Inclusion Compounds of Dehydrocholic Acid with Solvents

The host-guest inclusion of various organic solvents within dehydrocholic acid has been studied and the selectivity of enclathration determined by competition experiments.     

Determination of the Hydroxyl Value of Soybean Polyol by Attenuated Total Reflectance/Fourier Transform Infrared Spectroscopy

A rapid method for the quantitative determination of the hydroxyl value (OHV) of hydroxylated soybean oils by HATR/FTIR spectroscopy is described. Calibration standards were prepared by the formic acid/hydrogen peroxide method and OH values were determined by the official method of AOCS Tx 1a-66, covering an analytical range of 3.5–125 mg of KOH/g of sample. A partial least squares (PLS) calibration model for the prediction of the hydroxyl value (OHV) was developed based on eight different spectral subregions between 3,150 and 990 cm⁻¹ and combinations of them. On average, 36 samples were used for the modeling and 17 were used for external validation. The resulting calibration was linear over the analytical range and had a standard deviation of 2.334. Validation of the method was carried out by comparing the OHV of a series of hydroxylated soybean oils predicted by the PLS model to the values obtained by the AOCS standard method. A correlation coefficient of R ² = 0.9843 and RMSEC and RMSEP values of, respectively, 3.393 and 3.643 were obtained. After the calibration of the spectrometer, the OHV could be obtained in 2–3 min per sample, a major improvement over conventional wet chemical methods. The advantages of these methodologies are that they do not destroy the sample, have a lower cost, expedite the analysis and do not produce residues. Therefore, they may yield excellent results when used to quantify OHV of soybean polyols obtained by hydroxylation reaction.     

Effect of boron on the structural and electrochemical properties of nanocrystalline Ti2RuFeBx electrodes

The effect of the boron content on the structural and electrochemical properties of nanocrystalline Ti₂RuFeB_x (with x varying from 0 to 12) was studied. The nanocrystalline materials were prepared by high energy ball milling and their structural evolution was analyzed by X-ray and neutron diffraction. Through a detailed Rietveld refinement analysis of the structural data, it is shown that the nanocrystalline materials are mainly composed of a B2 structure at low boron content (0 < x < 2). At higher boron content, TiB₂ is mainly formed and the B2 structure disappears with the concurrent formation of a highly disordered Ru-rich phase. These electrodes were tested for the hydrogen evolution reaction in both NaOH and chlorate solutions. The best results are obtained for 4 ≤ x ≤ 6, with a cathodic overpotential at −250 mA/cm², η₂₅₀, of ∼−575 mV. Accelerated aging tests and continuous electrolysis tests show that η₂₅₀ does not vary with time, contrary to the case of Ti₂RuFe, which shows a rapid deterioration of the cathodic overpotential after a few hours of continuous electrolysis. This is explained by the lower solubility of hydrogen in Ti₂RuFeB₄ as opposed to Ti₂RuFe.     

The role of MCM-41 composition in the creation of basicity by alkali metal impregnation

Three types of mesoporous molecular sieves (silicate MCM-41, niobosilicate NbMCM-41, and aluminosilicate AlMCM-41) were impregnated with alkali metal acetates. The textural stability of the samples was estimated on the basis of XRD measurements and nitrogen adsorption/desorption methods. The acidic–basic properties of the obtained materials were tested in the cyclization of acetonylacetone and studied by FTIR spectroscopy after adsorption of methylacetylene (propyne) and pyridine. Two types of chemical reactions between mesoporous matrix and alkali metal salt/oxide were observed: the reaction between alkali metal salt and silica/silicate and the reaction between basic oxide and silanol groups or Na⁺ cations. In the first one the alkali metal silicate formation decreases from Li to Cs species and leads to the destruction of the material. The second reaction places alkali metal cations in extra framework positions, which increases from Li to Cs species and is only observed in the case of AlMCM-41 and NbMCM-41 materials. As a result of the second reaction Lewis acidity is generated. The average effect of these two interactions leads to the volcanic curve for basicity of M/AlMCM-41 and M/NbMCM-41 with the maximum for K-samples. In contrast, basicity of M/MCM-41 systematically increases from Li to Cs form since the second type of interaction does not occur for these samples.     

An efficient method for the synthesis of peptide aldehyde libraries employed in the discovery of reversible SARS coronavirus main protease (SARS-CoV Mpro) inhibitors

A method for the parallel solid-phase synthesis of peptide aldehydes has been developed. Protected amino acid aldehydes obtained by the racemization-free oxidation of amino alcohols with Dess-Martin periodinane were immobilized on threonyl resins as oxazolidines. Following Boc protection of the ring nitrogen to yield the N-protected oxazolidine linker, peptide synthesis was performed efficiently on this resin. A peptide aldehyde library was designed for targeting the SARS coronavirus main protease, SARS-CoV M(pro)(also known as 3CL(pro)), on the basis of three different reported binding modes and supported by virtual screening. A set of 25 peptide aldehydes was prepared by this method and investigated in inhibition assays against SARS-CoV M(pro). Several potent inhibitors were found with IC(50) values in the low micromolar range. An IC(50) of 7.5 muM was found for AcNSTSQ-H and AcESTLQ-H. Interestingly, the most potent inhibitors seem to bind to SARS-CoV M(pro) in a noncanonical binding mode.     

Characterisation of the adsorption sites of hydrogen on Pt/C fuel cell catalysts

A key component of a hydrogen fuel cell is a catalyst to dissociate dihydrogen to hydrogen atoms. In the present study, the adsorption of hydrogen on Pt/C fuel cell catalysts has been investigated by inelastic neutron scattering spectroscopy.

Monitoring a clean Pt(50%)/C catalyst with low energy neutron spectroscopy, after exposure to dihydrogen at 20 K, as it was heated to room temperature, showed three distinct temperature regimes: (i) a decrease in intensity from 10 to 60 K, (ii) a rise to a maximum between 60 and 120 K and then (iii) a slow fall-off towards room temperature. We assign the three regions as: (i) desorption of physisorbed dihydrogen, (ii) dissociation of dihydrogen to give an adsorbed layer and (iii) damping of the response by an increasing Debye–Waller factor.

The vibrational INS spectra of a series of Pt/C catalysts prepared under varying conditions were similar indicating that the same types of site are common to all the catalysts, although the relative proportions of each site are sample dependent. Features at 520, 950 and part of the intensity at 1300 cm⁻¹ are assigned to hydrogen on (1 1 1) faces, in good agreement with single crystal data. The mode at 640 cm⁻¹ is assigned as the doubly degenerate asymmetric stretch of Pt(1 0 0) faces with the symmetric stretch near 550 cm⁻¹.

We assign the bending mode of the on-top site to the feature at 470 cm⁻¹. The Pt–H stretch mode was observed at 2079 cm⁻¹. This is a significant result: this is the first time that hydrogen on the on-top sites has been observed on nanosized platinum particles supported on high surface area carbon black. The width of the INS peak is surprisingly large and may give additional information on the type and relative proportions of the crystallographic faces present on the catalyst particles.     

Prediction of Experimental Methanol Decomposition Rates on Platinum from First Principles

A microkinetic model for methanol decomposition on platinum is presented. The model incorporates competitive decomposition pathways, beginning with both O–H and C–H bond scission in methanol, and uses results from density functional theory (DFT) calculations [Greeley and Mavrikakis, J. Am. Chem. Soc. 124 (2002) 7193, Greeley and Mavrikakis, J. Am. Chem. Soc. 126 (2004) 3910]. Results from reaction kinetics experiments show that the rate of H₂ production increases with increasing temperature and methanol concentration in the feed and is only nominally affected by the presence of CO or H₂ with methanol. The model, based on the values of binding energies, pre-exponential factors and activation energy barriers derived from first principles calculations, accurately predicts experimental reaction rates and orders. The model also gives insight into the most favorable reaction pathway, the rate-limiting step, the apparent activation energy, coverages, and the effects of pressure. It is found that the pathway beginning with the C–H bond scission (CH₃OH→H₂COH→HCOH→CO) is dominant compared with the path beginning with O–H bond scission. The cleavage of the first C–H bond in methanol is the rate-controlling step. The surface is highly poisoned by CO, whereas COH appears to be a spectator species.     

Preparation and Characterization of Hyperbranched Polymer/Silica Hybrid Nanocoatings by Dual‐Curing Process

Summary: Organic‐inorganic nanocomposite hybrid coatings were prepared through a dual‐cure process involving cationic photopolymerization of a hyperbranched epoxy functionalized resin and subsequent condensation of an alkoxysilane inorganic precursor. All the formulations investigated gave rise to photocured films characterized by high gel content values. An increase in glass transition temperature and an increase in storage modulus above T_g in the rubbery plateau is observed with increasing TEOS content in the photocurable formulation. The important role of GPTS on reducing the inorganic domain size and avoiding macroscopic phase separation was demonstrated by TEM analyses.

TEM obtained for one of the cured films in the presence of GPTS.     

In situ electrochemical impedance spectroscopy/synchrotron radiation grazing incidence X-ray diffraction—A powerful new technique for the characterization of electrochemical surfaces and interfaces

A marriage of electrochemical impedance spectroscopy (EIS) and in situ synchrotron radiation grazing incidence X-ray diffraction (SR-GIXRD) has provided a powerful new technique for the elucidation of the mechanistic chemistry of electrochemical systems. In this study, EIS/SR-GIXRD has been used to investigate the influence of metal ion buffer calibration ligands, along with natural organic ligands in seawater, on the behaviour of the iron chalcogenide glass ion-selective electrode (ISE). The SR-GIXRD data demonstrated that citrate - a previously reported poor iron calibration ligand for the analysis of seawater - induced an instantaneous and total dissolution of crystalline GeSe and Sb₂Se₃ in the modified surface layer (MSL) of the ISE, while natural organic ligands in seawater and a mixture of ligands in a mimetic seawater ligand system protected the MSL's crystalline inclusions of GeSe and Sb₂Se₃ from oxidative attack. Expectedly, the EIS data showed that citrate induced a loss in the medium frequency time constant for the MSL of the ISE, while seawater's natural organic ligands and the mimetic ligand system preserved the medium frequency EIS response characteristics of the ISE's MSL. The new EIS/SR-GIXRD technique has provided insights into the suitability of iron calibration ligands for the analysis of iron in seawater.