Remote stereocontrol by the sulfinyl group: Mukaiyama aldol reactions of (S)-2-[2-(p-tolylsulfinyl)phenyl]acetaldehyde in the asymmetric synthesis of β-hydroxyacids and 1,3-diols

(S)-2-[2-(p-Tolylsulfinyl)phenyl]acetaldehyde reacts with different O-silylated ketenethioacetals in the presence of Yb(OTf)₃ yielding β-hydroxythioesters in high yields and diastereoselectivities. The obtained compounds were readily transformed into β-hydroxyacids and their corresponding diols. These Mukaiyama aldol reactions are a direct evidence of the ability of the sulfinyl group to control 1,5- and 1,6-asymmetric induction processes.     

Fast and efficient preparation of Baylis-Hillman-derived (E)-allylic azides and related compounds in aqueous medium

A practical access to alkyl- and aryl-substituted (E)-2-(azidomethyl)alkenoates and related azido compounds from the corresponding allylic bromides in aqueous acetone is described. An alternative method to obtain the starting bromides based on heterogeneous catalysis under mild conditions was also investigated.     

Modification of the surface state of rough substrates by two different varnishes and influence on the reflected light

Modification of the visual appearance when a rough surface is covered by a varnish is mostly attributed to the levelling of the substrate surface, which depends on the molecular weight of the varnish. The topography of varnished surfaces, however, has never been measured directly. Surfaces of varnishes applied over glass substrates of varying roughness were studied, therefore, using mechanical profilometry. Two different varnishes made with a low and a high molecular weight resin were studied. Both varnishes lower the r.m.s. roughness of the substrates and filter the high spatial frequencies. These results are amplified for the varnish containing the low molecular weight resin. The light reflected by the varnished samples is modelled from these topographical data. Its angular distribution, calculated from the probability density of slopes is presented, taking into account separately the air/varnish and the varnish/substrate interfaces. These analyses are presented in a back-scattering configuration. They show that varnishing significantly reduces the angular width of the reflected light and that this effect is magnified for the low molecular weight resin. Modelling furthermore shows that the influence of the roughness of the varnish/substrate interface is negligible in the total reflected light.     

二项式光场与级联三能级原子的量子纠缠

利用量子熵理论，研究了二项式光场与级联三能级原子的量子纠缠，讨论了光场与原子的初始参量对其量子纠缠性质的影响.结果表明，利用二项式光场的特性，可以揭示从相干态到数态之间的所有态光场与三能级原子相互作用时的量子纠缠性质.选择适当的系统参数可以制备稳定的光场-原子qutrit纠缠态. 关键词： 二项式光场 级联三能级原子 光场熵 量子纠缠     

Cosmic dust and our origins

The small solid particles in the space between the stars provide the surfaces for the production of many simple and complex molecules. Processes involving the effects of ultraviolet irradiation of the thin (hundredth micron) mantles are shown to produce a wide range of molecules and ions also seen in comets. Some of the more complex ones inferred from laboratory experiments are expected to play an important role in the origin of life. An outline of the chemical evolution of interstellar dust as observed and as studied in the laboratory is presented. Observations of comets are shown to provide substantial evidence for their being fluffy aggregates of interstellar dust as it was in the protosolar nebula, i.e. the interstellar cloud which collapsed to form the solar system. The theory that comets may have brought the progenitors of life to the earth is summarized.     

Lower Bounds from State Space Relaxations for Concave Cost Network Flow Problems

In this paper we obtain Lower Bounds (LBs) to concave cost network flow problems. The LBs are derived from state space relaxations of a dynamic programming formulation, which involve the use of non-injective mapping functions guaranteing a reduction on the cardinality of the state space. The general state space relaxation procedure is extended to address problems involving transitions that go across several stages, as is the case of network flow problems. Applications for these LBs include: estimation of the quality of heuristic solutions; local search methods that use information of the LB solution structure to find initial solutions to restart the search (Fontes et al., 2003, Networks, 41, 221–228); and branch-and-bound (BB) methods having as a bounding procedure a modified version of the LB algorithm developed here, (see Fontes et al., 2005a). These LBs are iteratively improved by penalizing, in a Lagrangian fashion, customers not exactly satisfied or by performing state space modifications. Both the penalties and the state space are updated by using the subgradient method. Additional constraints are developed to improve further the LBs by reducing the searchable space. The computational results provided show that very good bounds can be obtained for concave cost network flow problems, particularly for fixed-charge problems.     

Time Evolution of Vibration-Induced Excited State Decay

A simple model consisting of two electronic levels and one vibrational mode (phonon) was theoretically studied. The electronic-vibrational interaction was linear in the vibrational displacement. The vibrational mode was taken in the harmonic approximation and was attached to the thermal bath formed by the ambient environment. The kinetic constants of the vibrational dissipation were of the second order in the vibrational-bath coupling and were taken in the Markovian limit. Although, depending on the parameters of the model, different curves of the non-radiative vibration-induced excited state decay were obtained, in general, three time intervals, corresponding to different physical behaviour, were found. In the short-time interval, small oscillations superimposed on the excited state decay were observed. They were determined by the vibrational frequency and influenced by electronic-vibrational coupling. In the middle-time interval, almost quasi-exponential decay was detected; its rate constant increased with stronger electronic-vibrational interaction and speed of vibrational relaxation. In the long-time interval, the decay was very slow and, under special conditions, even an asymptotic non-zero excited state population was observed. Its value increased with the strength of the off-diagonal electron-vibrational coupling. Links of the parameters of the model with quantum chemical terms were estimated.     

Existence and Uniqueness of Endemic States for the Age-structured MSEIR Epidemic Model

The existence and uniqueness of positive steady states for the age-structured MSEIR epidemic model with age-dependent transmission coefficient is considered. Threshold results for the existence of endemic states are established; under certain conditions, uniqueness is also shown.     

A Facile Synthesis of α-Phenylthio-α,β-Unsatuated Esters

α-phenylthio-α，β-unsaturated esters 6 were synthesized by Witting reaction of 3.which were prepared by a phenylsulfenyllation-trans-ylidation reaction.     

Theoretical Study on the Reaction Mechanism between Dichlorocarbene and Armchair Single-walled Carbon Nanotubes

1 INTRODUCTION Carbon nanotubes have many potential applica- tions due to their unique structures and properties[1～4]. Physicists have been studying their electrical, me- chanical and other properties since their discove- ries[5, 6]. Recently, chemists are interested in carbon nanotubes because their properties can be altered by chemical functionalization[7～14], and these functiona- lized nanotubes can undergo further chemical trea- tment. So the potential application range of such na- …