A new copper acetate-bis(oxazoline)-catalyzed, enantioselective Henry reaction

A highly enantioselective, nitroaldol reaction catalyzed by a chiral Cu(II) bis(oxazoline) complex has been developed. The reaction scope includes both aromatic and aliphatic aldehydes (15 examples) affording products in good yields and enantioselectivities (87-94% ee). An X-ray structure of the catalyst has been provided along with a rationalization of the sense of asymmetric induction.     

Synthesis of new 3'-, 5-, and N(4)-modified 2'-O-methylcytidine libraries on solid support

A versatile solid phase combinatorial approach was developed and utilized for the rapid synthesis of new 2'-O-methylcytidine nucleoside libraries 1-7 containing 672 compounds with 3'-deoxy-3'-C-methyl, 3'-deoxy-3'-C-hydroxymethyl, and 5-alkyl/alkynyl modifications. The modified uridine scaffolds 8-10, 23-25, and 31 were loaded onto the 4-methoxytrityl chloride (MMT-Cl) polystyrene resin through the hydroxyl groups at the 5'-position as well as on the substituents at the 3'- and 5-positions. The scaffolds loaded on the resin were orthogonally protected by MMT group on the resin itself and TBDMS or acetyl protecting groups. The 4-position of the uridine derivatives was activated by 2,4,6-triisopropyl benzene sulfonyl chloride for further derivatization. The resins 14-16, 28-30, and 32 loaded with the corresponding activated scaffolds were reacted with the selected and validated amino building blocks in the 96 well format on the semiautomated synthesizer. The high-quality 2'-O-methylcytidine libraries 1-7 were thus generated and characterized by liquid chromatography-mass spectrometry (LC-MS) analysis with 63-99% successful rates.     

Detection of chlorinated methanes by tin oxide gas sensors

Tin oxide thin films prepared by thermal oxidation of Sn films were used for the detection of chlorinated methanes (CH2Cl2, CHCl3 and CCl4). This resulted in better chemical selectivity, sensitivity, response speed and detection limit than seen with previous detectors. The temperature dependence of the sensing of 1% CCl4 gas was studied and the best sensing behavior was observed at 300 degrees C. The films showed different chemical selectivity in both speed and direction of sensing response to each gas and were stable for more than 3 weeks under operating conditions. The films showed rapid gas sensing (<40 s to reach 90% of full response) and low detection limits (< 4 ppm CCl4). The role of oxygen in the detection of chlorinated methanes and in resistance changes without chlorinated methanes was also studied. The changes at the surface of the film after gas sensing were examined using scanning electron microscopy with energy-dispersive X-ray spectrometry.     

Discontinuous Galerkin finite element methods for linear elasticity and quasistatic linear viscoelasticity

Summary. We consider a finite-element-in-space, and quadrature-in-time-discretization of a compressible linear quasistatic viscoelasticity problem. The spatial discretization uses a discontinous Galerkin finite element method based on polynomials of degree r—termed DG(r)—and the time discretization uses a trapezoidal-rectangle rule approximation to the Volterra (history) integral. Both semi- and fully-discrete a priori error estimates are derived without recourse to Gronwall's inequality, and therefore the error bounds do not show exponential growth in time. Moreover, the convergence rates are optimal in both h and r providing that the finite element space contains a globally continuous interpolant to the exact solution (e.g. when using the standard ^k polynomial basis on simplicies, or tensor product polynomials, ^k, on quadrilaterals). When this is not the case (e.g. using ^k on quadri-laterals) the convergence rate is suboptimal in r but remains optimal in h. We also consider a reduction of the problem to standard linear elasticity where similarly optimal a priori error estimates are derived for the DG(r) approximation. Mathematics Subject Classification (2000):65N36Shaw and Whiteman would like to acknowledge the support of the US Army Research Office, Grant #DAAD19-00-1-0421, and the UK EPSRC, Grant #GR/R10844/01. Whiteman would also like to acknowledge support from TICAM in the form of Visiting Research Fellowships.     

The interaction of a laser-generated cavity with a solid boundary

In this paper new observations of a laser-generated cavitation bubble interacting with an inertial boundary are presented. Employing schlieren photography techniques and a thin film transducer placed on the surface of the boundary, the pressure stresses induced in the solid boundary and the surrounding fluid by collapsing bubbles, created very close to the solid surface, are experimentally measured. Liquid jet development, shock wave emission, and "splash" phenomena are identified. For different creation sites close to the boundary, the relevance of each of these phenomena with respect to potentially damaging pressure stresses in the boundary is speculated on.     

Observable effects of scalar fields and varying constants

We show by using the method of matched asymptotic expansions that a sufficient condition can be derived which determines when a local experiment will detect the cosmological variation of a scalar field which is driving the spacetime variation of a supposed constant of Nature. We extend our earlier analyses of this problem by including the possibility that the local region is undergoing collapse inside a virialised structure, like a galaxy or galaxy cluster. We show by direct calculation that the sufficient condition is met to high precision in our own local region and we can therefore legitimately use local observations to place constraints upon the variation of “constants” of Nature on cosmological scales.     

Synthesis of photocleavable poly(methyl methacrylate‐block‐d‐lactide) via atom‐transfer radical polymerization and ring‐opening polymerization

The synthesis and characterization of a photocleavable block copolymer containing an ortho‐nitrobenzyl (ONB) linker between poly(methyl methacrylate) and poly(d ‐lactide) blocks is presented here. The block copolymers were synthesized via atom transfer radical polymerization (ATRP) of MMA followed by ring‐opening polymerization (ROP) of d ‐Lactide and ROP of d ‐lactide followed by ATRP of MMA from a difunctional photoresponsive ONB initiator, respectively. The challenges and limitations during synthesis of the photocleavable block copolymers using the difunctional photoresponsive ONB initiator are discussed. The photocleavage of the copolymers occurs under mild conditions by simple irradiation with 302 nm wavelength UV light (Relative intensity at 7.6 cm: 1500 μW/cm²) for several hours. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4309–4316     

Determination of the configuration of histrelin,and LHRH analog,by chiral capillary gas chromatography

Summary Summary The assigned chirality at each center of the synthetic nonapeptide histrelin (L-pyroglutamyl-L-histidyl-L-tryptophyl-L-seryl-L-tyrosyl-D-N^im-benzyl-histidyl-L-leucyl-L-arginyl-L-proline-ethylamide) was verified using chiral gas chromatography. The procedure involved acid hydrolysis of histrelin to the constituent amino acids, derivatization as the N-pentafluoropropionyl/isopropyl esters and the analysis of the mixture using a commercially available 25m chiral capillary column (Chirasil-L-Val). There was no significant difference in the retention time of the amino acids obtained from the hydrolysate mixture when compared to the appropriate standards. Additionally, the hydrolysate was spiked with the D and L amino acids to prove the identity of closely eluting peaks. Luteinizing hormone-releasing hormone     

On-line nuclear orientation and relaxation studies of Cs isotopes

The hyperfine field of CsFe has been measured to be (+)40.8(0.7)T, using the technique of on-line low temperature nuclear orientation. The time dependent relaxation of¹²¹Cs^m Fe has also been investigated using a new technique, giving a Korringa constant C_k of 0.059 (15) sK. From this, an effective relaxation time of 3.0 (0.8)s can be deduced for the short lived¹¹⁸Cs^m(T_1/2=17s). This value has then been used to extract the magnetic moment of¹¹⁸Cs^m to be |μ|=5.4 (1.1) nm.