Stereoselective Cycloaddition of N-Acyliminium Ions with α,β-Unsaturated Ketones and Esters

The [4+2] reactions of N‐acyliminium ions, produced from 2‐aryl‐3‐hydroxy‐2,3‐dihydroisoindol‐1‐ones or 5‐hydroxy‐1‐phenyl‐2,5‐dihydro/2,3,4,5‐tetrahydropyrrol‐2‐ones in the presence of BF₃OEt₂, with α,β‐unsaturated ketones or esters were examined, and the dependence of these reactions on the substituents at double bonds was clarified. For β‐aryl substituted α,β‐unsaturated ketones and esters such as 4‐aryl‐3‐buten‐2‐ones, chalcones and methyl cinnamate, the [4+2] reactions could proceed smoothly at room temperature to afford 6‐acyl‐5,6,6a,11‐tetrahydroisoindolo[2,1‐a]quinolin‐11‐ones and 4‐acyl‐1,3a,4,5‐tetrahydropyrrolo[1,2‐a]quinolin‐ 1‐ones or 4‐acyl‐1,2,3,3a,4,5‐hexahydropyrrolo[1,2‐a]quinolin‐1‐ones in moderate to high yields; while for simple α,β‐unsaturated ketones and esters such as methyl crotonate and ethyl 3‐methylbut‐2‐enoate, except mesityloxide, the [4+2] reactions were difficult to proceed. The cycloaddition reactions were highly stereoselective, and only one stereoisomer was produced in each reaction.     

微波萃取-气相色谱法测定血液中的可卡因及其代谢物爱冈宁甲基酯

建立了血液中可卡因(cocaine, COC)及其代谢物爱冈宁甲基酯(ecgonine methyl ester, EME)的气相色谱-质谱(CG-MS)和气相色谱-氢火焰离子化检测(GC-FID)方法。该方法采用微波萃取提取血液中的COC和EME,优化并确定了最佳提取条件: 以氯仿-异丙醇(体积比为9:1)混合溶液为提取溶剂,用0.05 mol/L Na2CO3-NaHCO3缓冲溶液调节样品溶液的pH至10.0,在40 ℃下微波萃取6 min;采用GC-MS对萃取液中的COC和EME进行定性,采用GC-FID进行定量检测。COC和EME的平均回收率分别为79.91%～99.85%,相对标准偏差(RSD)均小于3.10%,检出限(S/N=3)分别为60 mg/L和40 mg/L。该方法无需衍生化,快速、准确、灵敏,可同时检测血液中的COC和EME。     

Approximation of convex bodies by multiple objective optimization and an application in reachable sets

In this paper, we focus on approximating convex compact bodies. For a convex body described as the feasible set in objective space of a multiple objective programme, we show that finding it is equivalent to finding the non-dominated set of a multiple objective programme. This equivalence implies that convex bodies can be approximated using multiple objective optimization algorithms. Therefore, we propose a revised outer approximation algorithm for convex multiple objective programming problems to approximate convex bodies. Finally, we apply the algorithm to solve reachable sets of control systems and use numerical examples to show the effectiveness of the algorithm.     

Lead Levels in Non-Occupationally Exposed Women with Preeclampsia

There are many controversies regarding the relationship between lead exposure andcomplications in pregnancy. Preeclampsia (PE) is a maternal hypertensive disorder which is one of the main causes of maternal and foetal mortality. The aim of our study was to assess blood lead level (BLL) in Polish women with PE (PE group, n = 66) compared with healthy, non-pregnant women (CNP group, n = 40) and healthy pregnant women (CP group, n = 40). BLL was determined by inductively coupled plasma mass spectrometry (ICP-MS). The systolic blood pressure (SBP), diastolic blood pressure (DBP) and BLL in the CP group were significantly lower than in the PE group (p < 0.001). Logistic regression analyses of BLL showed a significant positive relationship with the presence of PE. Furthermore, both the SBP and DBP values were positively associated with BLL. This study indicates that preeclamptic women tend to present with significantly higher BLL compared to healthy pregnant women. There were no differences in the BLL between the CP and CNP groups.     

Theoretical study on the mechanism for NH3BH3 reduction of ketones and imines

In spite of a potential hydrogen storage material, ammonia borane (AB) was recently found to be a good hydrogenation reagent. It can reduce certain ketones to alcohols or borate esters, and imines to amines. The mechanisms of these reactions are not fully understood yet, and have been systematically studied using high-level CCSD(T) calculations in this work. We have validated theoretically that the forming of alcohols and amines undergoes concerted double-hydrogen transfer (DHT) mechanism. Furthermore, we predicted that the DHT process is facile for more general ketones and imines. For the borate ester formation, we found a pretty high barrier for the experimentally derived stepwise mechanism. Alternatively, we propose that the reaction starts with the DHT process to form alcohol and NH₂BH₂, followed by alcoholysis of NH₂BH₂ to form the first B–O bond. This mechanism is in good agreement with the current experimental facts, and also explains why ketone reduction affords different products at different conditions. For these reaction systems, the performances of M06-2x and MP2 (underestimate the barrier by 5–7 kcal/mol, but with right trends) are better than B3LYP and BLYP methods (underestimate the barrier by 0–5 kcal/mol).     

The eastward displacement of a freely falling body on the rotating Earth: Newton and Hooke's debate of 1679

In this article I would like to tell the story of the beginning of modern theoretical physics, freed from all kinds of questionable anecdotes which have entered the scientific literature over the centuries. It all began in the seventeenth century when the mathematical theory of astronomy began to take shape. A major step in the history of modern science was taken when a few members of The Royal Society in London realized that the laws ruling the motions of heavenly bodies as manifested in Kepler's three laws are also effective in the dynamics of Earth‐bound particle motion. Everything started, not with I. Newton, but with R. Hooke. Not Newton's falling apple (Voltaire's invention), but a far‐reaching response by R. Hooke to a letter by I. Newton, dated November 28, 1679, ignited Newton's interest in gravity. That letter contained the famous spiral which a falling body would follow when released from a certain height above the surface of the Earth. Hooke's answer, based on Keplerian orbits, expressed the opinion that the body's trajectory would rather follow an elliptical path. In his spiral sketch Newton, however, predicted correctly that the falling body would be found to suffer an eastward deviation from the vertical in consequence of the Earth's rotation. In the course of time, many a researcher, including Hooke himself, was able to verify this conjecture. But it took until 1803 for the first satisfactory calculation of the eastward displacement of a freely falling body to be performed, and was provided by C.F. Gauss.     

Generation of three-dimensional block-structured grids based on rotation of two-dimensional multiply connected cross sections

An algorithm for generating curvilinear block-structured grids in axisymmetric three-dimensional domains of any connectivity is developed. The organization of the connection between the blocks is automated. The grids constructed are used to compute ideal gas steady flows past axisymmetric bodies at a nonzero angle of attack.     

EXACT SOLUTION TO THE PROBLEM OF A HALF-PLANE CRACK IN A TRANSVERSELY ISOTROPIC PIEZOELECTRIC BODY SUBJECTED TO ANTISYMMETRIC TANGENTIAL POINT FORCES

An exact and complete solution of the problem of a half-plane crack in an infinite transversely isotropic piezoelectric body is presented. The upper and lower crack faces are assumed to be loaded antisymmetrically by a couple of tangential point forces in opposite directions. The solution is derived through a limiting procedure from that of a penny-shaped crack. The expressions for the electroelastic field are given in terms of elementary functions. Finally, the numerical results of the second and third mode stress intensity factorsk ₂ andk ₃ of piezoelectric materials and elastic materials are compared in figures. Project supported by the National Natural Science Foundation of China (No. 19872060 and 69982009) and the Postdoctoral Foundation of China.