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61.
Exocyclic Olefinic Maleimides: Synthesis and Application for Stable and Thiol‐Selective Bioconjugation
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Dr. Dimpy Kalia Pushpa V. Malekar Manikandan Parthasarathy 《Angewandte Chemie (International ed. in English)》2016,55(4):1432-1435
Michael addition reactions between biological thiols and endocyclic olefinic maleimides are extensively used for site‐specific bioconjugation. The resulting thio‐succinimidyl linkages, however, lack stability because of their susceptibility to thiol exchange. Reported herein is that in contrast to their endocyclic counterparts, exocyclic olefinic maleimides form highly stable thio‐Michael adducts which resist thiol exchange at physiological conditions. A high‐yielding approach for synthesizing a variety of exocyclic olefinic maleimides, by 4‐nitrophenol‐catalyzed solvent‐free Wittig reactions, is reported. Mechanistic studies reveal that the catalyst facilitates the formation of the Wittig ylide intermediate through sequential proton donation and abstraction. Overall, this report details an improved thiol bioconjugation approach, a facile method for synthesizing exocyclic olefinic maleimides, and demonstrates that phenolic compounds can catalyze ylide formation. 相似文献
62.
An efficient Ru(II)-catalyzed amidation of 2-arylpyridines with isocyanates via C-H bond activation is described. 相似文献
63.
64.
D Dascier E Ji A Parthasarathy KS Schanze DG Whitten 《Langmuir : the ACS journal of surfaces and colloids》2012,28(31):11286-11290
Cationic end-only-functionalized oligo(arylene-ethynylene)s (EO-OPEs) have recently been found to be broad-spectrum and effective antimicrobial agents because of their unique structure and optical properties. In this study, we investigated their potential use for preventing and reducing Escherichia coli (E. coli) biofilms. The Calgary biofilm device (CBD) was used to form bacterial biofilms of E. coli; in these studies, the minimum inhibitory concentration (MIC) and the minimum biofilm eradication concentration (MBEC) were determined. E. coli biofilms uniformly grow on pegs of the CBD device lid. The MIC values determined for EO-OPEs are comparable to those found for standard antibiotics such as kanamycin (MIC = 11.2 μg/mL). About 10-30 times the concentration of EO-OPEs was required to eradicate E. coli biofilms and prevent regrowth in the dark. Near-UV irradiation of EO-OPEs enhanced their efficacy in killing biofilms. 相似文献
65.
Porel M Jockusch S Parthasarathy A Rao VJ Turro NJ Ramamurthy V 《Chemical communications (Cambridge, England)》2012,48(21):2710-2712
The efficient photoinduced electron transfer from a stilbene derivative incarcerated within a negatively charged organic nanocapsule to positively charged acceptors (methyl viologen and a pyridinium salt) adsorbed outside and the back electron transfer were controlled by supramolecular effects. 相似文献
66.
Parthasarathy K Han H Prakash C Cheng CH 《Chemical communications (Cambridge, England)》2012,48(52):6580-6582
A new method for the synthesis of various isochromen-6-ones and phenanthro[1,10-bc]oxepines via a palladium-catalyzed cascade carbocyclization of 2-iodobenzyl-3-phenylpropiolates and 1-iodo-2-(2-(phenylethynyl)benzyloxy)benzenes with arynes is described. The reactions involve interesting biscarbocyclization of alkynes and benzynes and C-H bond activation. 相似文献
67.
Selvarangam E. Kiruthika Rangarajan Amritha Paramasivan T. Perumal 《Tetrahedron letters》2012,53(26):3268-3273
A facile strategy for the synthesis of functionalized spirolactones from isatin, primary amines, and activated alkynes through Huisgen dipolar additions are discussed. A novel route for the formation of dispirodihydrofuranyl oxindoles from activated cyclic electrophiles, amines, and DMAD has also been developed. This method offers several advantages like high yield, readily available starting materials, and involves less hazardous chemical techniques. 相似文献
68.
In the theory of classical mechanics, the two-body central forcing problem is formulated as a system of the coupled nonlinear
second-order deterministic differential equations. The uncertainty introduced by the small, unmodeled stochastic acceleration
is not assumed in the particle dynamics. The small, unmodeled stochastic acceleration produces an additional random force
on a particle. Estimation algorithms for a two-body dynamics, without introducing the stochastic perturbation, may cause inaccurate
estimation of a particle trajectory. Specifically, this paper examines the effect of the stochastic acceleration on the motion
of the orbiting particle, and subsequently, the stochastic estimation algorithm is developed by deriving the evolutions of
conditional means and conditional variances for estimating the states of the particle-earth system. The theory of the nonlinear
filter of this paper is developed using the Kolmogorov forward equation “between the observations" and a functional difference
equation for the conditional probability density “at the observation." The effectiveness of the nonlinear filter is examined
on the basis of its ability to preserve perturbation effect felt by the orbiting particle and the signal-to-noise ratio. The Kolmogorov forward equation, however, is not appropriate for the numerical simulations, since it is the equation for
the evolution of “the conditional probability density." Instead of the Kolmogorov equation, one derives the evolutions for
the moments of the state vector, which in our case consists of positions and velocities of the orbiting body. Even these equations
are not appropriate for the numerical implementations, since they are not closed in the sense that computing the evolution
of a given moment involves the knowledge of higher order moments. Hence, we consider the approximations to these moment evolution
equations. This paper makes a connection between classical mechanics, statistical mechanics and the theory of the nonlinear
stochastic filtering. The results of this paper will be of use to astrophysicists, engineers and applied mathematicians, who
are interested in applications of the nonlinear filtering theory to the problems of celestial and satellite mechanics. Simulation
results are introduced to demonstrate the usefulness of an analytic theory developed, in this paper. 相似文献
69.
Parthasarathy Ramachandran 《理论物理通讯》2009,52(4):646-652
In this article, we study traffic flow in the presence ofspeed breaking structures. The speed breakers are typically used toreduce the local speed of vehicles near certain institutions such asschools and hospitals. Through a cellular automata model we study the impact of such structures on global traffic characteristics. The simulation results indicate that the presence of speed breakers could reduce the global flow under moderate global densities. However, under low and high global density traffic regime the presence of speed breakers does not have an impact on the global flow. Further the speed limit enforced by the speed breaker createsa phase distinction. For a given global density and slowdown probability, as the speed limit enforced by the speed breaker increases, the traffic moves from the reduced flow phase to maximum flow phase. This underlines the importance of proper design of these structures to avoid undesired flow restrictions. 相似文献
70.
Positive Definite Functions and Operator Inequalities 总被引:1,自引:0,他引:1
We construct several examples of positive definite functions,and use the positive definite matrices arising from them toderive several inequalities for norms of operators. 1991 MathematicsSubject Classification 42A82, 47A63, 15A45, 15A60. 相似文献