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1.
 Whereas glucose oxidase and related proteins are encapsulated readily in silica sol–gels, α-hydroxy enzymes such as lactate oxidase (LOx), are reported to be damaged by electrostatic interaction with these matrices. Based on a previous report, poly(ethyleneimine), PEI, was evaluated as a protecting compound under conditions suited to analytical measurements. With LOx and PEI co-encapsulated in a silica sol–gel, the enzyme retained 62% of its initial activity after 20 days. In the absence of PEI, activity was lost during the processing. Batch analytical measurements with enzyme-doped sol–gel yielded a linear response over the range 0.5–2.0 mM lactate and a detection limit of 0.03 mM lactate. Both simple incorporation of LOx in a silica sol–gel and an alternative protection method, blocking the ion-exchange sites on silica with La(III), failed. These negative results supported the hypothesis that the efficacy of PEI was related to its formation of a protective sheath around the enzyme. Author for correspondence. E-mail: coxja@muohio.edu Received July 29, 2002; accepted December 15, 2002 Published online May 19, 2003  相似文献   
2.
Understanding the interaction of chiral ligands, alkynes, and alkenes with cobaltcarbonyl sources is critical to learning more about the mechanism of the catalytic, asymmetric Pauson-Khand reaction. We have successfully characterized complexes of the type [Co2(alkyne)(binap)(CO)4] (BINAP=(1,1'-binaphthalene)-2,2'-diylbis(diphenylphosphine)) and shown that diastereomer interconversion occurs under Pauson-Khand reaction conditions when alkyne=HC[triple bond]CCO2Me. Attempts to isolate [Co2(alkyne)(binap)(CO)x] complexes with coordinated alkenes led to the formation of cobaltacyclopentadiene species.  相似文献   
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We characterize the phase shift induced by reflection on a multilayer mirror in the extreme UV range (80-93?eV) using two techniques: one based on high order harmonic generation and attosecond metrology (reconstruction of attosecond beating by interference of two-photon transitions), and a second based on synchrotron radiation and measurements of standing waves (total electron yield). We find an excellent agreement between the results from the two measurements and a flat group delay shift (±40?as) over the main reflectivity peak of the mirror.  相似文献   
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Covalent side-chain cross-linking has been shown to be a viable strategy to control peptide folding. We report here that an oxime side-chain linkage can elicit α-helical folds from peptides in aqueous solution. The bio-orthogonal bridge is formed rapidly under neutral buffered conditions, and the resulting cyclic oximes are capable of dynamic covalent exchange.  相似文献   
7.
We present a general purpose QM-MM-MD engine (DYNGA) designed to test alternative hybrid Hamiltonians geared towards the treatment of problems of interest in structural biology including the use of experimental data constraints. In this first presentation we use DYNGA to explore the behaviour of a traditional QM-MM approach in the treatment of the water—water interaction. We find the potential energy hypersurface for the water dimer computed with the HF 4–31G*/TIP3P hybrid Hamiltonian tends to be too flat. We also explore the effect of using traditional QM-MM techniques on proton wires and conclude there is a need for improvement, possibly addressed by using polarizable force fields.  相似文献   
8.
Abstract We analyze the efficiency of the international management of the Bay of Biscay anchovy. While a sharing agreement between France and Spain has been in place since 1992, the fish stock collapsed in 2005 and the fishery closed from 2005 to spring 2010. We consider differences in production technologies between both countries and calibrate our model using data from 1987 to 2009. Our results suggest two sources of rent dissipation under the existing sharing agreement: inefficient quota allocation and production inefficiencies due to inflexible national regulations. We discuss several alternatives to improve management.  相似文献   
9.
Recent significant improvements of the contrast ratio of chirped pulse amplified pulses allows us to extend the applicability domain of laser accelerated protons to very thin targets. In this framework, we propose an analytical model particularly suitable to reproducing ion laser acceleration experiments using high intensity and ultrahigh contrast pulses. The model is based on a self-consistent solution of the Poisson equation using an adiabatic approximation for laser generated fast electrons which allows one to find the target thickness maximizing the maximum proton (and ion) energies and population as a function of the laser parameters. Model furnished values show a good agreement with experimental data and 2D particle-in-cell simulation results.  相似文献   
10.
The fluctuating behavior of a Sulzer Metco F4 DC plasma gun has been investigated by simultaneous measurement of the time dependencies of the are voltage and of images from the nozzle interior. An end-on imaging arrangement using a mirror and a mask in the optical path from the are to the camera allows visualization of the anodic arc attachment by strongly attenuating the bright emission from the are column. With the torch operating in the restrike mode, sequences of images have been acquired in synchronization with several typical features of the are voltage fluctuations showing that the attachment nature changes during a restrike cycle. Multiple attachments which coexist at least during the 1 μs exposure time of the camera have been evidenced and are interpreted as a continuous process of creation/vanishing of successive arc roots with a smooth transfer of the current from one to the other. The anode wear is shown to have a strong effect on the root position over the anode periphery, with a preference for attachment in eroded regions. The effects of operation parameters such as current, gas flow and injector type on the attachment nature and position are also presented  相似文献   
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