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1.
Jesse L. Kuiper 《Journal of organometallic chemistry》2007,692(8):1653-1660
The reaction between the new hydroxy compound [PPh4][Ru(N)(OH)2Me2] and Pd(OSiMe3)2((−)-sparteine) produces (Me3Si)2O, H2O and a new heterobimetallic compound [PPh4][Ru(N)Me2(μ2-O)2Pd((−)-sparteine)] in good yield. The Ru/Pd bimetallic compound catalyzes the oxidation of aryl and allyl alcohols to the corresponding carbonyl compound in air and the rearrangement of allylic alcohols unsaturated aldehydes. It also oxidizes PPh3 to O-PPh3 under O2. 相似文献
2.
The ultrafast-folding 20-residue Trp-cage protein is quickly becoming a new benchmark for molecular dynamics studies. Already several all-atom simulations have probed its equilibrium and kinetic properties. In this work an all-atom Go model is used to accurately represent the side-chain packing and native atomic contacts of the Trp-cage. The model reproduces the hallmark thermodynamics cooperativity of small proteins. Folding simulations observe that in the fast-folding dominant pathway, partial alpha-helical structure forms before hydrophobic core collapse. In the slow-folding secondary pathway, partial core collapse occurs before helical structure. The slow-folding rate of the secondary pathway is attributed to the loss of side-chain rotational freedom, due to the early core collapse, which impedes the helix formation. A major finding is the observation of a low-temperature kinetic intermediate stabilized by a salt bridge between residues Asp-9 and Arg-16. Similar observations [R. Zhou, Proc. Natl. Acad. Sci. U.S.A. 100, 13280 (2003)] were reported in a recent study using an all-atom model of the Trp-cage in explicit water, in which the salt-bridge stabilized intermediate was hypothesized to be the origin of the ultrafast-folding mechanism. A theoretical mutation that eliminates the Asp-9-Arg-16 salt bridge, but leaves the residues intact, is performed. Folding simulations of the mutant Trp-cage observe a two-state free-energy landscape with no kinetic intermediate and a significant decrease in the folding rate, in support of the hypothesis. 相似文献
3.
Synthesis of some dibenzodiazepinone derivatives as potent and m2-selective antimuscarinic compounds
Victor I. Cohen Biyun Jin Miriam S. Gitler Rosanna A. La De Cruz Waclaw J. Rzeszotarski Barry R. Zeeberg Jesse Baumgold Richard C. Reba 《Journal of heterocyclic chemistry》1994,31(4):787-791
Two series of 5-[[4-[4-(dialkylamino)butyl]-l-cyclohexyl]acetyl], and 5-[(dialkylamino)acyl]-10,11-dihydro-5H- dibenzo[b,e][1,4]diazepin-11-ones were synthesized as potential m2-selective ligands 1,2. Their affinity and selectivity for the muscarinic cholinergic receptor m-AChR subtypes were determined. Replacing a nitrogen with CH in the piperidine ring of 5-[[4-[4-(dialkylamino)butyl]-l-piperidinyl]acetyl]-10,11-dihydro-5H-dibenzo-[b,e][1,4]diazepin-11-ones 3 significantly altered the affinity and selectivity to the muscarinic receptor subtypes. 相似文献
4.
Jakub Kołacz Henry G. Gotjen Robel Y. Bekele Jason D. Myers Jesse A. Frantz Michael Ziemkiewicz 《Liquid crystals》2020,47(4):531-539
ABSTRACTIn a planar dielectric waveguide, weak confinement of a propagating mode in a high index core leads to a measurable evanescent interaction with the cladding. In this work, we study the effect of a reorientable anisotropic cladding on the behaviour of Transverse Electric (TE) and Transverse Magnetic (TM) mode polarisations using a liquid crystal (LC)-clad waveguide architecture. The polarised evanescent field of a guided mode interacts with a voltage-tunable birefringent LC cladding to deflect an out-coupled beam. Experimental measurements are coupled with a theoretical framework and show good consistency with simulation results. We isolate the effect of mode confinement by changing the thickness of the high index core. Interactions between the LC index ellipsoid and the mode polarisation are probed by changing the initial alignment of the LC. Finally, we examine the difference in deflection between TE and TM modes, which incorporates both a change in mode confinement and a difference in LC index components. 相似文献
5.
Heterobimetallic hexanuclear cyano-bridged complexes, [{Fe(Tp)(CN)3}4{M(MeCN)(H2O)2}(2)].10H2O.2MeCN [M = Ni (1), Co (2), Mn (3); Tp = hydrotris(1-pyrazolyl)borate], have been synthesized in H2O-MeCN solution. Complexes 1-3 are isostructural and hexanuclear with [{Fe(Tp)(CN)3}4{M(MeCN)(H2O)2}2] units linked by hydrogen bonds to form a 2D-structure in the solid state. Complex 1 is a canted antiferromagnet that undergoes a field-induced spin-flop-like transition at approximately 1 T and 2 K. At 4.45 K 1 has a transition to paramagnetic state of noninteracting S = 4 magnetic clusters. However, 2 and 3 show antiferromagnetic intracluster coupling. Facile loss of solvent from 2 alters the local symmetry resulting in changing the intracluster interaction from antiferro- to ferromagnetic. 相似文献
6.
The MSR (muonium spin rotation) technique was used to measure the chemical reaction rate for Mu + F2 → MuF + F in N2 moderator at ≈ 1 atm from 295 to 383 K giving the Arrhenius expression: log10k (?/mole s) = (10.83 ± 0.20) - (200 ± 50)/T, with k = (1.46 ± 0.11) × 1010 ?/mole s at 300 K. This is at least 6.8 times the room temperature rate constant for the analogous H atom reaction. The measured activation energy and enhancement over the H reaction rate are indicative of significant tunnelling in the Mu reaction, in agreement with the recent collinear quantum mechanical calculations of Connor et al. 相似文献
7.
Conjugate additions utilizing the simple monosilylcuprate reagent Li[PhMe2SiCuI] to alpha,beta-unsaturated carbonyl compounds are described. The presence of dimethyl sulfide (DMS), either as a component originating from the (CuI)4(DMS)3 complex or as a solvent added, has an amazing influence on both chemical yield and the level of diastereomeric ratio (dr) of the products. Gilman-type silylcyanocuprates {Li(Ph2MeSi)2Cu/LiCN} have previously been used to guarantee good results in conjugate addition reactions. External additives such as HMPA, tributylphosphine, or dialkylzinc are not necessary in conjunction with the simple Li[PhMe2SiCuI] reagent. It is demonstrated that the monosilylcuprate reagent with DMS as the solvent is very useful with sterically hindered (beta,beta-disubstituted) enones, and provides very high yields of the beta-silylated 1,4-addition products. Since there is no oligomerization problem associated with the simple monosilylcuprate reagent, this reagent should be considered as a very useful 1,4-silyl donor to enals, enones, and enoates in conjugate addition reactions. 相似文献
8.
The hindered rotor transitions of H(2) adsorbed in the chemically related and prototypical porous metal-organic frameworks IRMOF-1, IRMOF-8, IRMOF-11, and MOF-177 were studied by inelastic neutron scattering to gain information on the specifics of H(2) binding in this class of adsorbents. Remarkably sharp and complex spectra of these materials signify a diversity of well-defined binding sites. Similarities in the spectral features as a function of H(2) loading and correlations with recent crystallographic studies were used to assign transitions ranging in rotational barrier from <0.04 to 0.6 kcal/mol as corresponding to localized adsorption sites on the organic and inorganic components of these frameworks. We find that binding of H(2) at the inorganic cluster sites is affected by the nature of the organic link and is strongest in IRMOF-11 in accord with our adsorption isotherm data. The sites on the organic link have lower binding energies, but a much greater capacity for increases in H(2) loading, which demonstrates their importance for hydrogen uptake by these materials. 相似文献
9.
On the RbNiCrF6 Type. III. New Fluorides of the Type CsZnMF6 (M = Al, Ga, In, Tl, Sc, Ti, V, Mn, Cu, Rh) Cubic compounds are CsZnGaF6 [3] (colourless, a = 10.29 Å); CsZnInF6 (colourless, a = 10.58 Å); CsZnTlF6 (colourless, a = 10.62 Å); CsZnScF6 (colourless, a = 10.58 Å); CsZnTiF6 (lightblue, a = 10.50 Å); CsZnVF6 (lightgreen, a = 10.43 Å); CsZnMnF6 (redbrown, a = 10.40 Å); CsZnCuF6 (light brown, a = 10.24 Å); CsZnRhF6 (redbrown, a = 10.41 Å), all RbNiCrF6 type of structure, in addition non cubic: CsZnAlF6 (colourless). The Madelung part of lattice energy, MAPLE, is calculated and discussed. 相似文献
10.
Dr. Yang Chen Dr. Elzbieta Trzop Jesse D. Sokolow Prof. Dr. Philip Coppens 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(49):16651-16655
The structures of three newly synthesized phosphonate‐substituted polyoxotitanates are reported. The Ti/O core of [Ti4O(OEt)12(PhenylPO3)] ( 1 ) is the building block for two larger phosphonate‐substituted nanoclusters, [Ti25O26(OEt)36(PhenylPO3)6] ( 2 ) and [Ti26O26(OEt)39(PhenylPO3)6]Br ( 3 ). All compounds exhibit a not previously recognized triply bridging binding mode of the phosphonate anchor with short connecting Ti? O bonds, the average of which is 2.010(7) Å. Comparison with previously reported work suggests that the binding mode of the phosphonate anchor is strongly dependent on the structure of the underlying substrate. 相似文献