Theoretical Prediction of Chiral 3D Hybrid Organic–Inorganic Perovskites

Hybrid organic–inorganic perovskites (HOIPs), in particular 3D HOIPs, have demonstrated remarkable properties, including ultralong charge‐carrier diffusion lengths, high dielectric constants, low trap densities, tunable absorption and emission wavelengths, strong spin–orbit coupling, and large Rashba splitting. These superior properties have generated intensive research interest in HOIPs for high‐performance optoelectronics and spintronics. Here, 3D hybrid organic–inorganic perovskites that implant chirality through introducing the chiral methylammonium cation are demonstrated. Based on structural optimization, phonon spectra, formation energy, and ab initio molecular dynamics simulations, it is found that the chirality of the chiral cations can be successfully transferred to the framework of 3D HOIPs, and the resulting 3D chiral HOIPs are both kinetically and thermodynamically stable. Combining chirality with the impressive optical, electrical, and spintronic properties of 3D perovskites, 3D chiral perovskites is of great interest in the fields of piezoelectricity, pyroelectricity, ferroelectricity, topological quantum engineering, circularly polarized optoelectronics, and spintronics.     

Asymmetric Hydrogenation of Activated Ketones on Platinum: Relevant and Spectator Species

The heterogeneous enantioselective hydrogenation of activated ketones over chirally modified platinum is reviewed with emphasis on identifying the role of the various species observed in this catalytic system. The past years have witnessed a continuous broadening of the scope of this catalytic system including new reactants and modifiers affording over 97% ee. New reaction pathways have been uncovered and the kinetic and mechanistic studies have been faced with a number of complicating factors caused by spectator species and interactions in solution and on the Pt surface. The previously proposed mechanistic models are critically assessed in the light of these new findings.     

高速波长可调液晶滤波器

描述了适用于光波分复接网络高速连续可调液晶滤波器。该滤波器利用手征近晶型液晶作为Ｆ－Ｐ标准具有源腔材料得到了微秒级开关速度。使用商品 ＢＤＨ７６４Ｅ液晶材料制成地光滤波器，开关速度小于１０μｓ，可调范围给３０ｎｍ，通带中心在１．５５μｍ。     

Enantioselective extraction of mandelic acid enantiomers based on chiral ligand exchange

Based on the chiral ligand exchange, the distribution behavior of mandelic acid enantiomers, and the partition of Cu^2 at different pH values were studied in a water/alcohol two-phase system containing Cu^2 and N-ndodecyl-L-proline(A). The influences of the solvent sort, the pH value, the concentrations of Cu^2 and chiral ligand on the partition coefficient(K) and separation factor(α) were discussed. The experimental results show that the A formed has more stable ternary complex with D-mandelic acid enantiomer than with L-mandelic acid enantiomer. There is an important influence of the pH value on K and a. When the pH values are less than 3.5, the formation of binary complexes is thermodynamically unfavourable. K and a become maximum when pH values are above 3.5 and the molar ratio of the chiral ligand to Cu^2 is 2:1.     

Selective recognition in molecularly imprinted polymer and its chromatographic characterization for cinchonine

A molecularly imprinting polymer (MIP) was synthesized via bulk polymerization under different conditions using anti-ague drug cinchonine (CN) as template. Infrared spectra (IR) results show that the template CNand functional monomer α-methyl acrylic acid (MAA) formed complexes before polymerization and the structure of complexes was simulated by Hyperchem. The results indicate that there are hydrogen bond or ionic bond between functional monomer and template molecule in acetonitrile solution. The MIP made in cold-initiated photo-polymerization has higher separation performance than that in the therm-initiated polymerization. The separation of the isomers CN and cinchonidine (CD) can be successfully obtained when its separate factor α reaches 1.82. Scatchard analysis suggests that the MIP recognizing CN with two classes of binding sites. The partition coefficient Kd, 1 and apparent maximum number nmax, 1 of binding sites with high affinity are 131.43 μmol/L and 58. 90 μmol/g, respectively,while Kd, 2 and nmax, 2 of binding sites with low affinity are 2.32 mmol/L and 169.08 mmol/g, respectively.     

Analysis of polarization plane rotation characteristic in 2D photonic crystal waveguide with chiral medium by condensed node spatial network

Using the photonic band gap in photonic crystals, the fundamental waveguide structures for the light wavelength range have been developed. Based on the fine structure of these many functional devices have been proposed by analytical or numerical simulation methods and the experiments of trial manufacture. In this paper, the treatment of chiral dielectric in the Condensed Node Spatial Network for the vector potential is explained, and we show the polarization plane rotation property in air‐hole and pillar type photonic crystal waveguide structures with the chiral medium substrate. Then, we show the fundamental advantage of the air‐hole type photonic crystal waveguide structure in application to a mode converter. © 2005 Wiley Periodicals, Inc. Electr Eng Jpn, 152(1): 7–14, 2005; Published online in Wiley InterScience ( www.interscience. wiley.com ). DOI 10.1002/eej.20098     

Role of Chiral Configuration in the Photoinduced Interaction of D- and L-Tryptophan with Optical Isomers of Ketoprofen in Linked Systems

The study of the L- and D-amino acid properties in proteins and peptides has attracted considerable attention in recent years, as the replacement of even one L-amino acid by its D-analogue due to aging of the body is resulted in a number of pathological conditions, including Alzheimer’s and Parkinson’s diseases. A recent trend is using short model systems to study the peculiarities of proteins with D-amino acids. In this report, the comparison of the excited states quenching of L- and D-tryptophan (Trp) in a model donor–acceptor dyad with (R)- and (S)-ketoprofen (KP-Trp) was carried out by photochemically induced dynamic nuclear polarization (CIDNP) and fluorescence spectroscopy. Quenching of the Trp excited states, which occurs via two mechanisms: prevailing resonance energy transfer (RET) and electron transfer (ET), indeed demonstrates some peculiarities for all three studied configurations of the dyad: (R,S)-, (S,R)-, and (S,S)-. Thus, the ET efficiency is identical for (S,R)- and (R,S)-enantiomers, while RET differs by 1.6 times. For (S,S)-, the CIDNP coefficient is almost an order of magnitude greater than for (R,S)- and (S,R)-. To understand the source of this difference, hyperpolarization of (S,S)-and (R,S)- has been calculated using theory involving the electron dipole–dipole interaction in the secular equation.     

超临界流体中的酶催化反应及研究进展

叙述了介质水含量、温度、压力、底物、产物含量及夹带剂等因素对超临界流体中酶催化反应的影响,并对超临界流体对手性药物的拆分和合成方法进行了归纳和综合。超临界流体中的酶催化已经有了一定研究,但目前大部分研究工作只停留在实验研究,而且流体和酶的选择过于集中。因此,如何使得这项技术应用于实际的大生产,尤其是在手性药物合成和拆分方面的应用将是今后研究的方向。