Non-statistical energy partitioning in the gas phase reactions of polyatomic molecules

The internal energy distributions in the HF products from the reactions of F atoms with H₂CO and HFCO have been determined via arrested-relaxation infrared chemiluminescence experiments. The results show that the HF vib-rotational levels are strongly excited and suggest that the HCO and FCO radical products are created with excitation in the ν₁ (asymmetric stretch) and ν₂ (bend) modes respectively.     

Synthetic and structural comparisons of bismuth(III) carboxylates synthesised under solvent-free and reflux conditions

Two synthetic approaches to the formation of bismuth(III) carboxylates have been explored and compared. Ph(3)Bi was reacted with a series of carboxylic acids (RCO(2)H) of varying pK(a) and functionality (R = PhCH[double bond, length as m-dash]CH, o-MeOC(6)H(4), m-MeOC(6)H(4), o-H(2)NC(6)H, o-O(2)NC(6)H(4), p-O(2)NC(6)H(4), 2-(C(5)H(4)N)) under reflux conditions in toluene and solvent-free. The thermochemical profiles of the solvent-free reactions were also studied by DSC-TGA. All reactions produced the tri-substituted bismuth carboxylates in comparable yields and purity with the exceptions of picolinic acid and p-nitrobenzoic acid. 2-Picolinic acid exclusively formed the di-substituted complex, [PhBi(2-(C(5)H(4)N)CO(2))(2)](4), by both methods, while p-nitrobenzoic acid gave the tri-substituted complex through reflux and the di-substituted complex under solvent-free conditions. Two of the complexes were structurally authenticated by single crystal X-ray diffraction: [PhBi(2-(C(5)H(4)N)CO(2))(2)](4) is tetrameric formed through five membered chelate rings involving the pyridyl N and O(-C) rather than the less stable carboxylate (-CO(2)) chelates, while [Bi(o-MeOC(6)H(4)CO(2))(3)](infinity), is a polymer in which dimeric units, constructed around two chelating and one unsymmetrical bridging carboxylate on each Bi centre, are then joined together through longer intermolecular Bi-O bridging bonds.     

Synthesis and structural characterisation of heavy alkaline earth N,N'-bis(aryl)formamidinate complexes

Treatment of calcium or strontium with 2.0 equivalents of N,N-bis(o-methylphenyl)formamidine (o-TolFormH), N,N-bis(2,6-dimethylphenyl)formamidine (XylFormH) or N,N-bis(o-phenylphenyl)formamidine (o-PhPhFormH) in the presence of 1.0 equivalent of Hg(C6F5)2 in tetrahydrofuran (thf) affords the bis(formamidinate) complexes [Ca(o-TolForm)2(thf)2] (1), [Ca(XylForm)2(thf)2] (2), [Ca(o-PhPhForm)2(thf)2].thf (3), [Sr(o-TolForm)2(thf)3] (4), [Sr(XylForm)2(thf)3].3thf (5) and [Sr(o-PhPhForm)2(thf)3].2thf (6). Analogous reactions with barium were generally unsatisfactory but [Ba(o-PhPhForm)2(thf)3].2thf (7) was successfully prepared. Compounds 1-7 have been characterised by various spectroscopic methods (1H, 13C{1H} NMR and IR), elemental analyses and, for 1, 2 and 4-6, X-ray crystallography. The calcium complexes are monomeric and six-coordinate with either transoid octahedral or trigonal prismatic geometry, whilst the larger radius of strontium accommodates an additional thf solvent donor to give seven-coordinate structures with two types of coordination polyhedra.     

Characterizing bitterness: identification of key structural features and development of a classification model

This work describes the first approach in the development of a comprehensive classification method for bitterness of small molecules. The data set comprises 649 bitter and 13 530 randomly selected molecules from the MDL Drug Data Repository (MDDR) which are analyzed by circular fingerprints (MOLPRINT 2D) and information-gain feature selection. The feature selection proposes substructural features which are statistically correlated to bitterness. Classification is performed on the selected features via a na?ve Bayes classifier. The substructural features upon which the classification is based are able to discriminate between bitter and random compounds, and thus we propose they are also functionally responsible for causing the bitter taste. Such substructures include various sugar moieties as well as highly branched carbon scaffolds. Cynaropicrine contains a number of the substructural features found to be statistically associated with bitterness and thus was correctly predicted to be bitter by our model. Alternatively, both promethazine and saccharin contain fewer of these substructural features, and thus the bitterness in these compounds was not identified. Two different classes of bitter compounds were identified, namely those which are larger and contain mainly oxygen and carbon and often sugar moieties, and those which are rather smaller and contain additional nitrogen and/or sulfur fragments. The classifier is able to predict 72.1% of the bitter compounds. Feature selection reduces the number of false-positives while also increasing the number of false negatives to 69.5% of bitter compounds correctly predicted. Overall, the method presented here presents both one of the largest databases of bitter compounds presently available as well as a relatively reliable classification method.     

A microfluidic SELEX prototype

Aptamers are nucleic acid binding species capable of recognizing a wide variety of targets ranging from small organic molecules to supramolecular structures, including organisms. They are isolated from combinatorial libraries of synthetic nucleic acid by an iterative process referred to as SELEX (Systematic Evolution of Ligands by Exponential Enrichment). Here we describe an automated microfluidic, microline-based assembly that uses LabView-controlled actuatable valves and a PCR machine, and which is capable of the selection and synthesis of an anti-lysozyme aptamer as verified by sequence analysis. The microfluidic prototype described is 1) a simple apparatus that is relatively inexpensive to assemble, making automated aptamer selection accessible to many investigators, and 2) useful for the continued “morphing” of macro→meso→microfabricated structures until a convergence to a few functional systems evolves and emerges, partly or completely achieving simpler, smaller and more rapid SELEX applications.     

A Lewis acid-catalyzed formal [3 + 3] cycloaddition of alpha,beta-unsaturated aldehydes with 4-hydroxy-2-pyrone, diketones, and vinylogous esters

[reaction: see text] A Lewis acid-catalyzed formal cycloaddition of alpha,beta-unsaturated aldehydes with 6-methyl-4-hydroxy-2-pyrone, 1,3-diketones, and vinylogous silyl esters is described here.     

Unstable Willmore surfaces of revolution subject to natural boundary conditions

In the class of surfaces with fixed boundary, critical points of the Willmore functional are naturally found to be those solutions of the Euler-Lagrange equation where the mean curvature on the boundary vanishes. We consider the case of symmetric surfaces of revolution in the setting where there are two families of stable solutions given by the catenoids. In this paper we demonstrate the existence of a third family of solutions which are unstable critical points of the Willmore functional, and which spatially lie between the upper and lower families of catenoids. Our method does not require any kind of smallness assumption, and allows us to derive some additional interesting qualitative properties of the solutions.