Evidence of anion-induced dimerization of a squaramide-based host in protic solvents

The combination of squaramide units with tetraalkylammonium groups leads two hosts that bind distinctively dianions in water-ethanol mixtures. The formation of complexes of 2:1 stoichiometry with host was supported by ITC, fluorescence, and (1)H NMR data.     

Synthesis, structural characterization and anion binding studies of palladium macrocycles with hydrogen-bonding ligands

The reactions between [Pd(P-P)(OTf)2] (where P-P=dppp or dppf) and two different bipyridyl ligands (=1,3-bis(4-pyridylmethyl)urea and=1,3- bis(pyridinylmethyl)benzenedicarboxamide) containing hydrogen-bonding units have been studied. The X-ray crystal structures of three of these assemblies have been solved showing them to be the [2+2] metallo-macrocycles [Pd(P-P)(n)]2(OTf)4 [P-P=dppp, n=1, (); P-P=dppp, n=2, (); P-P=dppf, n=1, ()]. To confirm whether the dimeric assembly of one of these species () is retained in solution, several investigations have been carried out. 1H NMR studies in DMSO and high resolution ESI mass spectrometry have shown that is in equilibrium with a larger [3+3] metallo-macrocycle. The equilibrium between these two species can be modified by changing the temperature, concentration or solvent. Also, addition of certain anions (e.g. [H2PO4]-) to the mixture shifts the equilibrium favoring the formation of the [2+2] metallo-macrocycle over the [3+3] (initially present in a larger proportion).     

Ultrafast shape recognition to search compound databases for similar molecular shapes

Finding a set of molecules, which closely resemble a given lead molecule, from a database containing potentially billions of chemical structures is an important but daunting problem. Similar molecular shapes are particularly important, given that in biology small organic molecules frequently act by binding into a defined and complex site on a macromolecule. Here, we present a new method for molecular shape comparison, named ultrafast shape recognition (USR), capable of screening billions of compounds for similar shapes using a single computer and without the need of aligning the molecules before testing for similarity. Despite its extremely fast comparison rate, USR will be shown to be highly accurate at describing, and hence comparing, molecular shapes.     

Self-assembly of a water-soluble endohedrally functionalized coordination cage including polar guests

Coordination cages containing endohedrally functionalized aromatic cavities are scarce in the literature. Herein, we report the self-assembly of a tetra-cationic super aryl-extended calix[4]pyrrole tetra-pyridyl ligand into a water-soluble Pd(ii)-cage featuring two endohedral polar binding sites. They are defined by the four pyrrole NHs of the calix[4]pyrrole unit and the four inwardly directed α-protons of the coordinated pyridyl groups. The efficient assembly of the Pd(ii)-cage requires the inclusion of mono- and ditopic pyridyl N-oxide and aliphatic formamide guests. The monotopic guests only partially fill the cage''s cavity and require the co-inclusion of a water molecule that is likely hydrogen-bonded to the endohedral α-pyridyl protons. The ditopic guests are able to completely fill the cage''s cavity and complement both binding sites. We observed high conformational selectivity in the inclusion of the isomers of α,ω-bis-formamides. We briefly investigate the uptake and release mechanism/kinetics of selected polar guests by the Pd(ii)-cage using pair-wise competition experiments.

A tetra-cationic calix[4]pyrrole tetra-pyridyl ligand self-assembles into a water-soluble Pd(ii)-cage featuring two endohedral polar binding sites. The Pd(ii)-cage encapsulates pyridyl N-oxide and aliphatic formamide guests in water.     

Embeddings of SL(2; ?) into the cremona group

Geometric and dynamic properties of embeddings of SL(2; ℤ) into the Cremona group are studied. Infinitely many nonconjugate embeddings that preserve the type (i.e., that send elliptic, parabolic and hyperbolic elements onto elements of the same type) are provided. The existence of infinitely many nonconjugate elliptic, parabolic and hyperbolic embeddings is also shown. In particular, a group G of automorphisms of a smooth surface S obtained by blowing up 10 points of the complex projective plane is given. The group G is isomorphic to SL(2; ℤ), preserves an elliptic curve and all its elements of infinite order are hyperbolic.     

Sodium and pH responsive hydrogel formation by the supramolecular system calix[4]pyrrole derivative/tetramethylammonium cation

We report and rationalize the formation of gels, responsive to sodium cations or pH changes, in aqueous media by a supramolecular system constituted of an aryl extended calix[4]pyrrole receptor and the tetramethylammonium guest.     

CASPT2 study of the potential energy surface of the HSO2 system

The importance of the HSO(2) system in atmospheric and combustion chemistry has motivated several works dedicated to the study of associated structures and chemical reactions. Nevertheless controversy still exists in connection with the reaction SH + O(2)→ H + SO(2) and also related to the role of the HSOO isomers in the potential energy surface (PES). Here we report high-level ab initio calculation for the electronic ground state of the HSO(2) system. Energetic, geometric, and frequency properties for the major stationary states of the PES are reported at the same level of calculations: CASPT2/aug-cc-pV(T+d)Z. This study introduces three new stationary points (two saddle points and one minimum). These structures allow the connection of the skewed HSOO(s) and the HSO(2) minima defining new reaction paths for SH + O(2) → H + SO(2) and SH + O(2) → OH + SO. In addition, the location of the HSOO isomers in the reaction pathways have been clarified.