Hydroboration of an alkene by amine-boranes catalysed by a [Rh(PR3)2]+ fragment. Mechanistic insight and tandem hydroboration/dehydrogenation

The catalytic hydroboration of tert-butylethene using H(3)B·NMe(3) gives RH(2)B·NMe(3). With H(3)B·NMe(2)H tandem hydroboration under mild conditions/dehydrocoupling occurs that produces R(2)B=NMe(2) (R = H, CH(2)CH(2)(t)Bu).     

Preparation of Fe2O3-exfoliated graphite composite and its electrochemical properties investigated in alkaline solution

In the present work, a simple method of preparation of FeCl₄⁻- graphite intercalation compounds from HCl/FeCl₃ solution with the aid of chemical oxidant is presented. Based on X-ray diffraction measurements it was concluded, that stages 8, 6, and 5 FeCl₄⁻-graphite intercalation compounds were obtained. The compounds thus obtained were thermally treated to obtain Fe₂O₃-exfoliated graphite composites. The dispersion of Fe₂O₃ in the exfoliated graphite flakes was examined with the aid of the energy dispersive X-ray analysis combined with a scanning electron microscopy. Electrochemical behavior of electrodes was investigated in 6 M KOH solution. Electrochemical investigations proved the formation of FeOOH on the surface of exfoliated graphite during the anodic process. Besides, electrochemical investigations showed that the lower limit potential strongly affects the redox behavior of the Fe₂O₃-EG electrode.     

Characterization of β-cyclodextrin inclusion complex with procaine hydrochloride by 1H NMR and ITC

The inclusion of local anesthetic drug procaine hydrochloride by β-cyclodextrin was investigated by 1D and 2D proton NMR spectroscopy and isothermal titration calorimetry (ITC) at 298 K. The stoichiometry of the complex was determinate by the method of continuous variation, using the chemical induced shift of both host and guest protons. The association constant K, of the obtained complex was calculated and found to be 293.17 M^?1. Rotating frame NOE spectroscopy, was used to ascertain the solution geometry of the host–guest complex. The result reveals that the procaine molecule penetrates into the β-cyclodextrin cavity with the aromatic ring. The energetics of complexation process is investigated by ITC technique. The analysis indicates that the complexation of procaine by β-CD is an exothermic process and show that both enthalpy and entropy contribute to the binding process. The obtained value for the association constant is in good agreement with that obtained from NMR.     

New evaporative light scattering detector for high temperature gel permeation chromatography

A new evaporative light scattering detector (ELSD) for the analysis of polyolefins by high temperature gel permeation chromatography (GPC) was recently introduced by Agilent Technologies. For the first time, we investigated the possibility to use this detector to measure the molecular weight distributions (MWD) of different type of polyolefines (polypropylene, linear, and low-density polyethylene). These samples were previously characterized by GPC with a differential refractive index (DRI) detector by several companies, in an interlaboratory study conducted by International Union of Pure and Applied Chemistry.^[1 Luruli, N. 2010. PHASE 1: IUPAC SEC/GPC Round Robin Project Report: Repeatability and Reproducibility of Sample Preparation and Analysis in High-Temperature SEC, http://media.iupac.org/projects/2005/2005-011-3-400_rpt-phase1_110510.pdf [Google Scholar]^] The excellent baseline stability of ELSD as compared with DRI was reflected in a better reproducibility of the measured average molecular weights. More importantly, after applying required corrections to linearize the response of the ELSD as a function of concentration, we obtained similar results as previously obtained with DRI for the MWD of analyzed resins, covering typical applications of polyolefins.     

Cross‐Linked Aptamer–Lipid Micelles for Excellent Stability and Specificity in Target‐Cell Recognition

The specific binding ability of DNA–lipid micelles (DLMs) can be increased by the introduction of an aptamer. However, supramolecular micellar structures based on self‐assemblies of amphiphilic DLMs are expected to demonstrate low stability when interacting with cell membranes under certain conditions, which could lead to a reduction in selectivity for targeting cancer cells. We herein report a straightforward cross‐linking strategy that relies on a methacrylamide branch to link aptamer and lipid segments. By an efficient photoinduced polymerization process, covalently linked aptamer–lipid units help stabilize the micelle structure and enhance aptamer probe stability, further improving the targeting ability of the resulting nanoassembly. Besides the development of a facile cross‐linking method, this study clarifies the relationship between aptamer–lipid concentration and the corresponding binding ability.     

Selective dissolution of TiO2 crystalline phases: Physicochemical characterization and photocatalytic activity

In this study, different commercially available TiO₂ powders (Degussa P25, pure anatase, and rutile) were submitted to selective dissolution treatments, with H₂O₂/NH₄OH and 10% HF, known to remove rutile and anatase from physical mixtures. The aim was to check whether a particular separation method designed to remove a specific crystalline phase influences the properties of the other phase from the mixture or not. More precisely, we have studied how the HF dissolution method designed to selectively remove the anatase affected the physicochemical and photocatalytic properties of rutile. In a similar way, the changes in the anatase properties were studied, after the H₂O₂/NH₄OH treatment, initially used to remove rutile from the mixture. All the samples were characterized by X-ray diffraction, nitrogen adsorption–desorption, transmission electron microscopy, diffuse reflectance (DR) ultraviolet–visible, and Raman spectroscopy. The photocatalytic activity of these powders was tested in the oxidation of p-chlorophenol from water. The selective treatment methods not only dissolved the target phase but also changed some physicochemical and the photocatalytic performances of the other TiO₂ crystalline phase in a considerable manner. These aspects should be taken into account in the studies regarding the synergistic effects of anatase and rutile, especially in reconstructed TiO₂ photocatalysts.     

Understanding the role of carbamate reactivity in fatty acid amide hydrolase inhibition by QM/MM mechanistic modelling

QM/MM modelling of FAAH inactivation by O-biphenyl-3-yl carbamates identifies the deprotonation of Ser241 as the key reaction step, explaining why FAAH is insensitive to the electron-donor effect of conjugated substituents; this may aid design of new inhibitors with improved selectivity and in vivo potency.