundamental understanding of the dyeing process and possible observed differences in dyeing behavior in dye–fiber systems. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007