Enhanced enantioselectivity in the heterogeneous catalytic hydrogenation of acetoacetate esters into the corresponding 3-hydroxybutyrates using commercial nickel powder

Heterogeneous catalytic hydrogenation of acetoacetic acid esters over tartaric acid/NaBr-modified Ni powder was determined to be a critical function of the steric bulk of the ester moiety to afford quantitatively 3-hydroxybutyrate in 94% enantiomeric excess when ethyl and i-butyl esters are used, providing a facile route to optically active 3-hydroxybutyrates.     

Asymmetric electrocarboxylation of 1-phenylethyl chloride catalyzed by electrogenerated chiral [CoI(salen)]− complex

The feasibility of asymmetric electrocarboxylation of 1-phenylethyl chloride catalyzed by the electrogenerated chiral [Co^I(salen)]⁻ complex has been investigated for the first time. Using this system, optically active 2-phenylpropionic acid in 37% yield and 83% ee is synthesized from 1-phenylethyl chloride and CO₂. The electrochemical behavior of the catalyst and the optimization of synthesis conditions are discussed. This study provides a new procedure for the asymmetric synthesis of a chiral compound and expands the applications of chiral Co^II(salen) in the electrochemical asymmetric fixation of CO₂.     

Mathematical modeling of electromagnetic wave propagation in heterogeneous lossy coaxial cables with variable cross section

In this work, we focus on the time-domain simulation of the propagation of electromagnetic waves in non-homogeneous lossy coaxial cables. The full 3D Maxwell equations, that described the propagation of current and electric potential in such cables, are classically not tackled directly, but instead a 1D scalar model known as the telegraphist's model is used. We aim at justifying, by means of asymptotic analysis, a time-domain “homogenized” telegraphist's model. This model, which includes a nonlocal in time operator, is obtained via asymptotic analysis, for a lossy coaxial cable whose cross section is not homogeneous.     

A viologen-urea-based anion receptor： Colorimetric sensing of dicarboxylate anions

Compound 1 bearing urea and viologen groups has been designed and synthesized.It could be used as a colorimetric receptor for dicarboxylate anions due to the significant color changes of the solution upon the addition of dicarboxylates.More importantly,the color changes were related to the chain lengths of the dicarboxylates tested.UV-vis,’H NMR and HRMS studies demonstrated that receptor 1 utilized hydrogen bonds and electrostatic interactions to form 1:1 stoichiometry complexes with these anions.In addition,the generation of cation radical 1’ during the complexation process was also detected by EPR.     

UV beam-assisted efficient formation of surface relief grating on azobenzene polymers

An efficient method is demonstrated to improve the formation of a surface relief grating (SRG) with a high amplitude. The SRG is realized by a two-beam interference technique (λ=532 nm) in an azobenzene side-chain copolymer. An UV laser beam (λ=355 nm), called assisting beam, was used to accelerate the photoisomerization process from cis-form to trans-form, resulting in a rapid cis-form ? trans-form cycle. This UV beam-assisted method allowed to increase the diffraction efficiency of the formed SRG as well as its depth. Stable gratings with modulation depth as high as 410 nm were obtained at room temperature with moderate laser power.     

A M?ssbauer spectroscopic study on the action of Ce in the catalyst for dehydrogenation of etylbenzene to styrene

Two series of Fe-K catalysts for dehydrogenation of ethylbenzene to styrene were prepared with different amounts and different compounds of the additional element Ce. M?ssbauer spectroscopy has been used to determine the Fe compound in the catalyst and to investigate the effect of Ce. The catalytic properties of the catalysts have also been measured. The results show that the element Ce in the catalyst is favorable to form the predecessor of the catalytic active phase, the compound KFe₁₁O₁₇ and that the optimal percentage of CeO₂ is 8%～15% in the catalyst which is favorable to the formation of KFe₁₁O₁₇ and to get better catalytic properties.     

Metal-Organic Frameworks with Novel Catenane-like Interlocking: Metal-Determined Photoresponse and Uranyl Sensing

The assembly of two tripyridinium-tricarboxylate ligands and different metal ions leads to seven isostructural MOFs, which show novel 2D→2D supramolecular entanglement featuring catenane-like interlocking of tricyclic cages. The MOFs show tripyridinium-afforded and metal-modulated photoresponsive properties. The MOFs with d¹⁰ metal centers ( 1-Cd , 1-Zn , 2-Cd , 2-Zn ) show fast and reversible photochromism and concomitant fluorescence quenching, 1-Ni displays slower photochromism but does not fluoresce, and 1-Co and 2-Co are neither photochromic nor fluorescent. It is shown here that the network entanglement dictates donor-acceptor close contacts, which enable fluorescence originated from interligand charge transfer. The contacts also allow photoinduced electron transfer, which underlies photochromism and concomitant fluorescence response. The metal dependence in fluorescence and photochromism can be related to energy transfer through metal-centered d-d transitions. In addition, 1-Cd is demonstrated to be a potential fluorescence sensor for sensitive and selective detection of UO₂²⁺ in water.     

Recent progresses on the development of thioxo-naphthalimides

Thioxo/dithioxo-naphthalimide is a class of rarely visited fluorophore, first synthesized in 1999. Facile chemistry was devised to achieve mono or dual thionation of the two carbonyl groups of 1,8-naphthalimide. Thionation effectively shifts absorption maximum to longer spectral wavelength, significantly increase absorption coefficients, and dramatically enhances intersystem crossing efficiency with respect to their oxo-analogues. They were first explored as potent photocleavers to induce DNA strand break and novel photosensitizers for photodynamic therapies. In recent years, the unique chemistry of thioxo groups has been harnessed to achieve new applications, such as fluorescent sensors for heave metal ions. These unique photochemical and photophysical characteristics revitalize them intriguing functional molecules to investigate. In this short review, we wish to revisit their first discovery, facile synthesis, and the endeavors on the use of thioxo/dithioxo-naphthalimides for novel chemical and biomedical applications.