Transition state modeling and catalyst design for hydrogen bond-stabilized enolate formation

[reaction: see text] A catalyst for enolate formation was designed that incorporates an amine base along with a thiourea to bind to the oxygen atom of the substrate and enolate through hydrogen bonding. A computational model of the transition state was developed in which the thiourea (modeled initially as a urea) and amine were separate molecules. This model and models incorporating one or two methanol molecules in place of the urea showed an out-of-plane hydrogen bond, apparently to the carbonyl pi-bond, in addition to an in-plane hydrogen bond to an unshared electron pair. In contrast, optimized complexes of the ketone and the fully formed enolate showed only in-plane hydrogen bonding. The transition state model with the urea and amine was used to define a database search with the computer program CAVEAT to identify structures suitable for linking the amine and urea/thiourea moieties in the transition state. On the basis of a group of structures identified from this search, a flexible but conformationally biased linker was designed to connect the two catalytic moieties. The molecule having the amine and thiourea moieties connected by this linker was synthesized and was shown to catalyze proton exchange between methanol and deuterated acetone. The catalyst was about 5-fold more efficient than the amine and thiourea as separate molecules and relative to a similar but less conformationally biased catalyst.     

Outcome regression-based estimation of conditional average treatment effect

Annals of the Institute of Statistical Mathematics - The research is about a systematic investigation on the following issues. First, we construct different outcome regression-based estimators for...     

Origin and manifestation of the anharmonic potential felt by an ion-cloud in an actual Paul trap

The anharmonic potential felt by a single-species ions confined in a rf quadrupole trap which results from a non-ideal trap configuration and the charge distribution of the ion cloud is studied. The rf resonance-absorption spectra are explained by a Duffing oscillator and a representation of the line-shape parameter is derived. For > 0.77, the electric signals will exhibit hysteresis. The relation with the anharmonic potential is discussed.     

Incomplete idempotent Schröder quasigroups and related packing designs

Summary In this paper it is proved that, for any positive integern 2, 3 (mod 4),n 7, there exists an incomplete idempotent Schröder quasigroup with one hole of size two IISQ(n, 2) except forn = 10. It is also proved that for any positive integern 0, 1 (mod 4), there exists an idempotent Schröder quasigroup ISQ(n) except forn = 5 and 9. These results completely determine the spectrum of ISQ(n) and provide an application to the packing of a class of edge-coloured block designs.Research supported by NSERC grant A-5320.Research supported by NSFC grant 19231060-2.     

Chapter 15 DEA/AR analysis of the 1988–1989 performance of the Nanjing textiles corporation

This article employs new data envelopment analysis/assurance region (DEA/AR) methods to evaluate the efficiency of the 35 textile factories of the Nanjing Textiles Corporation (NTC), Nanjing, China. The returns to scale (RTS) of these factories were studied without assuming that the optimal DEA solutions were unique. All DMUs are identified with pointsE (Extreme Efficient),E (Efficient but not an extreme point) andF (Frontier but not efficient). We then further identify the nonfrontier DMUs with pointsNE, NE andNF according to whether they are projected onto a point inE, E, orF en route to evaluating their performances. All of the inefficient factories were in classNF and had unique optimal primal-dual solution pairs. Consequently, the solution pairs satisfy the strong complementary slackness condition (SCSC). Application of cone-ratio (CR) ARs reduced significantly the number of factories in classE, and showed that some AR-efficient factories were more flexible in adopting the mixture of central planning and market economies that China currently is trying to use. Also, linked-cone (LC) ARs were applied to measure maximum and minimum profit ratios. The SCSC multiplier space approach was utilized to analyze the sensitivity of the efficiency results to potential errors in the data with and without ARs. The results in this article suggest that collective units had a better performance than state-owned units in the two consecutive years analyzed.This paper was written while the author was at the School of Economics and Management, Southeast University, Nanjing 210018, P.R. China.