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101.
Melin F  Choua S  Bernard M  Turek P  Weiss J 《Inorganic chemistry》2006,45(26):10750-10757
In addition to the need for functional models of cytochrome c oxidase, structural models are still required for a better understanding of the small reorganizations occurring during the catalytic cycle. An efficient synthetic approach has been designed to prepare several phenanthroline-strapped porphyrins, two of them bearing two pendant imidazoles. These built-in bases are both potentially able to act as axial bases for the metalloporphyrin and as complementary ligands for copper if necessary. Diamagnetic zinc(II) was used to demonstrate that the distal/proximal selectivity demonstrated by exogenic bases binding studies can be extended to the coordination of iron(III). Combination of EPR and paramagnetic 1H NMR shows that the imidazole binding on the zinc species can be further extended to the iron(III) species in dilute conditions.  相似文献   
102.
The reaction of lithiated trimethylsilyldiazomethane (LTMSD) with aldehydes and subsequent quenching with TMSCl furnished relatively stable alpha-silylated diazocompounds. Upon treatment of the alpha-silylated diazocompounds with Rh2(OAc)4 in refluxing toluene, alpha-silyl silyl enol ethers were formed from unbranched and branched aliphatic aldehydes through predominantly 1,2-migration of the C-H bond. In contrast, treatment of the alpha-silylated diazocompounds with Rh2(tfa)4 at room temperature gave alpha-silyl silyl enol ethers through exclusive and unusual 1,2-migration of the C-C bond. The origin of the selectivity observed from the two catalysts is discussed in relation to early and late transition states.  相似文献   
103.
In this paper, we present and apply a computer-assisted method to study steady states of a triangular cross-diffusion system. Our approach consist in an a posteriori validation procedure, that is based on using a fixed point argument around a numerically computed solution, in the spirit of the Newton–Kantorovich theorem. It allows to prove the existence of various non homogeneous steady states for different parameter values. In some situations, we obtain as many as 13 coexisting steady states. We also apply the a posteriori validation procedure to study the linear stability of the obtained steady states, proving that many of them are in fact unstable.  相似文献   
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106.
A stereocontrolled total synthesis of (+)-longicin, a representative of the class of mono-THF-acetogenins, is described. The strategy involves the utilization of d- and l-glutamic acids as chirons that correspond to two five-carbon segments harboring stereogenic centers at C4 and at C17 of the C(32) polyketide-derived natural product. The use of Grubbs' RCM reaction as a novel "chain elongation" strategy for the synthesis of acetogenin-type structures and a new protocol for butenolide incorporation are also described. [structure: see text]  相似文献   
107.
A new simple, rapid and high yielding synthesis of various 6-aryl-2-arylsulfonylmethyl-3-nitroimidazo[1,2-a]pyridines by Suzuki cross-coupling reaction is described using microwave irradiation in aqueous medium without organic co-solvent in the presence of tetrabutylammonium bromide.  相似文献   
108.
Analysis of single nucleotide polymorphisms (SNPs) has become an increasingly important area of research, with numerous applications in medical genetics, population genetics, forensic science, and agricultural biotechnology. Large-scale SNP analyses require the development of methodologies that are economical, flexible, accurate and capable of automation. Primer extension in conjunction with matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) is currently emerging as a potential method for high-throughput SNP genotyping. We have evaluated a number of published primer extension methods and refined a simple and robust protocol to analyze human autosomal disease-causing mutations and population genetic markers on the Y-chromosome. Twelve different variant sites were examined, and homozygotes, heterozygotes and hemizygotes were accurately typed. A 100% concordance was observed between SNP genotypes obtained using the MALDI-TOFMS technique and alternative genotyping methods, such as restriction fragment length polymorphism (RFLP) assays and denaturing high-performance liquid chromatography (DHPLC). Since multiple polymorphisms can be detected in single reactions, the method provides a cost-effective approach for SNP analysis. The protocol is also extremely flexible (able to accommodate new markers) and can be adapted to a number of platforms without the use of commercial kits.  相似文献   
109.
Novel 7,8,9,10‐tetrahydrothiazolo[5,4‐a]acridine and 1,2,3,4‐tetrahydro‐12H‐benzothiazolo[2,3‐b]‐quinazolin‐12‐one derivatives were synthesized in one step from the corresponding benzothiazoles. These two new tetracyclic skeletons were unambiguously characterized and are presently in pharmacological tests.  相似文献   
110.
University and older school students following scientific courses now use complex calculators with graphical, numerical and symbolic capabilities. In this context, the design of lessons for 11th grade pre-calculus students was a stimulating challenge.In the design of lessons, emphasising the role of mediation of calculators and the development of schemes of use in an 'instrumental genesis' was productive. Techniques, often discarded in teaching with technology, were viewed as a means to connect task to theories. Teaching techniques of use of a complex calculator in relation with 'traditional' techniques was considered to help students to develop instrumental and paper/pencil schemes, rich in mathematical meanings and to give sense to symbolic calculations as well as graphical and numerical approaches.The paper looks at tasks and techniques to help students to develop an appropriate instrumental genesis for algebra and functions, and to prepare for calculus. It then focuses on the potential of the calculator for connecting enactive representations and theoretical calculus. Finally, it looks at strategies to help students to experiment with symbolic concepts in calculus.This revised version was published online in September 2005 with corrections to the Cover Date.  相似文献   
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