Homolytic Cyclizations of N-Chloroalkenylamines

Many N-chloroalkylamines with double bond(s) dissociate homolytically to give chlorine atoms and aminyl radicals which undergo intramolecular cyclization reactions. Here, the nature of the aminyl radicals (neutral, protonated, or complexed to metal salts) appears to be important. The reactivity varies strongly from one species to another, and their selectivities can be different towards addition, substitution, abstraction, or dimerization reactions. A good synthetic tool appears to be the “complexed radical”, which is generated under mild conditions. A variety of β-functionalized, substituted, fused, or bridged azaheterocycles with alkaloid part structures thus become easily accessible in high yields, in a regio- and, possibly, stereoselective manner. Many examples are discussed illustrating the synthetic possibilities, limitations, and mechanistic features of this cyclization process.     

Involatile nanodroplets: an asymptotic analysis

The structure of nanometer-scale droplets of weakly volatile liquids arises through the interplay of strong intermolecular attraction, and core intermolecular repulsion, interfacial forces, and the large, negative chemical potential of the low density vapor with which it is in equilibrium. Using a van der Waals equation of state and a mesoscopic multiphase model, the structure of such nanodroplets is determined via an asymptotic analysis in terms of the ambient to critical temperature ratio. The structure of a spherical droplet is obtained as the solution of a simple "shooting" problem. The intradroplet pressure profile and a minimal droplet size are determined. The high pressure in the core of the droplet gives evidence for the preferred melting there for systems like water with a negative volume of melting. Our methodology can be generalized to multiphase droplets, as well as to composite structures wherein viruses or other nanoparticles are embedded.     

A Simple, Exact Density-Functional-Theory Embedding Scheme

Density functional theory (DFT) provides a formally exact framework for quantum embedding. The appearance of nonadditive kinetic energy contributions in this context poses significant challenges, but using optimized effective potential (OEP) methods, various groups have devised DFT-in-DFT methods that are equivalent to Kohn-Sham (KS) theory on the whole system. This being the case, we note that a very considerable simplification arises from doing KS theory instead. We then describe embedding schemes that enforce Pauli exclusion via a projection technique, completely avoiding numerically demanding OEP calculations. Illustrative applications are presented using DFT-in-DFT, wave-function-in-DFT, and wave-function-in-Hartree-Fock embedding, and using an embedded many-body expansion.     

Development of a chemiluminescence-based quantitative lateral flow immunoassay for on-field detection of 2,4,6-trinitrotoluene

Simple, rapid and highly sensitive assays, possibly allowing on-site analysis, are required in the security and forensic fields or to obtain early signs of environmental pollution. Several bioanalytical methods and biosensors based on portable devices have been developed for this purpose. Among them, Lateral Flow ImmunoAssays (LFIAs) offer the advantages of rapidity and ease of use and, thanks to the high specificity of antigen–antibody binding, allow greatly simplifying and reducing sample pre-analytical treatments. However, LFIAs usually employ colloidal gold or latex beads as labels and they rely on the formation of colored bands visible by the naked eye. With this assay format, only qualitative or semi-quantitative information can be obtained and low sensitivity is achieved. Recently, the use of enzyme-catalyzed chemiluminescence detection in LFIA has been proposed to overcome these problems. In this work, we describe the development of a quantitative CL-LFIA assay for the detection of 2,4,6-trinitrotoluene (TNT) in real samples. Thanks to the use of a portable imaging device for CL signal measurement based on a thermoelectrically cooled CCD camera, the analysis could be performed directly on-field. A limit of detection of 0.2 μg mL⁻¹ TNT was obtained, which is five times lower than that obtained with a previously described colloidal gold-based LFIA developed employing the same immunoreagents. The dynamic range of the assay extended up to 5 μg mL⁻¹ TNT and recoveries ranging from 97% to 111% were obtained in the analysis of real samples (post blast residues obtained from controlled explosion).     

Propeller wake flowfield analysis by means of LDV phase sampling techniques

 Two phase sampling techniques are developed for the analysis of the propellers wake by means of LDV. The first one (TTT) uses the detection of Doppler signal as trigger condition; each LDV sample, tagged with the blade angular position at the measurement time, is arranged inside angular slots. The other technique (ATT) follows an angular triggering method, with some enhancements to reduce measurement time. The implemented techniques are complementary from the accuracy and efficiency point of view. The TTT enables to quickly analyze the propellers wake, in view of the minimization of data acquisition time, particularly in poor flow seeding conditions. The ATT is instead suitable for accurate investigations of space-limited and highly turbulent flow regions. Received: 29 July 1998/Accepted: 18 February 1999     

Capto-dative Substituent Effects in Syntheses with Radicals and Radicophiles [New synthetic methods (32)]

The 100 yers old Wurster's salts have long been recognized as compounds with redical cations. Their unusual stabilization derives partly form capto-dative (cd) substitution. This principle is now discussed as one factor of radical stabilization and it is applied to simple methine derivatives. cd-Substitution has synthetically useful applications: cd-substituents on a carbon atom allow its selective dehydrodimerization. Olefines with geminal and thus cross-conjugated cd-substituents are “radicophilic” and permit twofold carbon radical addition. cd-Substituted olefines are useful antioxidants, polymerization inhibitors and are promising agents in the control of biological radical reactions. Generally, many reactions of cd-substituted molecules appear to involve radicals.     

Transformation des dienes conjugues en sulfones allyliques

The reaction of dienes with arenesulphinic acids or sodium arenesulphinates in acetic acid in the presence of palladium catalysts gives high yields of allylic sulphones containing large proportions of (sometimes exclusively) the more substituted isomer.     

NMR Conformational Study of Aminoalkylbenzamides,Aminoalkyl-o-anisamides,and Metoclopramide,a Dopamine Receptor Antagonist

The conformational behaviour of metoclopramide, a neuroleptic benzamide, and model compounds was investigated byt ¹ H-NMR spectroscopy. An intramolecular amide-methoxy H-bond is shown to exist in CDCl₃-solution, but not in D₂O-solution, independently of the length and protonation state of the basic side-chain. This H-bond creates a virtual cycle which may be a key feature for the binding of neuroleptic benzamides to the dopamine receptor. The conformational behaviour of the aminoethyl side-chain is shown to be markedly condition-dependent. For metoclopramide and its analogues in their protonated form, the gauche- and trans- rotamers have identical energies in D₂O-as well as in CDCl₃-solutins. For the non-protonated molecules, the trans-rotamer is favoured in D₂O-solutin, while the gauche-rotamer is favoured in CDCl₃-solution (ΔG°?|0.5|kcal/mol in both cases). The side-chain conformation of neuroleptic benzamides is discussed in terms of receptor affinity.     

On estimating a density using Hellinger distance and some other strange facts

Résumé On s'intéresse ici aux possibles vitesses d'estimation d'une densité à support compact dans ^m sous des hypothèses de régularité, lorsque la perte est mesurée par le carré de la distance de Hellinger (on regardera aussi le cas connu des normes pour 1q2) et le risque est le risque minimax sur la famille. On donne une méthode générale permettant de traiter les problèmes dans le cadre de la théorie de l'approximation sous des conditions concernant l'entropie métrique et l' -capacité des familles à estimer. Les rapports entre régularité et entropie métrique étant bien connus, nous pourrons aussi traiter les cas classiques et d'autres qui le sont moins. Sous des conditions de bornes inférieures les vitesses sont celles observées pour la norme mais elles diffèrent dans le cas général. On montre aussi que les restrictions sur la compacité du support ou la régularité sont indispensables et que leur absence mène à l'impossibilité d'obtenir une estimation raisonnable en ce sens que n'importe quelle suite d'estimateurs sera arbitrairement mauvaise en un point au moins. Un résultat analogue est vrai sous des conditions de régularité.

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This work was carried out during a visit of the author at the Mathematical Sciences Research Institute at Berkeley     

The influence of captodative effect on the dienophilicity of olefins. The easy diels-alder reaction of α-methylthioacrylonitrile with cyclohexadiene

We show that the cycloaddition of α-methylthioacrylonitrile to cyclohexadiene is faster than that of acrylonitrile. This indicates that the captodative substitution exerts an accelerating effect on the Diels-Alder reaction despite the larger steric bulk of the methylthio group compared to hydrogen.