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71.
A simple one-pot and efficient method is described for the synthesis of pyrazinothienopyrimidines 6 by domino processes involving aza-Wittig/intermolecular nucleophilic addition/intramolecular cyclization. A tandem aza-Wittig reaction of phosphazenes 7, derived from 6, with heterocumulenes (isocyanates, carbon disulfide or carbon dioxide) generates the pyrazinothienotriazolopyrimidinones 9, 11 and 12, respectively. Pyrazino[2′,3′:4,5]thieno[3,2-d]-1,2,4-triazolo[1,5-a]pyrimidin-4(3H)-ones 15 and bis(pyrazinothienotriazolopyrimidinones) 17 were synthesized by the intermolecular aza-Wittig reaction of phosphazenes 7 with acyl chlorides or α,ω-dichlorides followed by heterocyclization via imidoyl chloride intermediate 16. Further S-alkylation of 11 and reaction of 6 with phosgeniminium chloride produce 2-alkylthio- and 2-N,N-dimethylaminopyrazinothienotriazolopyrimidinones 13 and 19, respectively. 相似文献
72.
Palazzo G Francia F Mallardi A Giustini M Lopez F Venturoli G 《Journal of the American Chemical Society》2008,130(29):9353-9363
We report on the effects of water activity and surrounding viscosity on electron transfer reactions taking place within a membrane protein: the reaction center (RC) from the photosynthetic bacterium Rhodobacter sphaeroides. We measured the kinetics of charge recombination between the primary photoxidized donor (P(+)) and the reduced quinone acceptors. Water activity (aW) and viscosity (eta) have been tuned by changing the concentration of cosolutes (trehalose, sucrose, glucose, and glycerol) and the temperature. The temperature dependence of the rate of charge recombination between the reduced primary quinone, Q(A)(-), and P(+) was found to be unaffected by the presence of cosolutes. At variance, the kinetics of charge recombination between the reduced secondary quinone (Q(B)(-)) and P(+) was found to be severely influenced by the presence of cosolutes and by the temperature. Results collected over a wide eta-range (2 orders of magnitude) demonstrate that the rate of P(+)Q(B)(-) recombination is uncorrelated to the solution viscosity. The kinetics of P(+)Q(B)(-) recombination depends on the P(+)Q(A)(-)Q(B) <--> P(+)Q(A)Q(B)(-) equilibrium constant. Accordingly, the dependence of the interquinone electron transfer equilibrium constant on T and aW has been explained by assuming that the transfer of one electron from Q(A)(-) to Q(B) is associated with the release of about three water molecules by the RC. This implies that the interquinone electron transfer involves at least two RC substates differing in the stoichiometry of interacting water molecules. 相似文献
73.
Andrés Abeliuk Gerardo Berbeglia Manuel Cebrian Pascal Van Hentenryck 《4OR: A Quarterly Journal of Operations Research》2016,14(1):57-75
Motivated by applications in retail, online advertising, and cultural markets, this paper studies the problem of finding an optimal assortment and positioning of products subject to a capacity constraint in a setting where consumers preferences can be modeled as a discrete choice under a multinomial logit model that captures the intrinsic product appeal, position biases, and social influence. For the static problem, we prove that the optimal assortment and positioning can be found in polynomial time. This is despite the fact that adding a product to the assortment may increase the probability of selecting the no-choice option, a phenomenon not observed in almost all models studied in the literature. We then consider the dynamics of such a market, where consumers are influenced by the aggregate past purchases. In this dynamic setting, we provide a small example to show that the natural and often used policy known as popularity ranking, that ranks products in decreasing order of the number of purchases, can reduce the expected profit as times goes by. We then prove that a greedy policy that applies the static optimal assortment and positioning at each period, always benefits from the popularity signal and outperforms any policy where consumers cannot observe the number of past purchases (in expectation). 相似文献
74.
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76.
Gehová López-González Gerardo Altamirano-Gómez Eduardo Bayro-Corrochano 《Advances in Applied Clifford Algebras》2016,26(3):1045-1059
Traditional methods for geometric entities resort to the Hough transform and tensor voting schemes for detect lines and circles. In this work, the authors extend these approaches using representations in terms of k-vectors of the Conformal Geometric Algebra. Of interest is the detection of lines and circles in images, and planes, circles, and spheres in the 3-D visual space; for that, we use the randomized Hough transform, and by means of k-blades we code such geometric entities. Motivated by tensor voting, we have generalized this approach for any kind of geometric entities or geometric flags formulating the perceptual saliency function involving k-vectors. The experiments using real images show the performance of the algorithms. 相似文献
77.
Surface modification of thermoplastics--towards the plastic biochip for high throughput screening devices 总被引:2,自引:0,他引:2
Diaz-Quijada GA Peytavi R Nantel A Roy E Bergeron MG Dumoulin MM Veres T 《Lab on a chip》2007,7(7):856-862
Microarrays have become one of the most convenient tools for high throughput screening, supporting major advances in genomics and proteomics. Other important applications can be found in medical diagnostics, detection of biothreats, drug discovery, etc. Integration of microarrays with microfluidic devices can be highly advantageous in terms of portability, shorter analysis time and lower consumption of expensive biological analytes. Since fabrication of microfluidic devices using traditional materials such as glass is rather expensive, there is great interest in employing polymeric materials as a low cost alternative that is suitable for mass production. A number of commercially available plastic materials were reviewed for this purpose and poly(methylmethacrylate) Zeonor 1060R and Zeonex E48R were identified as promising candidates, for which methods for surface modification and covalent immobilization of DNA oligonucleotides were developed. In addition, we present proof-of-concept plastic-based microarrays with and without integration with microfluidics. 相似文献
78.
Advances in NMR and mass spectrometry as well as in peptide biochemistry coupled to modern methods in electrophysiology have permitted the isolation and identification of numerous products from spider venoms, previously explored due to technical limitations. The chemical composition of spider venoms is diverse, ranging from low molecular weight organic compounds such as acylpolyamines to complex peptides. First, acylpolyamines (< 1000 Da) have an aromatic moiety linked to a hydrophilic lateral chain. They were characterized for the first time in spider venoms and are ligand-gated ion channel antagonists, which block mainly postsynaptic glutamate receptors in invertebrate and vertebrate nervous systems. Acylpolyamines represent the vast majority of organic components from the spider venom. Acylpolyamine analogues have proven to suppress hippocampal epileptic discharges. Moreover, acylpolyamines could suppress excitatory postsynaptic currents inducing Ca+ accumulation in neurons leading to protection against a brain ischemic insult. Second, short spider peptides (< 6000 Da) modulate ionic currents in Ca2+, Na+, or K+ voltage-gated ion channels. Such peptides may contain from three to four disulfide bridges. Some spider peptides act specifically to discriminate among Ca2+, Na+, or K+ ion channel subtypes. Their selective affinities for ion channel subfamilies are functional for mapping excitable cells. Furthermore, several of these peptides have proven to hyperpolarize peripheral neurons, which are associated with supplying sensation to the skin and skeletal muscles. Some spider N-type calcium ion channel blockers may be important for the treatment of chronic pain. A special group of spider peptides are the amphipathic and positively charged peptides. Their secondary structure is alpha-helical and they insert into the lipid cell membrane of eukaryotic or prokaryotic cells leading to the formation of pores and subsequently depolarizing the cell membrane. Acylpolyamines and peptides from spider venoms represent an interesting source of molecules for the design of novel pharmaceutical drugs. 相似文献
79.
Marchesini GR Haasnoot W Delahaut P Gerçek H Nielen MW 《Analytica chimica acta》2007,586(1-2):259-268
Fluoroquinolones (FQs) are synthetic antibiotics of broad-spectrum antibacterial activity widely used to treat infections in farmed fish, turkeys, pigs, calves and poultry. Monitoring these substances residues is therefore regulated by law. For the detection of FQs, we studied the feasibility of coupling the simultaneous screening of several FQs, using a dual surface plasmon resonance (SPR) biosensor immunoassay (BIA), in parallel, with an analytical chemical methodology for their identification. Six FQs were simultaneously screened at or below their maximum residue level (MRL) in chicken muscle using a multi-FQ BIA for norfloxacin, ciprofloxacin, enrofloxacin, difloxacin and sarafloxacin, and a specific BIA for flumequine. The two BIAs were serially coupled in a multi-channel SPR biosensor featuring a dual BIA in a competitive inhibition format. The samples non-compliant during the screening with the dual BIA were further concentrated and fractionated with gradient liquid chromatography (LC). The effluent was splitted toward two 96-well fraction collectors resulting in two identical 96-well plates. One was re-screened with the dual BIA to identify the immunoactive fractions and direct the identification efforts toward the relevant fractions in the second well-plate with high resolution LC-electrospray time-of-flight mass spectrometry (ESI-TOFMS). The system not only allows the possibility to screen and identify known FQs, but also to discover unknown chemicals of similar structure which show activity in the dual BIA. 相似文献
80.
Manuel Snchez-Chaves Gerardo Martínez Enrique Lpez Madruga 《Journal of polymer science. Part A, Polymer chemistry》1999,37(15):2941-2948
2-Hydroxyethyl methacrylate (HEMA) and styrene (S) have been copolymerized in a 3 mol · L−1N,N′-dimethylformamide (DMF) solution using 2,2′azobis (isobutyronitrile) (AIBN) as an initiator over a wide composition and conversion range. From low-conversion experiments and 1H-NMR analysis, the monomer reactivity ratios were determined according to the Mayo–Lewis terminal model. The comparison of the obtained results with those previously reported for copolymerization in bulk and in toluene reveals a relatively small but noticeable solvent effect that can be qualitatively explained by the bootstrap model. Cumulative copolymer composition as a function of conversion is satisfactorily described by the integrated Mayo–Lewis equation; overall copolymerization rate increases with increasing the HEMA/S ratio, and individual monomer conversion is closely related to the monomer molar fraction in the feed. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2941–2948, 1999 相似文献