The concepts of conjugation and hyperconjugation play an important role to provide an explanation for several fundamental phenomena observed in organic chemistry. Because these effects cannot be directly measured experimentally, their assessment became a primary concern for chemists from the very beginning. In general, the stabilization produced by both phenomena has been studied by means of isodesmic reactions and energy based analysis such as the energy decomposition analysis. In recent years, electronic delocalization measures have been successfully applied to elucidate the nature of chemical bonding and the aromatic character of all kind of molecules. Because conjugation and hyperconjugation stabilizations are strongly linked to the concept of electron delocalization, this paper will give an account of both effects from the point of view of electronic delocalization measures calculated within the framework of the quantum theory of atoms in molecules. In particular, we focus our attention in the controversial case of the stabilization by conjugation in 1,3-butadiyne and 1,3-butadiene. Unexpectedly, theoretical calculations based on the scheme proposed by Kistiakowsky to quantify the extent of stabilization due to conjugation predicted that the conjugation of 1,3-butadiyne was zero. Subsequent energetic analyses contradicted this observation. These studies pointed out the presence of hyperconjugation stabilization in the hydrogenated product of 1,3-butadiyne and 1,3-butadiene that were used as reference systems in the Kistiakowsky's scheme. Consequently, the extra stabilization of 1-butyne due to hyperconjugation hides the stabilization by conjugation of 1,3-butadiyne. Our results based on electron delocalization measures confirm both the presence of conjugation in 1,3-butadiene and 1,3-butadiyne and hyperconjugation stabilization in their respective hydrogenated products, 1-butene and 1-butyne. 相似文献
In this article I briefly review Molecular Dynamics Simulations studies relevant to the understanding of the physical origin of the controversial Hydration Force. The focus of the review is in simulations of realistic models of hydrophilic surfaces. The results reviewed here show a molecular perspective on how this repulsive, stabilizing force comes from interfacial water. 相似文献
Structure-guided re-design of the acceptor binding site of D-fructose-6-phosphate aldolase from E. coli leads to the construction of FSA A129S/A165G double mutant with an activity between 5- to >900-fold higher than that of wild-type towards N-Cbz-aminoaldehyde derivatives. 相似文献
The homogeneous catalysis of water oxidation by transition‐metal complexes has experienced spectacular development over the last five years. Practical energy‐conversion schemes, however, require robust catalysts with large turnover frequencies. Herein we introduce a new oxidatively rugged and powerful dinuclear water‐oxidation catalyst that is generated by self‐assembly from a mononuclear catalyst during the catalytic process. Our kinetic and DFT computational analysis shows that two interconnected catalytic cycles coexist while the mononuclear system is slowly and irreversibly converted into the more stable dinuclear system: an extremely robust water‐oxidation catalyst that does not decompose over extended periods of time. 相似文献
Privacy-preserving data splitting is a technique that aims to protect data privacy by storing different fragments of data in different locations. In this work we give a new combinatorial formulation to the data splitting problem. We see the data splitting problem as a purely combinatorial problem, in which we have to split data attributes into different fragments in a way that satisfies certain combinatorial properties derived from processing and privacy constraints. Using this formulation, we develop new combinatorial and algebraic techniques to obtain solutions to the data splitting problem. We present an algebraic method which builds an optimal data splitting solution by using Gröbner bases. Since this method is not efficient in general, we also develop a greedy algorithm for finding solutions that are not necessarily minimally sized.
We present a new branch and bound algorithm for weighted Max-SAT, called Lazy which incorporates original data structures and inference rules, as well as a lower bound of better quality. We provide experimental
evidence that our solver is very competitive and outperforms some of the best performing Max-SAT and weighted Max-SAT solvers
on a wide range of instances. 相似文献
The reactions of a series of Pd(II) methyl compounds of general formula LPd(NCCH(3))CH(3), where L is a bulky phenoxydiazene or phenoxyaldimine ligand with the polar olefin acrylonitrile (AN), are reported. The compounds react with an excess of AN to give the products of 2,1 insertion into the Pd-Me bond, yielding dimers and/or trimers which feature bridging alpha-cyano groups. The reactions were studied by low temperature (1)H NMR spectroscopy, revealing an initial formation of compounds featuring N-bound AN, which isomerized to an (unobserved) pi-bound species that rapidly underwent 2,1 insertion into the Pd-Me bond. Intermediate oligomeric complexes retaining a Pd-Me function were observed at low [AN] in these reactions. Under pseudo first-order conditions, k(obs) values of 8.5 x 10(-5) to 2.68 x 10(-3) M(-1) (-22 degrees C to 10 degrees C, 100 equiv of AN) and activation parameters of DeltaH++ = 14.4(5) kcal mol(-1) and DeltaS++ = -19(5) eu were obtained in one case. Comparison of the overall rates of insertion between two LPd(NCCH(3))CH(3), differing in the overall charge on the supporting ligand L, showed that the complex bearing a negatively charged ligand reacts with AN twice as fast as one with no anionic charge. The rates of insertion in both of these complexes are significantly faster than reported rates for analogous reactions in cationic Pd(II) derivatives, indicating that increasing the negative charge on the complex enhances the rate of AN insertion. These results provide fundamental mechanistic insights into a crucial reaction for incorporation of polar comonomers into alpha olefins via a coordination polymerization mechanism. 相似文献