Lanthanide MOFs for inducing molecular chirality of achiral stilbazolium with strong circularly polarized luminescence and efficient energy transfer for color tuning

We present herein an innovative host–guest method to achieve induced molecular chirality from an achiral stilbazolium dye (DSM). The host–guest system is exquisitely designed by encapsulating the dye molecule in the molecule-sized chiral channel of homochiral lanthanide metal–organic frameworks (P-(+)/M-(−)-TbBTC), in which the P- or M-configuration of the dye is unidirectionally generated via a spatial confinement effect of the MOF and solidified by the dangling water molecules in the channel. Induced chirality of DSM is characterized by solid-state circularly polarized luminescence (CPL) and micro-area polarized emission of DSM@TbTBC, both excited with 514 nm light. A luminescence dissymmetry factor of 10⁻³ is obtained and the photoluminescence quantum yield (PLQY) of the encapsulated DSM in DSM@TbTBC is ∼10%, which is close to the PLQY value of DSM in dilute dichloromethane. Color-tuning from green to red is achieved, owing to efficient energy transfer (up to 56%) from Ln³⁺ to the dye. Therefore, this study for the first time exhibits an elegant host–guest system that shows induced strong CPL emission and enables efficient energy transfer from the host chiral Ln-MOF to the achiral guest DSM with the emission color tuned from green to red.

Homochiral Ln-MOFs are synthesized to encapsulate achiral dyes to induce strong circularly polarized luminescence with a luminescence dissymmetry factor of 10⁻³.     

Magnetic, electronic, and structural characterization of nonstoichiometric iron oxides at the nanoscale

We have investigated the structural, magnetic, and electronic properties of nonstoichiometric iron oxide nanocrystals prepared by decomposition of iron(II) and iron(0) precursors in the presence of organic solvents and capping groups. The highly uniform, crystalline, and monodisperse nanocrystals that were produced enabled a full structural and compositional survey by electron microscopy and X-ray diffraction. The complex and metastable behavior of nonstoichiometric iron oxide (wüstite) at the nanoscale was studied by a combination of Mossbauer spectroscopy and magnetic characterization. Deposition from hydrocarbon solvents with subsequent self-assembly of iron oxide nanocrystals into superlattices allowed the preparation of continuous thin films suitable for electronic transport measurements.     

液膜法处理含氟废水

为了防止含氟废水的污染,人们研究了多种除氟方法,液膜技术是一项新的分离工艺,它操作简单,试剂用量少,有机相可重复利用。本文利用伯胺作迁移载体处理高含量的含氟废水,分离效率较好。 伯胺N_(1923)(简写RNH_2)为流动载体,上胺N_(205)(上海石油化工厂)为表面活性剂,煤油为溶剂。将内相CaCl_2,溶液与油相(含N_(1923)、N_(205)和煤油)按一定体积比例混合,高速搅拌,制成W/O     

Analysis and simulation on the performance of a gyro-penitron amplifier

A cylindrical waveguide gyro-peniotron amplifier is analysed theoretically in this paper. By a ballistic method and directly using the energy conservation in the beam-wave system, a set of interaction equations for the cylindrical waveguide gyro-peniotron amplifier is derived. Computer simulation shows that under defined conditions an interaction efficiency of 47%, an output power of 240kW at a gain of 22. 5 dB and a 3 dB-instantaneous bandwidth of 1. 9% for a central frequency of 35GHz, TE₀₃ mode gyro-peniotron amplifier could be achieved. The influence of the operation parameters on the amplifier performance is also presented.     

ULTRASONICALLY DISPERSED POTASSIUM AS DEPROTONATING AND COUPLING AGENT──SYNTHESIS OF 1，6－DINITRILES IN SITU

ＵＬＴＲＡＳＯＮＩＣＡＬＬＹ　ＤＩＳＰＥＲＳＥＤ　ＰＯＴＡＳＳＩＵＭ　ＡＳ　ＤＥＰＲＯＴＯＮＡＴＩＮＧ　ＡＮＤ　ＣＯＵＰＬＩＮＧ　ＡＧＥＮＴ──ＳＹＮＴＨＥＳＩＳ　ＯＦ　１，６－ＤＩＮＩＴＲＩＬＥＳ　ＩＮ　ＳＩＴＵＵＬＴＲＡＳＯＮＩＣＡＬＬＹＤＩＳＰ...     

Photoacoustic Spectrometry Investigation and Determination of Rare Earth Ions Ho3+ and Nd3+ in a Solution

A home-made high sensitive photoacoustic transducer was used to determine the photoacoustic signal in a solution. The photoacoustic spectra of Ho in different solvents were measured and comparedwith its absorption spectrum. The affection factors of photoacousticsensitivity are discussed. The trivalent rare earth ions Ho3+ and Nd3+in an aqueous acetonitrile solution were determined. The detection limit is 5×10-8 mol/L for Ho3+ and 1.0 ×10-7 mol/L for Nd3+, and corresponds to the absorbance of 1.5×10 and 6.3×10-7.respectively.     

Effects of thioamide substitutions on the conformation and stability of alpha- and 3(10)-helices

Thiopeptides, formed by replacing the amide oxygen atom with a sp(2) sulfur atom, are useful in protein engineering and drug design because they confer resistance to enzymatic degradation and are predicted to be more rigid. This report describes our free molecular dynamics simulations with explicit water and free energy calculations on the effects of thio substitutions on the conformation of alpha-helices, 3(10)-helices, and their relative stability. The most prominent structural effect of thio substitution is the increase in the hydrogen bond distance from 2.1 A for normal peptides to 2.7 A for thiopeptides. To accommodate for the longer C[double bond]S...H-N hydrogen bond, the (phi, psi) dihedral angles of the alpha-helix changed from (-66 degrees, -42 degrees) to (-68 degrees, -38 degrees), and the rise per turn increased from 5.5 to 6.3 A. For 3(10)-helices, the (phi, psi) dihedral angles (-60 degrees, -20 degrees) and rise per turn (6.0 A) changed to (-66 degrees, -12 degrees) and 6.8 A, respectively. In terms of relative stability, the most prominent change upon thio substitution is the decrease in the free energy difference, Delta A(alpha --> 3(10)), from 14 to 3.5 kcal/mol. Therefore, normal peptides are less likely to form 3(10)-helix than are thiopeptides. Component analysis of the Delta A(alpha --> 3(10)) reviews that the entropy advantage of the 3(10)-helix for both Ac-Ala(10)-NHMe and Act-Alat(10)-NHMe is attributed to the 3(10)-helix being more flexible than the alpha-helix. Interestingly, upon thio substitution, this differential flexibility is even more apparent because the alpha-helix conformation of Act-Alat(10)-NHMe becomes more rigid due to the bulkier sulfur atom.