排序方式: 共有21条查询结果,搜索用时 15 毫秒
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Dr. Sarah E. Maurer Dr. Michael S. DeClue Anders N. Albertsen Dr. Mark Dörr Dr. David S. Kuiper Dr. Hans Ziock Dr. Steen Rasmussen Dr. James M. Boncella Dr. Pierre‐Alain Monnard 《Chemphyschem》2011,12(4):828-835
One of the essential elements of any cell, including primitive ancestors, is a structural component that protects and confines the metabolism and genes while allowing access to essential nutrients. For the targeted protocell model, bilayers of decanoic acid, a single‐chain fatty acid amphiphile, are used as the container. These bilayers interact with a ruthenium–nucleobase complex, the metabolic complex, to convert amphiphile precursors into more amphiphiles. These interactions are dependent on non‐covalent bonding. The initial rate of conversion of an oily precursor molecule into fatty acid was examined as a function of these interactions. It is shown that the precursor molecule associates strongly with decanoic acid structures. This results in a high dependence of conversion rates on the interaction of the catalyst with the self‐assembled structures. The observed rate logically increases when a tight interaction between catalyst complex and container exists. A strong association between the metabolic complex and the container was achieved by bonding a sufficiently long hydrocarbon tail to the complex. Surprisingly, the rate enhancement was nearly as strong when the ruthenium and nucleobase elements of the complex were each given their own hydrocarbon tail and existed as separate molecules, as when the two elements were covalently bonded to each other and the resulting molecule was given a hydrocarbon tail. These results provide insights into the possibilities and constraints of such a reaction system in relation to building the ultimate protocell. 相似文献
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First, the basic concept of the vector derivative in geometric algebra is introduced. Second, beginning with the Fourier transform
on a scalar function we generalize to a real Fourier transform on Clifford multivector-valued functions
Third, we show a set of important properties of the Clifford Fourier transform on Cl3,0 such as differentiation properties, and the Plancherel theorem. Finally, we apply the Clifford Fourier transform properties
for proving an uncertainty principle for Cl3,0 multivector functions. 相似文献
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DeClue MS Baldridge KK Kast P Hilvert D 《Journal of the American Chemical Society》2006,128(6):2043-2051
The versatile biosynthetic intermediate isochorismate decomposes in aqueous buffer by two competitive pathways, one leading to isoprephenate by a facile Claisen rearrangement and the other to salicylate via elimination of the enolpyruvyl side chain. Computation suggests that both processes are concerted but asynchronous pericyclic reactions, with considerable C-O cleavage in the transition state but relatively little C-C bond formation (rearrangement) or hydrogen atom transfer to the enolpyruvyl side chain (elimination). Kinetic experiments show that rearrangement is roughly 8-times more favorable than elimination. Moreover, transfer of the C2 hydrogen atom to C9 was verified by monitoring the decomposition of [2-(2)H]isochorismate, which was prepared chemoenzymatically from labeled shikimate, by (2)H NMR spectroscopy and observing the appearance of [3-(2)H]pyruvate. Finally, the isotope effects obtained with the C2 deuterated substrate are in good agreement with calculations assuming pericyclic reaction mechanisms. These results provide a benchmark for mechanistic investigations of isochorismate mutase and isochorismate pyruvate lyase, the enzymes that respectively catalyze the rearrangement and elimination reactions in plants and bacteria. 相似文献
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Relaxation of toroidal discharges is described by the principle of minimum energy dissipation together with the constraint
of conserved global helicity. The resulting Euler-Lagrange equation is solved in toroidal coordinates for an axisymmetric
torus by expressing the solutions in terms of Chandrasekhar-Kendall (C-K) eigenfunctions analytically continued in the complex
domain. The C-K eigenfunctions are obtained as hypergeometric functions that are solutions of scalar Helmholtz equation in
toroidal coordinates in the large aspect-ratio approximation. Equilibria are constructed by assuming the current to vanish
at the edge of plasma. For the m=0, n=0 (m and n are the poloidal and toroidal mode numbers respectively) relaxed states, the magnetic field, current, q (safety factor) and pressure profiles are calculated for a given value of aspect-ratio of the torus and for different values
of the eigenvalue λ
r
0. The new feature of the present model is that solutions allow for both tokamak as well as RFP-like behaviour with increase
in the values of λ
r
0, which is related directly to volt-sec in the experiment. 相似文献
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Polysiloxane acts as a modular scaffold for macromolecular reagent development. Two separate components were covalently integrated into one material, one constituent provided reagent functionality, the other modulated solubility. In particular cinchona alkaloid based ligands used in the osmium tetroxide catalyzed asymmetric dihydroxylation (AD) reaction were covalently attached to commercially available polysiloxane. To enhance the reactivity of these polymeric ligands, multifunctional reagents were designed to include both the cinchona alkaloid and an alkoxyethylester solubilizing moiety providing random co-polymers. While the mono-functional materials led to heterogeneous conditions, the bi-functional polymers resulted in homogeneous reaction mixtures. Although both reagent types provided diol products with excellent yield and selectivity (>99% ee in nearly quantitative yield) the homogeneous analog has nearly twice the reactivity. Every repeat unit in the heterogeneous material was functionalized along the polysiloxane backbone while approximately half of these sites contained ligand in the homogeneous version. This approach led to macromolecular catalysts with high loadings of ligand and therefore materials with very low equivalent weights. Although these polymers are highly loaded they do maintain reactivity on a par with their free ligand counterpart. Using straightforward purification techniques (i.e. precipitation, simple filtration, or ultrafiltration) these polymeric ligands were easily separated from diol product and reused multiple times. Polysiloxane is a viable support for the catalysis of AD reactions and may provide a generally useful backbone for other catalytic systems. 相似文献
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Sandip N.Gavade Ravi S.Balaskar Madhav S.Mane Pramod N.Pabrekar Murlidhar S.Shingare Dhananjay V.Mane 《中国化学快报》2011,22(6):675-678
The coupling reaction of phenylurea with different functionalized aryl halides in the presence of air stable CuI,N,N-dimethylethylenediamine as a ligand,and K3PO4 as a base gives symmetrical and unsymmetrical diarylureas in relatively high yields.This method is milder than the palladium catalyzed arylation and avoids the use of toxic phosphine ligands. 相似文献
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