Simulation of Three-Spin Interaction in Coupled Cavities Chain

We generalize usual second-order effective Hamiltonian approximation into third-order. Employing the generalized method, we propose a scheme to generate three-spin interaction using coupled cavity chain. We show that the third order term not only improves two parties interaction but also induces direct three-spin interaction which has not been simulated before. By controlling the frequency of laser field, one can obtain next nearest neighbor interaction on the same order with the nearest neighbor’s or the three-spin interaction on the same order as next nearest neighbor’s.     

镝掺杂LaPO4拉曼光谱变化规律的探讨

采用水热法和后续热处理合成出单斜相LaPO4以及LaPO4:Dy3+,通过XRD对样品进行物相分析,结果表明:所得样品为LaPO4,且XRD图谱及拉曼光谱中峰位的偏移表明Dy的存在,即Dy被掺杂到LaPO4基质中。通过研究用Dy对LaPO4进行不同量掺杂后其拉曼光谱的变化规律,进而找出用Dy对LaPO4进行不同量掺杂后其内部结构的变化规律。结果显示,用Dy对LaPO4进行不同量掺杂后,随着掺杂比例的增大,晶格畸变程度先上升后下降,且在镧镝物质的量比例为1∶0.06时对基体晶格结构影响最大。     

Construction of Hybrid Bimetallic Uranyl Compounds Based on a Preassembled Terpyridine Metalloligand

Six hybrid uranyl–transition metal compounds [UO₂Ni(cptpy)₂(HCOO)₂(DMF)(H₂O)] ( 1 ), [UO₂Ni(cptpy)₂(BTPA)₂] ( 2 ), [UO₂Fe(cptpy)₂(HCOO)₂(DMF)(H₂O)] ( 3 ), [UO₂Fe(cptpy)₂(BTPA)₂] ( 4 ), [UO₂Co(cptpy)₂(HCOO)₂(DMF)(H₂O)] ( 5 ), and [UO₂Co(cptpy)₂(BTPA)₂] ( 6 ), based on bifunctional ligand 4′-(4-carboxyphenyl)-2,2′:6′,2′′-terpyridine (Hcptpy) are reported (H₂BTPA = 4,4′-biphenyldicarboxylic acid). Single-crystal XRD revealed that all six compounds feature similar metalloligands, which consist of two cptpy⁻ anions and one transition metal cation. The metalloligand M(cptpy)₂ can be considered to be an extended linear dicarboxylic ligand with length of 22.12 Å. Compounds 1 , 3 , and 5 are isomers, and all of them feature 1D chain structures. The adjacent 1D chains are connected together by hydrogen bonds and π–π interactions to form a 3D porous structure, which is filled with solvent molecules and can be exchanged with I₂. Compounds 2 , 4 , and 6 are also isomers, and all of them feature 2D honeycomb (6,3) networks with hexagonal units of dimensions 41.91×26.89 Å, which are the largest among uranyl compounds with honeycomb networks. The large aperture allows two sets of equivalent networks to be entangled together to result in a 2D+2D→3D polycatenated framework. Remarkably, these uranyl compounds exhibit high catalytic activity for cycloaddition of carbon dioxide. Moreover, the geometric and electronic structures of compounds 1 and 2 are systematically discussed on the basis of DFT calculations.     

Certifying convergence of Lasserre’s hierarchy via flat truncation

Consider the optimization problem of minimizing a polynomial function subject to polynomial constraints. A typical approach for solving it globally is applying Lasserre’s hierarchy of semidefinite relaxations, based on either Putinar’s or Schmüdgen’s Positivstellensatz. A practical question in applications is: how to certify its convergence and get minimizers? In this paper, we propose flat truncation as a certificate for this purpose. Assume the set of global minimizers is nonempty and finite. Our main results are: (1) Putinar type Lasserre’s hierarchy has finite convergence if and only if flat truncation holds, under some generic assumptions; the same conclusion holds for the Schmüdgen type one under weaker assumptions. (2) Flat truncation is asymptotically satisfied for Putinar type Lasserre’s hierarchy if the archimedean condition holds; the same conclusion holds for the Schmüdgen type one if the feasible set is compact. (3) We show that flat truncation can be used as a certificate to check exactness of standard SOS relaxations and Jacobian SDP relaxations.     

Multi-Step Continuous-Flow Organic Synthesis: Opportunities and Challenges

Continuous-flow multi-step synthesis takes the advantages of microchannel flow chemistry and may transform the conventional multi-step organic synthesis by using integrated synthetic systems. To realize the goal, however, innovative chemical methods and techniques are urgently required to meet the significant remaining challenges. In the past few years, by using green reactions, telescoped chemical design, and/or novel in-line separation techniques, major and rapid advancement has been made in this direction. This minireview summarizes the most recent reports (2017–2020) on continuous-flow synthesis of functional molecules. Notably, several complex active pharmaceutical ingredients (APIs) have been prepared by the continuous-flow approach. Key technologies to the successes and remaining challenges are discussed. These results exemplified the feasibility of using modern continuous-flow chemistry for complex synthetic targets, and bode well for the future development of integrated, automated artificial synthetic systems.     

A novel azide-free asymmetric synthesis of oseltamivir phosphate (Tamiflu) starting from Roche’s epoxide

A novel azide-free asymmetric synthesis of oseltamivir phosphate 1 (Tamiflu®) starting from Roche’s epoxide is described. Roche epoxide 2 was converted into N-acetyl aminoalcohol 3 in 95% yield via a BF₃·OEt₂-catalyzed epoxide-opening with acetonitrile as a nucleophile. Compound 3 was then transformed into a methanesulfonate 4 in 98% yield. Compound 4 was converted into aziridine 5 in 91% yield. Aziridine 5 was subsequently converted into oseltamivir phosphate 1 via two paths (a and b). In the path a, compound 5 underwent aziridine-opening with diallylamine as a nucleophile to afford compound 7 in 93% yield; compound 7 could then be converted into oseltamivir phosphate 1 in 88% yield. In path b, compound 5 underwent aziridine-opening with isopropyl 2,2,2-trichloroacetimidate as a nucleophile to afford compound 8 in 94% yield, which was then converted into oseltamivir phosphate 1 in 82% yield.     

Computational insight into asymmetric uranyl‐salophen coordinated with α, β‐unsaturated aldehydes and ketones

The study of the catalytic activity and activation mechanism of asymmetric uranyl‐salophens with α, β‐unsaturated aldehydes or α, β‐unsaturated ketones, is a research hotspot. In this paper, the complexes of the uranyl–salophen(U‐S) modified by unilateral benzene, coordinated with cyclohexenone, cyclopentenone and acrolein, were investigated using density functional theory calculations at the level of B3LYP/6‐311G(d, p) basis set. The results showed that the uranyl‐salophen(U‐S) weakened the large π bond between C = C and C = O of the α, β‐unsaturated aldehydes and ketones, making the unsaturated aldehydes and ketones activated. In addition, the molecular‐recognition selectivity of the asymmetrical uranyl‐salophen for cyclohexenone and cyclopentenone were much higher than for acrolein.     

Complex dynamic behavior in a viral model with state feedback control strategies

With the consideration of mechanism of prevention and control for the spread of viral diseases, in this paper, we propose two novel virus dynamics models where state feedback control strategies are introduced. The first model incorporates the density of infected cells (or free virus) as control threshold value; we analytically show the existence and orbit stability of positive periodic solution. Theoretical results imply that the density of infected cells (or free virus) can be controlled within an adequate level. The other model determines the control strategies by monitoring the density of uninfected cells when it reaches a risk threshold value. We analytically prove the existence and orbit stability of semi-trivial periodic solution, which show that the viral disease dies out. Numerical simulations are carried out to illustrate the main results.