Modeling the interactions between peptide functions and Sr2+: formamide-Sr2+ reactions in the gas phase

The interactions between formamide, which can be considered a prototype of a peptide function, and Sr(2+) have been investigated by combining nanoelectrospray ionization/mass spectrometry techniques and G96LYP DFT calculations. For Sr an extended LANL2DZ basis set was employed, together with a 6-311+G(3df,2p) basis set expansion for the remaining atoms of the system. The observed reactivity seems to be dominated by the Coulomb explosion process yielding [SrOH](+) + [HNCH](+), which are the most intense peaks in the MS/MS spectra. Nevertheless, additional peaks corresponding to the loss of HNC and CO indicate that the association of Sr(2+) to water or to ammonia leads to long-lived doubly charged species detectable in the timescale of these experimental techniques. The topology of the calculated potential energy surface permits us to establish the mechanisms behind these processes. Although the interaction between the neutral base and Sr(2+) is essentially electrostatic, the polarization triggered by the doubly charged metal ion results in the activation of several bonds, and favors different proton transfer mechanisms required for the formation of the [SrOH](+), [SrOH(2)](2+) and [SrNH(3)](2+) products.     

Titan Based Hybrid Organic-Inorganic Gels Comprising Carbohydrate Moiety

Abstract

A series of titanium based gels comprising carbohydrate moieties was synthesized. The sugars used include a specific hydrazide group as complex forming agent. Additionally, this group forms stable hydrates which allow further slow water release. As a result, the compounds used in this study form transparent and stable gels with titanium alkoxide without addition of external water. Interpretation of the IR-spectra reveals that some compounds form monodentate ligands and other bidentate ligands. Further Tian-Calvet calorimetric measurements confirmed our IR-based conclusions. This strategy of synthesis gives a new opportunity to obtain hybrid materials by addition of natural chelating ligands to slow down the hydrolysis/condensation reactions that occur during the sol-gel process. Therefore, carbohydrate moieties have been incorporated in the gels obtained and different type of Ti coordination was proposed based on the IR spectroscopy studies. SEM investigations show the influence of the ligand on the morphology of the xerogel.

GRAPHICAL ABSTRACT      

A Simple and Efficient Procedure for the Preparation of Benzal Chlorides and Benzal Bromides

Benzal chlorides and benzal bromides were conveniently synthesized by reaction of aryl aldehydes with a Vilsmeier type reagent formed in situ by reduction of CC1₄ or CBr₄ in dimethylformamide (DMF) as solvent.     

Stereoselective Synthesis of Versatile Intermediates for Clerodanes Total synthesis

The stereoselective synthesis of compounds 2a-d, attractive intermediates for the synthesis of clerodane diterpenes is described in 6 to 9 steps in good overall yields from commercially available racemic Wieland-Miescher ketone.     

Anion-π Interaction for Molecular Recognition of Anions: Focus on Cooperativity with Hydrogen Bonding

Anion recognition represents an active area of research in supramolecular chemistry. The last two decades have been marked by spectacular advances in the design of new anion receptors. Moreover, the development of approaches combining experimental and theoretical studies has proved to be particularly relevant, allowing for a better understanding and rationalization of the phenomena involved in anion complexation processes. In this context, the combination of weak interactions within the same receptor and their synergistic effects, called cooperativity, has attracted increasing interest within the scientific community. This Review focuses on the combination of anion-π and hydrogen bonds and the emerging concept of cooperativity. The most relevant anion-π donor families are presented. The concept of cooperativity is illustrated using the most recent examples present in current literature.