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In all silica-gel adsorption processes driven by low-grade heat, the kinetics of adsorption of water on silica-gel is very important in order to optimize design and becomes an essential factor in ultra-low grade heat applications. A new approach for the determination of the mass transfer coefficient of water in commercial silica-gel is proposed and demonstrated with measurements on a single particle using the zero length column technique. Under equilibrium conditions the methodology offers the key advantage to acquire equilibrium isotherms with thousands of points in less than one day. This allows to obtain the relationship between vapour concentration and equilibrium adsorbed amount through numerical interpolation. At higher flowrates, the system operates under kinetic control therefore allowing the determination of the mass transfer coefficient. The novel approach calculates all the elements needed to obtain the mass transfer coefficient from the measured signals without the need to use a specific model. Adsorption and desorption experiments were carried out at different flowrates and three different temperatures. The kinetic responses can be used to determine an average mass transfer coefficient, which is consistent with literature values, but a complex behaviour is observed with surface diffusion as the main contribution to the transport process.

In the present work, adsorption of anionic azo dye, new coccine (NCC) on silica and silica-gel in an aquatic environment was discovered. Effective conditions such as adsorption time, pH, the influence of dosage on NCC adsorption using strong polycation, poly-diallyl-dimethylammonium chloride (PDADMAC) modified silica (PMS) and PDADMAC modified silica-gel (PMSG) were systematically studied. The removal of NCC using PMS and PMSG were much higher than that using raw silica and silica-gel without PDADMAC in all pH ranges from 3 to 10. The adsorption of NCC onto PMS and PMSG was achieved maxima at the same conditions of contact time 30 min, pH 6. The optimum adsorbent dosages of PMS and PMSG for NCC removal were 10 and 20 mg·mL−1, respectively. Experimental results of NCC adsorption isotherms onto PMS and PMSG at different ionic strength were fitted by Langmuir and Freundlich models. The NCC removal efficiencies using PMS and PMSG were higher than 87%, indicating that PMS and PMSG are novel and reusable adsorbents for removal of anionic dye. Based on adsorption isotherms, and surface group changes after PDADMAC modification and NCC adsorption examined by Fourier transform infrared spectroscopy (FTIR), we demonstrate that electrostatic interaction between positively charged adsorbents’ surfaces and negative sulfonic groups of NCC are the main driving force for anionic azo dye adsorption onto PMS and PMGS adsorbents.

A huge number of studies and work in the drug delivery literature are focused on understanding and modeling transport phenomena, the pivotal point for a good device design. The rationalization of all phenomena involved is fundamental, but several concerns arise leaving many issues unsolved. In order to change the point of view we decided to focus our attention on the parallelisms between two fields that seem to be very far from each other: chromatography and drug release. Taking advantages of the studies conducted by many researchers using chromatographic columns we decided to explain all the phenomena involved in drug delivery considering sodium ibuprofen (IP) molecules as analytes and hydrogel as a stationary phase. In particular, we considered not only diffusion, but also drug-polymer interactions as adsorption on the stationary phase and drug-drug interactions as aggregation of analytes. The hydrogel investigated is a promising formulation made of agarose and carbomer 974p (AC) loaded with IP, a non-steroidal common anti- inflammatory drug. The self-diffusion coefficient of IP in AC formulations was measured by using an innovative method based on a magic angle spinning NMRspectroscopic technique to produce high resolution ( liquid-like) spectra. This method (HR-MAS NMR) is used in combination with pulsed field gradient spin echo (PGSE)liquid-state techniques. The model predictions satisfactorily match with the experimental data obtained in water and the gel environment, indicating that the model presented here, despite its simplicity, is able to describe the key phenomena governing the device behavior and could be used to rationalize the experimental activity.

As world population is growing the need for fresh water is increasing. Many technologies have been investigated for seawater desalination but each one has its own drawbacks. Desalination process with adsorption technology has gained interest in the last few years due to its ability to use waste heat sources leading to minimal energy requirements and reduced CO 2 emissions. This work mathematically investigates the effect of evaporator and condenser temperatures on the adsorption cycle performance for the production of potable water and cooling effect using silica-gel as the adsorbent material. It was found that as condenser temperature decreases, more water is produced and higher specific cooling capacity was achieved. Moreover, as evaporator temperature increases, similar improvements in water production and cooling were achieved. Results showed that for 10 o C condenser water temperature and 30 o C evaporator inlet water temperature, potable water production of 10 m 3 /tonne silica-gel/day and specific cooling capacity (SCC) of 77 Rton/tonne silica-gel were achieved highlighting the potential of this cycle.

The performances of well-known porous metal/metalloid oxide adsorbents (zeolite 13X, zeolite 4A and silica gel) and less explored Engelhard titanosilicate ETS-10 for water adsorption heating systems (AHSs) were compared with the aid of computational modelling and simulations. The developed model contemplated adsorption equilibrium, one-dimensional heat and mass transfer in the bed, external heat transfer limitations, and intraparticle mass transport. The pair zeolite 13X/water seemed most promising for the AHS partly due to a higher amount of heat generated per cycle, and favourable water-adsorption isotherm features. Based on sensitivity studies, for zeolite particle diameters in the range 0.2-0.6 mm, the coefficient of performance was 1.48 and the specific heating power was in the range 1141-1254 W Kg(s)(-1) Aiming at inferior computational and numerical efforts, the impact of considering some simplified postulations (e.g. constant thermal conductivity of the adsorbent; constant isosteric heat of adsorption; constant linear driving force coefficient), while ensuring comparable predictions of the performances of the AHSs, was successfully investigated. (C) 2016 Elsevier Ltd. All rights reserved.

Thiols are smoothly and efficiently oxidized to disulfides (RSSR) with air in the presence of gold nanoparticles supported on CeO2 in absence of solvent, as well as in aqueous solutions and neutral pH. It is shown that the reaction can occur through the coupling of two sulphur radicals on the metal surface. The sulphur radicals are formed from thiols by one-electron oxidation with the metal. This reaction mechanism strongly resembles that found for sulfhydryl oxidases, a class of enzymes which are involved in the oxidative protein folding through de novo formation of disulfides from thiols., lFinancial support by Consolider-Ingenio 2010 (project MULTICAT), Spanish MICINN (Projects MAT2006-14274-C02-01 and MAT2011-28009), Generalitat Valenciana (Project PROMETEO/2008/130) and Fundacion Areces are gratefully acknowledged. T.R. expresses her gratitude to Consejo Superior de Investigaciones Cientificas for an I3-P fellowship.

Diet composition and energy content modulate free fatty acid (FFA) release. The aim of this study was to evaluate the dose–response effects of euenergetic variations in dietary carbohydrate and fat content on postabsorptive FFA release. The rate of appearance (Ra) of palmitate was measured by infusion of [2,2-2H2]palmitate after an overnight fast in six healthy men on three separate occasions, i.e. after 7 d on euenergetic control, high-carbohydrate and high-fat diets. The protein content and composition was identical for each diet. Postabsorptive plasma fatty acid concentrations were not different between the high-carbohydrate and control diets (0·36 (SE 0·07) V. 0·43 (se 0·04) mmol/l), but were increased after the high-fat diet (0·75 (se 0·09) mmol/l, (Pa palmitate was not different between the high-carbohydrate and control diets (1·36 (se 0·20) v. 1·47 (se 0·15) μmol/kg per min). However, Ra palmitate was increased to 2·36 (se 0·26) μmol/kg per min after the high-fat diet (PP

The porous organosilica framework containing Troger's base (TB) prepared by mild sol-gel synthesis from 2,8-bis-silylated TB precursor contains a mixture of two point attached TB and one point attached TB units, resulting from unexpected partial Si-C bond cleavage as demonstrated by (29)Si MAS NMR spectroscopy and by selective chemo-desorption of the anchored organic part of the hybrid material., We are thankful for financial support by Consolider-Ingenio 2010 (MULTICAT project). E.M. thanks Ministerio de Ciencia y Innovacion by the support through Juan de la Cierva contract. The authors are indebted to Dr Alejandro Vidal-Moya for technical assistance and fruitful discussion on 13C and 29Si MAS NMR spectroscopies.

New probes for kinetic intracellular measurements in the millisecond range are desirable to monitor protein biochemical dynamics essential for catalysis, allosteric regulation and signalling. Good candidates to this aim are the photo-switchable mutants of the Green Fluorescent Protein, whose anionic fluorescence, primed by blue light, is markedly enhanced under an additional excitation at a shorter wavelength and relaxes within few milliseconds. The aim of this report is to study how the brightness enhancement kinetics depends on the physical-chemical and spectroscopic parameters and to provide proof-of-concepts experiments for the use of the fluorescence enhancement in conditions in which the protein diffusion is hindered and thereby photo-bleaching can be a limiting critical issue. Future, direct applications of photo-chromic mutants for modulated excitation imaging would in fact require such a detailed knowledge. We present here an extensive study of the photo-switching mechanism of the E222Q mutant of GFPMut2 (Mut2Q), pumped by visible 488 nm light and probed at 400-420 nm, as a function of pH, viscosity, temperature and light intensity. In solution, two characteristic photo-switching times are found by means of modulated double beam fluorescence correlation spectroscopy in the 1-30 ms range, depending on the solution pH. The photo-switching kinetics is solved in terms of the eigenvalues and the eigenvectors of a specific energy diagram and directly used to fit the data, suggesting that the observed photo-switching amplitudes and kinetics are related to a single three-levels transition loop. Finally we give in-vitro examples of the use of modulated excitation microscopy, based on fluorescence enhancement amplitude and kinetics detection, on Mut2Q protein samples immobilized in acrylamide gels.

Surfactant free ternary systems formulated with organic solvents such as alpha-pinene or n-hexane, short chain alcohols and water, were used as new reaction media to maximize the catalytic performance of chloroperoxidase from Caldariomyces fumago (CPO) towards the oxidation of hydrophobic compounds including olefins and terpenols. The influence of the composition and the hydration state of the system, the nature of the oxidizing agent as well as substrate availability on the catalytic behavior and stability of the enzyme was investigated, using the chlorination of monochlorodimedone (MCD) and the epoxidation of styrene as model reactions. Based on residual chlorination activity measurements, which were in accordance with differential scanning calorimetry (DSC) findings, it was concluded that in low water systems formulated with alpha-pinene CPO stability is significantly increased compared to other reaction media (up to 65% residual activity after 24 h of incubation at 30 degrees C). Electron paramagnetic resonance (EPR) spectroscopy indicated that in low water content systems the ferric environment of the active site of CPO does not undergo severe modifications. Total turnover numbers (TTN) obtained for the oxidation of various olefins and terpenols in alpha-pinene-based systems, were up to 25,000 which is 2-170 times higher than previously reported values. The results indicate that such ternary systems can be efficiently employed as reaction media leading to highly enhanced stability and increase CPO potential as practical catalyst for oxidation of large amounts of hydrophobic compounds in a single-step biocatalytic process. (c) 2007 Elsevier B.V. All rights reserved. Journal of Molecular Catalysis B-Enzymatic

Hindered tertiary nitriles can be hydrolyzed under neutral and mild conditions to the corresponding amides using platinum(II) catalysts with dimethylphosphine oxide or other secondary phosphine oxides (SPOs, phosphinous acids) as ligands. We have found that this procedure also works well for nitriles with acid- or base-sensitive groups, which is unprecedented in terms of yield and selectivity. The catalyst loading can be as low as 0.5 mol %. Amides are isolated as the only product in high yield, and no further hydrolysis to the corresponding acids takes place. Reactions are carried out at 80 degrees C but take place even at room temperature. When enantiopure secondary phosphine oxide ligands are used in the hydrolysis of racemic nitriles, no kinetic resolution is observed, presumably due to racemization of the ligand during the reaction.

Journal article We report a novel fluorescence-lifetime-based pH sensing method that utilizes acridine incorporated into Nation (AcNaf) as the fluorescent indicator. The AcNaf sensor is excited using a 380 nm light emitting diode (LED) and the fluorescence lifetimes are measured at 450 and 500 nm. The fluorescence behavior of acridine as a function of pH in aqueous phosphate buffers and incorporated into the Nation membrane has been investigated. The results show that incorporating acridine into Nation changes the apparent ground-state pK(a) from similar to5.45 to similar to9, while the apparent excited-state pK(a)* is only slightly changed (similar to9.4 in 0.1 M phosphate buffer). The AcNaf film shows a good pH response with a change in average lifetime of similar to19 ns (at an emission wavelength of 450 nm) over the pH 8 to 10 range. We also show that excited-state protonation does not occur in the AcNaf sensor film and that chloride quenching cannot occur because of the permselective nature of Nafion. We also discuss how the unique structure of Nation affects the fluorescence behavior of acridine at various pH values and examine the impact of buffer concentration on apparent pK(a) and pH sensing ability. NUI Galway Millennium Research Grant; Enterprise Ireland Research Innovation Fund (IF/2001/061); HEA Programme for Research peer-reviewed

Airborne particulates of either natural or anthropogenic origin constitute a significant portion of atmospheric pollution. Environmental xenobiotics, among which are polynuclear aromatic hydrocarbons (PAHs) and pesticides, often adsorb to aerosols and as such are transported through the atmosphere with the physicochemical properties of the aerosols determining the lifetime of these organic compounds. As an example, the resistance of some PAHs against the photolysis is explained by the effect of the aerosol's "inner filter" that reduces the intensity of incident light reaching the mineral particles. On the other hand, some constituents of the aerosols can act as catalytic and/or stoichiometric reagents in atmospheric reactions on the solid surfaces. In the study described here the photoacoustic (PA) spectroscopy in the UV-Vis was used to investigate natural and model aerosols. The PA spectra obtained from coal and wood ashes and of Saharan sand, all three representatives of airborne aerosols, provide the evidence for the existence of the "inner filter." Furthermore, valuable information about the different nature of the interaction between the model aerosols and adsorbed organics (e.g., PAH-pyranthrene and silica, alumina, and MgO) has been obtained. Finally, the outcome of the study conducted with powdered mixtures of chalk and black carbon suggests that the PA method is a candidate method for determination of carbon content in stack ashes.

International audience; (-)-Ephedrine, used as a model beta-amino alcohol, was covalently anchored on mesoporous micelle templated aluminosilicates (Al-MTS) through nucleophilic substitution of halogenoalkyl(aryl)silane chains previously grafted on the surface. The covalent grafting was performed either by silylation (method a) or b Surface sol-gel (method 6). The latter method provided higher loading. However, the higher loading lowers the resulting mesoporous volume. The coupling alkyl halide moiety was then substituted with (1R,2S)-(-)-ephedrine. Used as chiral auxiliaries in the heterogeneous enantioselective catalysis of the alkylation of benzaldehyde by diethylzine, these materials showed properties which depend mainly on the grafting method. The best results (activity, enantioselectivity) were obtained with catalysts prepared from Supports featuring high initial pore diameter. The effect of the regular porosity on the efficiency and enantioselectivity was shown. Dilution of catalytic sites by alkyl groups and rigidification of the linker were also studied.

Chromatographic behaviour of six anti hypertensive drugs from the class of ACE inhibitors was studied under conditions of salting-out thin-layer chromatography on silica-gel, cellulose and polyacrylonitrile (PANS) as sorbents. For this purpose, different concentrations of aqueous ammonium sulphate solutions were used as solvents. In all cases studied, it was established that hR(F) values decrease with increasing salt concentrations in the chromatographic solvent Systems used. In addition, a linear relationship of the corresponding R-M values and ammonium sulphate content in the solvent was observed. To explain these results, a separation mechanism based on hydrophobic interaction between the sorbend and sorbent is proposed.

Direct enantiomeric separations of 17 chiral amidotetralins by means of high performance liquid chromatography were performed on stationary phases composed of tris(3,5-dimethylphenylcarbamate) derivatives of cellulose and amylose, coated on silica gel. The enantiomers of 15 out of 17 amidotetralins were resolved with a resolution of more than 1.5 by at least one of the chiral stationary phases. The stationary phases showed complementary results with regard to the separation of the amidotetralins, that is, pairs that did not separate on the cellulose-type column were well separated on the amylose-type column, and vice versa. There was no significant correlation between the chromatographic properties of the chiral stationary phases. (C) 1993 Wiley-Liss, Inc.