Removal of a single minor-groove functional group eliminates A-tract curvature

Much of the work in studying the phenomenon of A-tract curvature has involved the insertion of modified residues into the A-tract sequence and then cross-correlation of the structural differences with the resulting curvature effects. In the A-tract sequence d(A-T)5, removal of a single functional group (the O2-carbonyl of the central dT residue) by its replacement with hydrogen completely eliminates the curvature properties. This atom-specific change was accomplished by using the C-nucleoside dm32P in which the O2-carbonyl is replaced with -H but normal Watson-Crick hydrogen bonding is maintained. Similar derivatives with -F (dF62P) or -CH3 (dm62P) when present for the central dT residue also eliminate curvature. Finally, we have shown that the extent of curvature for sequences containing this carbonyl are sensitive to the [Mg2+], while those lacking the carbonyl show little to no Mg2+ dependence, strongly suggesting, we believe, a role for Na+/Mg2+ cooperative interactions in the minor groove to explain the curvature phenomenon.     

Synthesis of a naphthyridone p38 MAP kinase inhibitor

Compound 1 is a p38 MAP kinase inhibitor potentially useful for the treatment of rheumatoid arthritis and psoriasis. A novel six-step synthesis suitable for large-scale preparation was developed in support of a drug development program at Merck Research Laboratories. The key steps include a tandem Heck-lactamization, N-oxidation, and a highly chemoselective Grignard addition of 4-(N-tert-butylpiperidinyl)magnesium chloride to a naphthyridone N-oxide. The N-oxide exerted complete chemoselectivity via chelation in directing the Grignard addition to the alpha position as opposed to 1,4-addition on the ene-lactam. The dihydropyridyl adduct was in situ aromatized with isobutylchloroformate followed by heating in pyridine. Syntheses of Grignard precursor, N-tert-butyl-4-chloro-piperidine, were accomplished via transamination with a quaternary ammonium piperidone or via addition of methylmagnesium chloride to an iminium ion. Utilizing this chemistry, multi-kilogram preparation of compound 1 was successfully demonstrated.     

Reactions of Nb2 and Nb3 with CO, D2, N2, and O2: reconciling experimental kinetics with density functional theory-calculated reaction profiles

Calculated energy profiles for the reactions of neutral Nb(2) and Nb(3) metal clusters with CO, D(2), N(2), and O(2) are presented. In each reaction path, both a physisorption energy minimum, where the reactant remains intact, and a chemisorption energy minimum, where the reactant has dissociated, are calculated and linked by saddle points. We calculate branching ratios for the forward (dissociative) and reverse reactions which we compare with the experimental kinetic data. It is found that a combination of average thermal energies and barrier heights leads to wide variation in branching ratios which compares favourably to previously determined experimental reaction rates.     

Long Time Behavior of the Continuum Limit¶of the Toda Lattice, and the Generation¶of Infinitely Many Gaps from C∞ Initial Data

We analyze a continuum limit of the finite non-periodic Toda lattice through an associated constrained maximization problem over spectral density functions. The maximization problem was derived by Deift and McLaughlin using the Lax–Levermore approach, initially developed for the zero dispersion limit of the KdV equation. It encodes the evolution of the continuum limit for all times, including evolution through shocks. The formation of gaps in the support of the maximizer is indicative of oscillations in the Toda lattice and the lack of strong convergence of the continuum limit. For large times, the maximizer tends to have zero gaps, which is the continuum analogue of the sorting property of the finite lattice. Using methods from logarithmic potential theory, we show that this behavior depends crucially on the initial data. We exhibit initial data for which the zero gap ansatz holds uniformly in the spatial parameter (at large times), and other initial data for which this uniformity fails at all times. We then construct an example of C ^∞ smooth initial data generating, at a later time, infinitely many gaps in the support of the maximizer, while for even larger times, all gaps have closed. Received: 8 May 2000 / Accepted: 27 March 2001     

Mutual diffusion in dense supercritical fluids

An expression for the mutual diffusion coefficient of a dense binary system of hard spheres, derived by using the Percus-Yevick approximation for the contact radial distribution function, together with Thorne's extension of the Enskog theory, is used to study the variation of the mutual diffusion coefficient with pressure, composition and ratio of the molecular diameters. Applications are made to real systems.     

Photosensitized addition of isopropanol to furanones in a continuous-flow dual capillary microreactor

A novel continuous-flow photoreactor with parallel capillaries was constructed and successfully tested for the DMBP-sensitized addition of isopropanol to furanones. Complete conversions were achieved after a maximum of 10 min of irradiation with a single 350 nm lamp. The results were compared to analogous batch experiments using a conventional Rayonet chamber reactor equipped with 16 UVA lamps. The capillary tower generally showed higher space-time yields.     

Allene-alkyne cross-coupling for stereoselective synthesis of substituted 1,4-dienes and cross-conjugated trienes

Titanium-mediated cross-coupling of allenic alcohols with alkynes has been investigated. Divergent reaction pathways were discovered that provide either stereodefined 1,4-dienes or substituted cross-conjugated trienes. In short, allene substitution plays a critical role in the determination of reaction pathway.     

Some observations on the substructure lattice of a Δ1 ultrapower

Given a (nontrivial) Δ₁ ultrapower ?/??, let ??_U denote the set of all Π₂‐correct substructures of ?/??; i.e., ??_U is the collection of all those subsets of |?/??| that are closed under computable (in the sense of ?/??) functions. Defining in the obvious way the lattice ??(?/??)) with domain ??_U, we obtain some preliminary results about lattice embeddings into – or realization as – an ??(?/??). The basis for these results, as far as we take the matter, consists of (1) the well‐known class of (non‐trivial) minimal ?/??'s, which function as atoms, and (2) the class of minimalfree ?/??'s, to whose nonemptiness a substantial section of the paper is devoted. It is shown that an infinite, convergent monotone sequence together with its limit point is embeddable in an ??(?/??), and that the initial segment lattices {0, 1,…, n } are not just embeddable in (as is trivial), but in fact realizable as, lattices ??(?/??). Finally, the diamond is (easily) embeddable; and if it is not realizable, then either the 1 ‐ 3 ‐ 1 lattice or the pentagon is at least embeddable (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Ramanujan-Slater type identities related to the moduli 18 and 24

We present several new families of Rogers-Ramanujan type identities related to the moduli 18 and 24. A few of the identities were found by either Ramanujan, Slater, or Dyson, but most are believed to be new. For one of these families, we discuss possible connections with Lie algebras. We also present two families of related false theta function identities.