Studies of Brønsted acid-base equilibria in water and nonaqueous media

http://www.ester.ee/record=b4328691~S58*es

Basicities of Strong Bases in Water: A Computational Study

Aqueous pKa values of strong organic bases – DBU, TBD, MTBD, different phosphazene bases, etc – were computed with CPCM, SMD and COSMO-RS approaches. Explicit solvent molecules were not used. Direct computations and computations with reference pKa values were used. The latter were of two types: (1) reliable experimental aqueous pKa value of a reference base with structure similar to the investigated base or (2) reliable experimental pKa value in acetonitrile of the investigated base itself. The correlations of experimental and computational values demonstrate that direct computations do not yield pKa predictions with useful accuracy: mean unsigned errors (MUE) of several pKa units were observed. Computations with reference bases lead to MUE below 1 pKa unit and are useful for predictions. Recommended aqueous pKa values are proposed for all investigated bases taking into account all available information: experimental pKa values in acetonitrile and water (if available), computational pKa values, common chemical knowledge

No tillage in rainfed Aragon (NE Spain): Effect on organic carbon in the soil surface horizon

25 Pags., 7 Figs. The definitive version is available at: http://www.sciencedirect.com/science/journal/01671987Conservation tillage has been encouraged as a management alternative to preserve soil and water resources in semiarid Aragon (NE Spain). In fact, its adoption by farmers, and especially of no tillage (NT) systems, has increased in recent years. However, little information concerning the soils on which these techniques are applied is available for this region. The objective of this study was to assess the potential of NT to increase organic carbon content at the soil surface (0–20 cm) in rainfed Aragon. To this aim, 22 pairs of adjacent farm fields under NT and conventional tillage (CT) were compared in different cereal production areas. The fields were under continuous NT between 5 and 19 years but half were over 10 years. Soil organic carbon (SOC) in NT ranged from 7.06 to 18.53 g kg−1 (0–20 cm depth) and was higher than 12 g kg−1 in nearly 30% of the fields. These contents represented between 8% less (only one case) and 55% more SOC under NT than under CT with an average gain of 20% in favour of NT. The highest SOC contents were found in the NT fields of longer duration (>10 years) and/or managed with practices that enhance the return of more crop biomass to the soil (complete residue return, cropping intensification and manure application). The identification of the current management practices used by farmers has allowed us to know the diversity of the NT-based cropping systems and the reality of the conservation agriculture in our region. Overall, results from this on-farm study indicate that NT can be recommended as a viable alternative to CT to increase organic carbon at the soil surface in cereal production areas of Aragon.This research was supported by the Comisión Interministerial de Ciencia y Tecnología of Spain (Grants AGL2010-22050-CO3-02/AGR and AGL2007-66320-C02-02/AGR) and the European Union (FEDER Funds). N. Blanco-Moure was awarded with a PhD fellowship (FPI Program) by the Spanish Ministry of Science and Innovation.Peer reviewe

Biphasic pKa Values

A novel approach – termed here as biphasic pKa values – is presented for quantifying the acidity/basicity of lipophilic compounds embedded in water-immiscible media (membranes or solutions) at equilibrium with aqueous solution. In this approach the hydrogen ion activity is determined in the aqueous phase, while the concentration ratio of protonated and deprotonated forms of acid/base is measured in the lipophilic phase with any suitable technique. The approach has been demonstrated on the example of biphasic pKa values of some lipophilic indicator bases in the octanol:water system, measured using UV-Vis spectrophotometry. The measurement is straightforward if the counterion identity and concentration and overall ionic strength in the aqueous phase are included in the standard state definition. Biphasic pKa values are envisaged to be useful for characterizing lipophilic indicators, synthetic receptors, phase transfer catalysts and other implements that are used in hydrophobic media (e.g. in sensor membranes) in contact with water. This work is licensed under a Creative Commons Attribution 4.0 International License

Inducing a pH-dependent conformational response by competitive binding to Zn2+ of a series of chiral ligands of disparate basicity

Molecules that change shape in response to environmental conditions are central to biological molecular communication devices and their synthetic chemical analogues. Here we report a molecular system in which a series of chiral anionic ligands of differing basicity are selectively protonated according to the pH of the medium. A cationic circular dichroism (CD) reporter complex responds to anion binding by selecting one of two alternative enantiomeric conformations. Exploiting the principle that less basic anions have, in general, weaker electrostatic interactions than more basic anions, a set of three chiral acids with large (>5 unit) pK(a) differences and differing configurations were sequentially deprotonated in acetonitrile by addition of base, allowing the most basic anion in the mixture at any time to bind to the reporter complex. A characteristic CD output resulted, which changed in sign as the next-most basic anion was revealed by the next deprotonation in the series. Four cycles of switching between three ligand-bound states were achieved with minimal changes in signal magnitude, by alternating addition of base and acid. The pH-dependent conformational response was used to transduce a signal by appending to the binding site a 2-aminoisobutyric acid (Aib) oligomer, whose M or P helical conformation depended on the chirality of the bound ligand, and was reported by a remote (13)C-labelled NMR reporter group. The multicomponent system thus converts a pH signal into a programmable conformational response which induces a remote spectroscopic effect

TrainMiC, Training in Metrology in Chemistry.

Abstract not availableJRC.D-Institute for Reference Materials and Measurements (Geel

Electrochemistry and Reactivity of Chelation‐stabilized Hypervalent Bromine(III) Compounds

Hypervalent bromine(III) reagents possess a higher electrophilicity and a stronger oxidizing power compared to their iodine(III) counterparts. Despite the superior reactivity, bromine(III) reagents have a reputation of hard‐to‐control and difficult‐to‐synthesize compounds. This is partly due to their low stability, and partly because their synthesis typically relies on the use of the toxic and highly reactive BrF3 as a precursor. Recently, we proposed chelation‐stabilized hypervalent bromine(III) compounds as a possible solution to both problems. First, they can be conveniently prepared by electro‐oxidation of the corresponding bromoarenes. Second, the chelation endows bromine(III) species with increased stability while retaining sufficient reactivity, comparable to that of iodine(III) counterparts. Finally, their intrinsic reactivity can be unlocked in the presence of acids. Herein, an in‐depth mechanistic study of both the electrochemical generation and the reactivity of the bromine(III) compounds is disclosed, with implications for known applications and future developments in the field.Deutsche Forschungsgemeinschaft http://dx.doi.org/10.13039/501100001659European Regional Development Fund http://dx.doi.org/10.13039/501100008530HORIZON EUROPE European Research Council http://dx.doi.org/10.13039/100019180Estonian Research Competency Council http://dx.doi.org/10.13039/501100005189Peer Reviewe

Synthesis and cathodic cleavage of a set of substituted benzenesulfonamides including the corresponding tert-butyl sulfonylcarbamates: pKa of sulfonamides

From a series of Substituted benzenesulfonic acids, most of which have previously been employed for the protection of amino functions and including a few such known to facilitate cleavage by acid, benzylamides 1a-k have been derived and studied. Initially their electrochemical cleavage potentials were determined by cyclic voltammetry in order to further explore selective deprotection within this substance group. In parallel, the corresponding tert-butyl sulfonylcarbamates 2a-k have also been prepared and studied. Among the sulfonamides investigated S-N bond cleavage was found to take place over a wide range of potentials from -1.67 to -2.64 V (excluding the nitro derivative), the most acid-labile groups requiring more negative potentials, whereas this cleavage was facilitated by 0.19-0.30 V for the sulfonylcarbamates. Small scale electrolyses of 2 at controlled potential with determination of the cleavage products formed were subsequently performed. For the N-benzylbenzenesulfonamides 1, the pK(a)s in DMSO and in some cases also in water have been determined and found to be in the range 14.0-16.4 and 10.07-11.53, respectively