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.     

面向二十一世纪的生物农药

简述了农药的发展经历，介绍了国内外生物农药的研究、发展和应用的现状及发展趋势。     

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.     

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     

有机磷灭蚊剂投放浓度和时间对水体总磷的影响

为分析新型低毒有机磷杀虫剂“1%双硫磷颗粒”投放对河道水质的影响,设置不同药剂投放浓度和不同反应时间的室内试验,以TP、NH₃-N及S^2-为目标因子,分析该药剂投放后水体污染物浓度。结果表明:不同试验组水样中S^2-质量浓度均小于0.02 mg/L,NH₃-N质量浓度处于0.029~0.036 mg/L之间,均达到地表水Ⅰ类标准;不同浓度药剂投放1 h后,水体TP质量浓度已达到稳定状态,且在60 h内均保持稳定,药剂投加量与水体TP质量浓度呈显著正相关(R²=0.85);不同处理组的药剂在水体中的TP释放量无明显差异,均在1.06~1.30 mg/g之间。“1%双硫磷颗粒”推荐适宜投放量不会使河道水质恶化到劣Ⅴ类,但增加药剂投放量会增加水体TP污染及富营养化风险。     

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.