Asymmetric synthesis of (1R,2S,3R)-3-methylcispentacin and (1S,2S,3R)-3-methyltranspentacin by kinetic resolution of tert-butyl (+/-)-3-methylcyclopentene-1-carboxylate

Conjugate addition of lithium dibenzylamide to tert-butyl (+/-)-3-methylcyclopentene-1-carboxylate occurs with high levels of stereocontrol, with preferential addition of lithium dibenzylamide to the face of the cyclic alpha,beta-unsaturated acceptor anti- to the 3-methyl substituent. High levels of enantiorecognition are observed between tert-butyl (+/-)-3-methylcyclopentene-1-carboxylate and an excess of lithium (+/-)-N-benzyl-N-alpha-methylbenzylamide (10 eq.) (E > 140) in their mutual kinetic resolution, while the kinetic resolution of tert-butyl (+/-)-3-methylcyclopentene-1-carboxylate with lithium (S)-N-benzyl-N-alpha-methylbenzylamide proceeds to give, at 51% conversion, tert-butyl (1R, 2S, 3R,alphaS)-3-methyl-2-N-benzyl-N-alpha-methylbenzylaminocyclopentane-1-c arboxylate consistent with E > 130, and in 39% yield and 99 +/- 0.5% de after purification. Subsequent deprotection by hydrogenolysis and ester hydrolysis gives (1R, 2S, 3R)-3-methylcispentacin in > 98% de and 98 +/- 1% ee. Selective epimerisation of tert-butyl (1R, 2S, 3R, alphaS)-3-methyl-2-N- benzyl-N-alpha-methylbenzylaminocyclopentane-1-carboxylate by treatment with (KOBu)-Bu-t in (BuOH)-Bu-t gives tert-butyl (1S, 2S, 3R, alphaS)-3-methyl-2-N-benzyl-N-alpha-methylbenzylaminocyclopentane-1-carb oxylate in quantitative yield and in > 98% de, with subsequent deprotection by hydrogenolysis and ester hydrolysis giving (1S, 2S, 3R)-3-methyltranspentacin hydrochloride in > 98% de and 97 +/- 1% ee.

The local adsorption geometry and electronic structure of alanine on Cu{110}

The adsorption of alanine on Cu {110} was studied by a combination of near edge X-ray absorption fine structure (NEXAFS) spectroscopy, X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT). Large chemical shifts in the C 1s, N 1s, and O 1s XP spectra were found between the alanine multilayer and the chemisorbed and pseudo-(3 x 2) alaninate layers. From C, N, and O K-shell NEXAFS spectra the tilt angles of the carboxylate group (approximate to 26 degrees in plane with respect to [1 (1) over bar0] and approximate to 45 degrees out of plane) and the C-N bond angle with respect to [1 (1) over bar0] could be determined for the pseudo-(3 x 2) overlayer. Using this information three adsorption geometries could be eliminated from five p(3 x 2) structures which lead to almost identical heats of adsorption in the DFT calculations between 1.40 and 1.47 eV/molecule. Due to the small energy difference between the remaining two structures it is not unlikely that these coexist on the surface at room temperature. (c) 2006 Elsevier B.V. All rights reserved.

Dissociation of water on oxygen-covered Rh{111}

The adsorption of water and coadsorption with oxygen on Rh{111} under ultrahigh vacuum conditions was studied using synchrotron-based photoemission and photoabsorption spectroscopy. Water adsorbs intact on the clean surface at temperatures below 154 K. Irradiation with x-rays, however, induces fast dissociation and the formation of a mixed OH+H(2)O layer indicating that the partially dissociated layer is thermodynamically more stable. Coadsorption of water and oxygen at a coverage below 0.3 monolayers has a similar effect, leading to the formation of a hydrogen-bonded network of water and hydroxyl molecules at a ratio of 3:2. The partially dissociated layers are more stable than chemisorbed intact water with the maximum desorption temperatures up to 30 K higher. For higher oxygen coverage, up to 0.5 monolayers, water does not dissociate and an intact water species is observed above 160 K, which is characterized by an O 1s binding energy 0.6 eV higher than that of chemisorbed water and a high desorption temperature similar to the partially dissociated layer. The extra stabilization is most likely due to hydrogen bonds with atomic oxygen.

The physics of baking: rheological and polymer molecular structure-function relationships in breadmaking

Molecular size and structure of the gluten polymers that make up the major structural components of wheat are related to their rheological properties via modern polymer rheology concepts. Interactions between polymer chain entanglements and branching are seen to be the key mechanisms determining the rheology of HMW polymers. Recent work confirms the observation that dynamic shear plateau modulus is essentially independent of variations in MW amongst wheat varieties of varying baking performance and is not related to variations in baking performance, and that it is not the size of the soluble glutenin polymers, but the structural and rheological properties of the insoluble polymer fraction that are mainly responsible for variations in baking performance. The rheological properties of gas cell walls in bread doughs are considered to be important in relation to their stability and gas retention during proof and baking, in particular their extensional strain hardening properties. Large deformation rheological properties of gas cell walls were measured using biaxial extension for a number of doughs of varying breadmaking quality at constant strain rate and elevated temperatures in the range 25oC to 60oC. Strain hardening and failure strain of cell walls were both seen to decrease with temperature, with cell walls in good breadmaking doughs remaining stable and retaining their strain hardening properties to higher temperatures (60oC), whilst the cell walls of poor breadmaking doughs became unstable at lower temperatures (45oC to 50oC) and had lower strain hardening. Strain hardening measured at 50oC gave good correlations with baking volume, with the best correlations achieved between those rheological measurements and baking tests which used similar mixing conditions. As predicted by the Considere failure criterion, a strain hardening value of 1 defines a region below which gas cell walls become unstable, and discriminates well between the baking quality of a range of commercial flour blends of varying quality. This indicates that the stability of gas cell walls during baking is strongly related to their strain hardening properties, and that extensional rheological measurements can be used as predictors of baking quality.

Water adsorption on O-covered Ru{0001}: coverage-dependent change from dissociation to molecular adsorption

When water is coadsorbed with oxygen at coverages above 0.25ML an intact water species is observed in high resolution X-ray photoelectron spectroscopy up to 220 K, which is significantly more stable than intact water on the clean surface. The presence of this species causes a shift in the O 1s binding energy of the pre-adsorbed oxygen, which indicates the formation of hydrogen bonds between the two adsorbates. Low coverages of oxygen induce partial dissociation and recombinative desorption in the same temperature range, which illustrates that desorption temperatures alone cannot be used to determine whether water is molecularly intact or not.

Effect of oxygen adsorption on the chiral pt{531} surface

The adsorption of oxygen on the chiral Pt{531} surface was studied by high-resolution X-ray photoelectron spectroscopy (HRXPS) and low energy electron diffraction (LEED). After the surface is annealed in oxygen (3 x 10(-7) mbar), three O 1s peaks are observed in XPS. One peak, at 529.5 eV, is assigned to chemisorbed oxygen; it disappears after annealing in vacuo to temperatures above 900 K. The other two peaks at 530.8 and 532.3 eV are stable up to at least 1250 K. They are associated with oxide clusters on the surface. These clusters readily react with coadsorbed carbon monoxide at temperatures between 315 and 620 K.

Asymmetric synthesis of cyclic β-amino acids and cyclic amines via sequential diastereoselective conjugate addition and ring closing metathesis

Diastereoselective conjugate addition of lithium (S)-N-allyl-N-alpha-methylbenzylamide to a range of alpha,beta-unsaturated esters followed by ring closing metathesis is used to afford efficiently a range of substituted cyclic beta-amino esters in high d.e. Alternatively, conjugate addition to alpha,beta-unsaturated Weinreb amides, functional group conversion and ring closing metathesis affords cyclic amines in high d.e. The further application of this methodology to the synthesis of a range of carbocyclic beta-amino esters via conjugate addition, enolate alkylation and ring closing metathesis is also described. Application of this methodology affords, after deprotection, (S)-homoproline, (S)-homopipecolic acid, (S)-coniine and (1S,2S)-trans-pentacin.

Where the interaction is: collisions of the situated and mediated in living room interactions

This article presents three ethnographic tales of interactions with living room media to help recreate the experience of significant moments in time, of affective encounters at the interface in which there is a collision or confusion of situated and virtual worlds. It draws on a year-long video ethnography of the practice and performance of everyday interactions with living room media. By studying situated activity and the lived practice of (new) media, rather than taking an exclusive focus on the virtual as a detached space, this ethnographic work demonstrates how the situated and mediated clash, or are crafted into complex emotional encounters during everyday living room life.

Formation of novel photoadducts from irradiation of 5(S)-5-O-tert-butyldimethylsiloxymethylfuran-2(5H)-one

Irradiation of 5S-5-O-tert-butyldimethylsiloxymethylfuran-2(5H)-one 1 in acetonitrile yields the C2-symmetric bis(lactone), 1S,2S,6S,7S-[3S,10S]-bis-tert-butyldimethylsiloxymethyl-4,9-dioxatricyclo[5.3.0.02,6]deca-5,8-dione 6, and a 3-substituted intramolecular product resulting from an apparent 8-endo-trig cyclisation.

The development of organized structures in polyethylene crystallized from a sheared melt, analyzed by WAXS and TEM

The development of global orientation and morphological features in linear polyethylene crystallizing from a sheared melt are studied using in-situ time-resolving wide angle X-ray scattering (WAXS) and ex-situ transmission electron microscopy. It is found that samples subjected to a shear rate above a critical value of ~1s-1 result in macroscopically oriented structures in the crystallized sample. This critical shear rate appears to be independent of the differences in molecular weight distribution of the samples studied although the morphologies which develop are sensitive to quite small differences in molecular weight distributions. The presence of shish kebabs in the morphology is shown to differ markedly according to variations in the upper molecular weight fraction of the molecular weight distribution, even though the resulting global orientation does not. The WAXS also reveals that areas which evidence no row nucleated structures still realize high degrees of molecular orientation. It is proposed that the formation of shish kebab or lamellar morphologies in these samples is dependent on the critical density of contiguous elongated crystallization nuclei rather than any specific global criteria.

On the spectra and pseudospectra of a class of non-self-adjoint random matrices and operators

In this paper we develop and apply methods for the spectral analysis of non-selfadjoint tridiagonal infinite and finite random matrices, and for the spectral analysis of analogous deterministic matrices which are pseudo-ergodic in the sense of E. B. Davies (Commun. Math. Phys. 216 (2001), 687–704). As a major application to illustrate our methods we focus on the “hopping sign model” introduced by J. Feinberg and A. Zee (Phys. Rev. E 59 (1999), 6433–6443), in which the main objects of study are random tridiagonal matrices which have zeros on the main diagonal and random ±1’s as the other entries. We explore the relationship between spectral sets in the finite and infinite matrix cases, and between the semi-infinite and bi-infinite matrix cases, for example showing that the numerical range and p-norm ε - pseudospectra (ε > 0, p ∈ [1,∞] ) of the random finite matrices converge almost surely to their infinite matrix counterparts, and that the finite matrix spectra are contained in the infinite matrix spectrum Σ. We also propose a sequence of inclusion sets for Σ which we show is convergent to Σ, with the nth element of the sequence computable by calculating smallest singular values of (large numbers of) n×n matrices. We propose similar convergent approximations for the 2-norm ε -pseudospectra of the infinite random matrices, these approximations sandwiching the infinite matrix pseudospectra from above and below.

The tensor-kinetic field in nuclear collisions

The role of the tensor terms in the Skyrme interaction is studied for their effect in dynamic calculations where non-zero contributions to the mean-field may arise, even when the starting nucleus, or nuclei are even-even and have no active time-odd potentials in the ground state. We study collisions in the test-bed 16O-16O system, and give a qualitative analysis of the behaviour of the time-odd tensor-kinetic density, which only appears in the mean field Hamiltonian in the presence of the tensor force. We find an axial excitation of this density is induced by a collision.

Mulsemedia: state of the art, perspectives, and challenges

Mulsemedia—multiple sensorial media—captures a wide variety of research efforts and applications. This article presents a historic perspective on mulsemedia work and reviews current developments in the area. These take place across the traditional multimedia spectrum—from virtual reality applications to computer games—as well as efforts in the arts, gastronomy, and therapy, to mention a few. We also describe standardization efforts, via the MPEG-V standard, and identify future developments and exciting challenges the community needs to overcome.

Global climatology of surface water temperatures of large lakes by remote sensing

Lake surface water temperatures (LSWTs) of 246 globally distributed large lakes were derived from Along-Track Scanning Radiometers (ATSR) for the period 1991–2011. The climatological cycles of mean LSWT derived from these data quantify on a global scale the responses of large lakes' surface temperatures to the annual cycle of forcing by solar radiation and the ambient meteorological conditions. LSWT cycles reflect the twice annual peak in net solar radiation for lakes between 1°S to 12°N. For lakes without a lake-mean seasonal ice cover, LSWT extremes exceed air temperatures by 0.5–1.7 °C for maximum and 0.7–1.9 °C for minimum temperature. The summer maximum LSWTs of lakes from 25°S to 35°N show a linear decrease with increasing altitude; −3.76 ± 0.17 °C km−1 (inline image = 0.95), marginally lower than the corresponding air temperature decrease with altitude −4.15 ± 0.24 °C km−1 (inline image = 0.95). Lake altitude of tropical lakes account for 0.78–0.83 (inline image) of the variation in the March to June LSWT–air temperature differences, with differences decreasing by 1.9 °C as the altitude increases from 500 to 1800 m above sea level (a.s.l.) We define an ‘open water phase’ as the length of time the lake-mean LSWT remains above 4 °C. There is a strong global correlation between the start and end of the lake-mean open water phase and the spring and fall 0 °C air temperature transition days, (inline image = 0.74 and 0.80, respectively), allowing for a good estimation of timing and length of the open water phase of lakes without LSWT observations. Lake depth, lake altitude and distance from coast further explain some of the inter-lake variation in the start and end of the open water phase.