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961.
The interaction of an external effector, ZnII ions, with a constitutional dynamic library of fluorescent polyiminofluorenes leads to component exchange, which generates an entity responding by a change in emission to the effector that has induced its formation. The overall coupled system displays a tuning of optical signal, resulting from two synergistic processes: adaptative constitutional reorganization and self-sensing. In broader terms, this work highlights the perspectives opened by constitutional dynamic chemistry toward the design of smart materials, capable of expressing different latent properties in response to environmental conditions. 相似文献
962.
Weibel N Charbonnière LJ Guardigli M Roda A Ziessel R 《Journal of the American Chemical Society》2004,126(15):4888-4896
The synthesis of a new ligand LH(4) based on a glutamic acid skeleton bis-functionalized on its nitrogen atom by 6-methylene-6'-carboxy-2,2'-bipyridine chromophoric units is described. UV-vis spectrophotometric titrations revealed the formation of 1:1 M:L complexes with lanthanide(III) cations, and complexation of LH(4) with equimolar amounts of hydrated LnCl(3) salts (Ln = Eu, Gd, and Tb) gave water-soluble and stable complexes of the general formula [LnL(H(2)O)]Na, which were characterized by elemental analysis, IR, UV-vis absorption spectroscopy, (1)H NMR (Ln = Eu), and mass spectrometry. The conditional stability constant for formation of the [EuL(H(2)O)]Na complex was determined by competitive complexation experiments to be log K = 16.5 +/- 0.6 in 0.01 M TRIS/HCl buffer (pH = 7.0). In water solution, the [EuL(H(2)O)]Na and [TbL(H(2)O)]Na complexes were highly luminescent with quantum yields of 8% and 31%, respectively, despite the presence of ca. one water molecule in the first coordination sphere of the metal ions. Activation of the appended carboxylate function of the glutamate moiety in the form of an N-hydroxysuccinimidyl ester allows for the covalent linking of the complexes to primary amino groups of biological compounds. Bovine serum albumin (BSA) was labeled with both Eu or Tb complexes, and the Ln-BSA conjugates were characterized by UV-vis absorption and emission spectroscopy and MALDI-TOF mass spectrometry. Labeling ratios (number of complex molecules per BSA) of ca. 8:1 and 7:1 were established for Eu-BSA and Tb-BSA, respectively. The suitability of the tagged compound for use in bioanalytical time-resolved luminescence microscopy was established by comparison with fluorescein-labeled probes. 相似文献
963.
Synthesis of the novel 2'-Se-cytidine phosphoramidite was achieved via transformation of the uridine analogue to the cytidine derivative in high yield. This 2'-Se-cytidine phosphoramidite was used to synthesize selenium-derivatized DNA and RNA oligonucleotides for X-ray crystallography using MAD. The nucleotide coupling yield using this novel phosphoramidite was over 99% when 5-benzylmercaptotetrazole (5-BMT) was used as the coupling reagent. 相似文献
964.
We report here the first study of enzymatic synthesis of two phosphoroselenoate (PSe) DNAs using the two alpha-Se-TTP diastereomers (Sp and Rp) and DNA polymerase. The experimental results indicate that Klenow equally recognizes the two individual diastereomers at the same level as natural TTP. The incorporations of the PSe groups at the expected sites have been confirmed by the digestion resistance to exonuclease III, and the different patterns of the digestion resistance of DNA I and II indicate the configurational differences of the PSe centers (Sp or Rp). Unlike chemical synthesis, which is limited to short DNAs and where the separation of the PSe DNA diastereomers is necessary, this enzymatic method can be used to prepare longer DNAs without diastereomer separation. This quantitative enzymatic approach is particular valuable for the synthesis of longer DNAs with multiple PSe groups in large scale for their X-ray crystal structure determination by the MAD phasing technique. 相似文献
965.
Nicolaou KC Hao J Reddy MV Rao PB Rassias G Snyder SA Huang X Chen DY Brenzovich WE Giuseppone N O'Brate A Giannakakou P 《Journal of the American Chemical Society》2004,126(40):12897-12906
As an especially unique target for chemical synthesis, diazonamide A has the potential to be constructed through a plethora of synthetic routes, each attended by different challenges and opportunities for discovery. In this article, we detail our second total synthesis of diazonamide A through a sequence entirely distinct from that employed in our first campaign, one whose success required the development of several special strategies and tactics. We also disclose our complete studies regarding the chemical biology of diazonamide A and its structural congeners, and more fully delineate the scope of our protocol for Robinson-Gabriel cyclodehydration using pyridine-buffered POCl(3). 相似文献
966.
We extend the abstract frameworks for the multigrid analysis for nonconforming finite elements to the case where the assumptions of the second Strang lemma are violated. The consistency error is studied in detail for finite element discretizations on domains with curved boundaries. This is applied to prove the approximation property for conforming elements, stabilized -elements, and nonconforming elements for linear elasticity on nonpolygonal domains.
967.
Fournier Nicolas Giet Jean-Sébastien 《Methodology and Computing in Applied Probability》2004,6(2):219-231
The Smoluchowski coagulation equation describes the concentration c(t,x) of particles of mass x [ 0,] at the instant t 0, in an infinite system of coalescing particles. It is well-known that in some cases, gelation occurs: a particle with infinite mass appears. But this infinite particle is inert, in the sense that it does not interact with finite particles. We consider the so-called Marcus–Lushnikov process, which is a stochastic finite system of coalescing particles. This process is expected to converge, as the number of particles tends to infinity, to a solution of the Smoluchowski coagulation equation. We show that it actually converges, for t [0,], to a modified Smoluchowski equation, which takes into account a possible interaction between finite and infinite particles. 相似文献
968.
Nicolas Bergeron 《Comptes Rendus Mathematique》2004,339(11):751-756
We show how our recent results (arXiv: math.NT/0403407 v1 24 Mar 2004) together with a criterion of Venkataramana can be used to get explicit conditions for the virtual non-vanishing of the product of two cohomology classes of certain Shimura varieties. To cite this article: N. Bergeron, C. R. Acad. Sci. Paris, Ser. I 339 (2004). 相似文献
969.
A beam tracing method for interactive architectural acoustics 总被引:1,自引:0,他引:1
Funkhouser T Tsingos N Carlbom I Elko G Sondhi M West JE Pingali G Min P Ngan A 《The Journal of the Acoustical Society of America》2004,115(2):739-756
A difficult challenge in geometrical acoustic modeling is computing propagation paths from sound sources to receivers fast enough for interactive applications. This paper describes a beam tracing method that enables interactive updates of propagation paths from a stationary source to a moving receiver in large building interiors. During a precomputation phase, convex polyhedral beams traced from the location of each sound source are stored in a "beam tree" representing the regions of space reachable by potential sequences of transmissions, diffractions, and specular reflections at surfaces of a 3D polygonal model. Then, during an interactive phase, the precomputed beam tree(s) are used to generate propagation paths from the source(s) to any receiver location at interactive rates. The key features of this beam tracing method are (1) it scales to support large building environments, (2) it models propagation due to edge diffraction, (3) it finds all propagation paths up to a given termination criterion without exhaustive search or risk of under-sampling, and (4) it updates propagation paths at interactive rates. The method has been demonstrated to work effectively in interactive acoustic design and virtual walkthrough applications. 相似文献
970.
We propose a scheme for measuring the squeezing, purity, and entanglement of Gaussian states of light that does not require homodyne detection. The suggested setup needs only beam splitters and single-photon detectors. Two-mode entanglement can be detected from coincidences between photodetectors placed on the two beams. 相似文献