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91.
Lighting-up the dynamics of telomerization and DNA replication by CdSe-ZnS quantum dots 总被引:7,自引:0,他引:7
Patolsky F Gill R Weizmann Y Mokari T Banin U Willner I 《Journal of the American Chemical Society》2003,125(46):13918-13919
CdSe-ZnS core-shell quantum dots (QDs) act as photochemical centers for lighting-up the dynamics of telomerization or DNA replication. 相似文献
92.
Electronic tunneling in a complex molecular network of N(>2) donor/acceptor sites, connected by molecular bridges, is analyzed. The "deep" tunneling dynamics is formulated using a recursive perturbation expansion, yielding a McConnell-type reduced N-level model Hamiltonian. Applications to models of molecular junctions demonstrate that the donor-bridge contact parameters can be tuned in order to control the tunneling dynamics and particularly to direct the tunneling pathway to either one of the various acceptors. 相似文献
93.
We introduce, analyse and optimize the class of Bernoulli random polling systems. The server movescyclically among N channels (queues), butChange-over times between stations are composed ofwalking times required to move from one channel to another andswitch-in times that are incurredonly when the server actually enters a station to render service. The server uses aBernoulli random mechanism to decide whether to serve a queue or not: upon arrival to channeli, it switches in with probabilityp
i
, or moves on to the next queue (w.p. 1 —p
i
) without serving any customer (e.g. packet or job). The Cyclic Bernoulli Polling (CBP) scheme is independent of the service regime in any particular station, and may be applied to any service discipline. In this paper we analyse three different service disciplines under the CBP scheme: Gated, Partially Exhaustive and Fully Exhaustive. For each regime we derive expressions for (i) the generating functions and moments of the number of customers (jobs) at the various queues at polling instants, (ii) the expected number of jobs that an arbitrary departing job leaves behind it, and (iii) the LST and expectation of the waiting time of a cutomer at any given queue. The fact that these measures of performance can be explicitly obtained under the CBP is an advantage over all parameterized cyclic polling schemes (such as the k-limited discipline) that have been studied in the literature, and for which explicit measures of performance are hard to obtain. The choice of thep
i
's in the CBP allows for fine tuning and optimization of performance measures, as well as prioritization between stations (this being achieved at a low computational cost). For this purpose, we develop a Pseudo-conservation law for amixed system comprised of channels from all three service disciplines, and define a Mathematical Program to find the optimal values of the probabilities {p
i
}
i
N
=1 so as to minimize the expected amount of unfinished work in the system. Any CBP scheme for which the optimalp
i
's are not all equal to one, yields asmaller amount of the expected unfinished work in the system than that in the standard cyclic polling procedure with equivalent parameters. We conclude by showing that even in the case of a single queue, it is not always true thatp
1=1 is the best strategy, and derive conditions under which it is optimal to havep
1 < 1.Supported by a Grant from the France-Israel Scientific Cooperation (in Computer Science and Engineering) between the French Ministry of Research and Technology and the Israeli Ministry of Science and Technology, Grant Number 3321190. 相似文献
94.
Carbanion 1, obtained by a nucleophilic attack of PhSe- on 3-chlorobicyclobutane-carbonitrile in DME undergoes both protonation and elimination as shown in eq 1. Alcohols of increasing acidity in the following order: t-BuOH, i-PrOH, MeOH, trifluoroethanol (TFE), and hexafluoro2-propanol (HFIP) were used as proton donors. An Eigen-type plot of the log of the product ratio (protonation/elimination) vs the pK(a) of the alcohols, levels off for the two most acidic alcohols, TFE and HFIP which react at a diffusion-controlled rate. The partitioning of the products between protonation and elimination enables, therefore, the determination of the rate constant for the internal elimination as approximately 3 x 10(10) s(-1). Ab initio calculations at the B3LYP/6-31G level show that the elimination from a model carbanion (4, eq 4) occurs in a barrierless process. Simulation of the experimental reaction by including solvation effects using the Onsager model, shows that using the dielectric constant of DME (7.2) stabilizes, as expected, the carbanion and prevents a spontaneous elimination. In the absence of solvation effects, using Me- as a base, a complete elimination of HCl (proton removal and leaving-group expulsion) took place from 3-chlorocyclobutanecarbonitrile in a barrierless process without the formation of any discrete intermediate. 相似文献
95.
Godsi O Turner B Suwinska K Peskin U Eichen Y 《Journal of the American Chemical Society》2004,126(41):13519-13525
The enolpyridine, OH-ketoenamime, NH equilibrium in crystals of 1,3-bis(pyridin-2-yl)propan-2-one was studied using temperature-dependent single-crystal X-ray diffraction. The relative population of the different tautomers was found to be sensitive to the temperature in the range of 100-300 K, illustrating the small thermodynamic difference between these two tautomers. This energy resemblance is partially attributed to the molecular packing in the crystal, where the molecules are arranged in the form of dimers. Ab initio electronic energy calculations (HF/6-31G** and MP2/6-31G**) reveal the effect of dimerization in the crystal on the electronic energy levels. Several tautomeric states were identified in the dimer of 1,3-bis(pyridin-2-yl)propan-2-one. A model is proposed in which four of these dimer states are populated in the crystal at ambient temperatures. The crystallographic data were treated according to this four-state dimer model, suggesting that the free energy of the OH-NH dimers is higher than that of the OH-OH dimers by 120 +/- 10 cal mol(-1) and that the NH-NH dimers are yet higher in free energy by 50 +/- 10 cal mol(-1). 相似文献
96.
97.
98.
A topological spaceX is called weakly first countable, if for every pointx there is a countable family {C
n
x
|n ∈ω} such thatx ∈C
n
+1x
⊆C
n
x
and such thatU ⊂X is open iff for eachx ∈U someC
n
x
is contained inU. This weakening of first countability is due to A. V. Arhangelskii from 1966, who asked whether compact weakly first countable
spaces are first countable. In 1976, N. N. Jakovlev gave a negative answer under the assumption of continuum hypothesis. His
result was strengthened by V. I. Malykhin in 1982, again under CH. In the present paper we construct various Jakovlev type
spaces under the weaker assumption b=c, and also by forcing.
The second author was supported by the Ben-Gurion University Center for Advanced Studies in Mathematics, Be’er Sheva.
The third author was supported by OTKA grant no. 37758 of Hungary. 相似文献
99.
Pratim Sengupta Uri Wilensky 《International Journal of Computers for Mathematical Learning》2009,14(1):21-50
Electricity is regarded as one of the most challenging topics for students of all ages. Several researchers have suggested
that na?ve misconceptions about electricity stem from a deep incommensurability (Slotta and Chi 2006; Chi 2005) or incompatibility (Chi et al.
1994) between na?ve and expert knowledge structures. In this paper we argue that adopting an emergent levels-based perspective
as proposed by Wilensky and Resnick (1999), allows us to reconceive commonly noted misconceptions in electricity as behavioral evidences of “slippage between levels,”
i.e., these misconceptions appear when otherwise productive knowledge elements are sometimes activated inappropriately due
to certain macro-level phenomenological cues only. We then introduce NIELS (NetLogo Investigations In Electromagnetism), a
curriculum of emergent multi-agent-based computational models. NIELS models represent phenomena such as electric current and
resistance as emergent from simple, body-syntonic interactions between electrons and other charges in a circuit. We discuss results from a pilot
implementation of NIELS in an undergraduate physics course, that highlight the ability of an emergent levels-based approach
to provide students with a deep, expert-like understanding of the relevant phenomena by bootstrapping, rather than discarding their existing repertoire of intuitive knowledge.
相似文献
Pratim SenguptaEmail: |
100.
Gill R Freeman R Xu JP Willner I Winograd S Shweky I Banin U 《Journal of the American Chemical Society》2006,128(48):15376-15377
CdSe/ZnS QDs enable the optical probing of the biocatalytic oxidation of tyrosine derivatives and of the scission of peptides by thrombin. CdSe/ZnS QDs were modified with tyrosine methyl ester or with a tyrosine-containing peptide. The tyrosine units were reacted with tyrosinase/O2 to yield the respective l-DOPA and quinone derivatives. The luminescence of QDs modified by the enzyme-generated quinone units is quenched. The quinone-functionalized peptide associated with the QDs was cleaved by thrombin, a process that restored the luminescence of the QDs. 相似文献