Experiment and theory of low-pressure nitrogen adsorption in organic layers supported or grafted on inorganic adsorbents: toward a tool to characterize surfaces of hybrid organic/inorganic systems

We report experimental nitrogen adsorption isotherms of organics-coated silicas, which exhibit a low-pressure desorption branch that does not meet the adsorption branch upon emptying of the pores. To address the physical origin of such a hysteresis loop, we propose an equilibrium thermodynamic model that enables one to explain this phenomenon. The present model assumes that, upon adsorption, a small amount of nitrogen molecules penetrate within the organic layer and reach adsorption sites that are located on the inorganic surface, between the grafted or adsorbed organic molecules. The number of accessible adsorption sites thus varies with the increasing gas pressure, and then we assume that it stays constant upon desorption. Comparison with experimental data shows that our model captures the features of nitrogen adsorption on such hybrid organic/inorganic materials. In particular, in addition to predicting the shape of the adsorption isotherm, the model is able to estimate, with a reasonable number of adjustable parameters, the height of the low-pressure hysteresis loop and to assess in a qualitative fashion the local density of the organic chains at the surface of the material.     

Acidity of Alginate Aerogels Studied by FTIR Spectroscopy of Probe Molecules

Supercritical drying of alginate gels is an efficient way to prepare aerogels with high surface area (>300 m² · g⁻¹). FTIR spectroscopy allows to monitor the adsorption of NH₃ from the gas phase onto the acid sites of the alginate. Free carboxylic groups are effective Brønsted sites, whereas the divalent cations used in the ionotropic gelation present the properties of Lewis sites. The ratio between Brønsted and Lewis sites provides infomation on the role of pH in alginate gelation and suggests that non-buffered gelation by transition-metal cations is a mixed ionotropic-acid process.     

Experiences in the measurement of RBC-bound IgG as markers of cell age

An immunologically mediated pathway has been largely accepted to be one of the mechanisms involved in the clearance of senescent or prematurely damaged RBC. According to this pathway, RBC removal is mediated by binding of naturally occurring IgG to clustered integral membrane proteins, followed by complement deposition. The validation of an immunoenzymatic method for the detection of RBC-bound autologous IgG is presented. The use of RBC-bound IgG as an index related to red cell age was evaluated by measuring IgG binding in RBC treated with the clustering agent ZnCl2, in density fractionated RBC and in a selected group of patients expected to have an altered RBC life span. The immunoenzymatic method for IgG detection resulted to be reproducible (CV = 3.4%). IgG binding to in vitro clustered RBC was found to be enhanced to a very great extent, about 20 times higher with respect to untreated RBC. A slight but significant increase (about 1.8-fold) in membrane-bound IgG was observed in the highest density fraction of normal RBC, which constituted 1% of the total cells. A significantly greater number of RBC-bound IgG was measured in splenectomized beta-thalassemia intermedia patients and in subjects with secondary decreases in the C3 complement fraction concentration.     

Enzymes Hosted in Reverse Micelles in Hydrocarbon Solution

Reverse micelles are spheroidal aggregates formed by certain surfactants in apolar media. In contrast to normal micelles in water, the polar head groups of the surfactant molecules are directed towards the interior of the aggregate and form a polar core which can solubilize water (the “water pool”); the lipophilic chains are exposed to the solvent. The water of the water pool exhibits properties that (depending on the mole ratio of water to surfactant) differ from those of bulk water. Surprisingly, these reverse micelles are able to solubilize in hydrocarbon solvents hydrophilic molecules, e.g., enzymes and even plasmids, that are much larger than the original water-pool diameter. These biopolymer-containing reverse micelles can be viewed as novel microreactors, whose physical properties can be controlled through the water content. Remarkable is the ability of enzyme-containing micelles to react with water-insoluble, hydrocarbon-soluble substrates, as in the example of lipoxygenase with linoleic acid.     

Combinatorial sums through Riordan arrays

The aim of this work is to show how Riordan arrays are able to generate and close combinatorial identities, by means of the method of coefficients (generating functions). We also show how the same approach can be used to deal with other combinatorial problems, for instance asymptotic approximation and combinatorial inversion. Finally, we propose a method for generating new combinatorial sums by extending the concept of Riordan arrays to bi-infinite matrices.     

A multireference perturbation theory study on the vertical electronic spectrum of thiophene

The vertical electronic spectrum of the thiophene molecule is investigated by means of second and third order multireference perturbation theory (NEVPT). Single-state and quasi-degenerate NEVPT calculations of more than 25 singlet excited states have been performed. The study is addressed to the theoretical characterization of the four lowest-energy valence states, as well as the 3s, 3p and 3d Rydberg states. In addition, the excitation energies of two and valence states are also reported. For almost all the excited states, coupled cluster calculations (CCSD and CCSDR(3)) have been also carried out, using the same geometry and basis set used for the NEVPT ones, in order to make the comparison between the results of the two methods meaningful. A remarkable accordance between the NEVPT and CC excitation energies is found. The present results, over all, confirm the experimental assignments but, above all, represent an important contribution to the assignments of some low-energy states, valence and Rydberg, for which a firm interpretation is not available in the literature.     

Catalysis of the beta-elimination of HF from isomeric 2-fluoroethylpyridines and 1-methyl-2-fluoroethylpyridinium salts. Proton-activating factors and methyl-activating factors as a mechanistic test to distinguish between concerted E2 and E1cb irreversible mechanisms

Second-order rate constants, k(OH)(N), M(-)(1) s(-)(1), for the beta-elimination reactions of HF with 2-(2-fluoroethyl)pyridine (2), 3-(2-fluoroethyl)pyridine (3), and 4-(2-fluoroethyl)pyridine (4) in OH(-)/H(2)O, at 50 degrees C and mu = 1 M KCl, are = 0.646 x 10(-)(4) M(-)(1) s(-)(1), = 2.97 x 10(-)(6) M(-)(1) s(-)(1), and = 5.28 x 10(-)(4) M(-)(1) s(-)(1), respectively. When compared with the second-order rate constants for the same processes with the nitrogen-methylated substrates 1-methyl-2-(2-fluoroethyl)pyridinium iodide (5), 1-methyl-3-(2-fluoroethyl)pyridinium iodide (6), and 1-methyl-4-(2-fluoroethyl)pyridinium iodide (7), the methyl-activating factor (MethylAF) can be calculated from the ratio k(OH)(NCH)3/, and a value of 8.7 x 10(5) is obtained with substrates 5/2, a value of 1.6 x 10(3) with 6/3, and a value of 2.1 x 10(4) with 7/4. The high values of MethylAF are in agreement with an irreversible E1cb mechanism (A(N)D(E) + D(N)) for substrates 5 and 7 and with the high stability of the intermediate carbanion related to its enamine-type structure. In acetohydroxamate/acetohydroxamic acid buffers (pH 8.45-9.42) and acetate/acetic acid buffers (pH 4.13-5.13), the beta-elimination reactions of HF, with substrates 2 and 4, occur at NH(+), the substrates protonated at the nitrogen atom of the pyridine ring, even when the [NH(+)] is much lower than the [N], the unprotonated substrate, due to the high proton-activating factor (PAF) value observed: 3.6 x 10(5) for 2 and 6.5 x 10(4) for 4 with acetohydroxamate base. These high PAF values are indicative of an irreversible E1cb mechanism rather than a concerted E2 (A(N)D(E)D(N)) mechanism. Finally, the rate constant for carbanion formation from NH(+) with 2 is k(B)(NH)+ = 0.35 M(-)(1) s(-)(1), which is lower than when chlorine is the leaving group ( = 1.05 M(-)(1) s(-)(1); Alunni, S.; Busti, A. J. Chem. Soc., Perkin Trans. 2 2001, 778). This is direct experimental evidence that some lengthening of the carbon-leaving group bond can occur in the intermediate carbanion. This is a point of interest for interpreting a heavy-atom isotope effect.     

Comparative study of water dissociation on Rh(111) and Ni(111) studied with first principles calculations

The dissociation and formation of water on the Rh(111) and Ni(111) surfaces have been studied using density functional theory with generalized gradient approximation and ultrasoft pseudopotentials. Calculations have been performed on 2x2 surface unit cells, corresponding to coverages of 0.25 ML, with spot checks on 3x3 surface unit cells (0.11 ML). On both surfaces, the authors find that water adsorbs flat on top of a surface atom, with binding energies of 0.35 and 0.25 eV, respectively, on Rh(111) and Ni(111), and is free to rotate in the surface plane. Barriers of 0.92 and 0.89 eV have to be overcome to dissociate the molecule into OH and H on the Rh(111) and Ni(111) surfaces, respectively. Further barriers of 1.03 and 0.97 eV need to be overcome to dissociate OH into O and H. The barriers for the formation of the OH molecule from isolated adsorbed O and H are found to be 1.1 and 1.3 eV, and the barriers for the formation of the water molecule from isolated adsorbed OH and H are 0.82 and 1.05 eV on the two surfaces. These barriers are found to vary very little as coverage is changed from 0.25 to 0.11 ML. The authors have also studied the dissociation of OH in the presence of coadsorbed H or O. The presence of a coadsorbed H atom only weakly affects the energy barriers, but the effect of O is significant, changing the dissociation barrier from 1.03 to 1.37 and 1.15 eV at 0.25 or 0.11 ML coverage on the Rh(111) surface. Finally, the authors have studied the dissociation of water in the presence of one O atom on Rh(111), at 0.11 ML coverage, and the authors find a barrier of 0.56 eV to dissociate the molecule into OH+OH.