Single-handed helical polyethers synthesized via anionic polymerization of optically active 3-(9-alkylfluoren-9-yl)propene oxides

A series of optically active 3-(9-alkylfluoren-9-yl)propene oxides were synthesized by the reaction of 9-alkylfluoren-9-yllithium with the optically active epichlorohydrin at −70 °C and polymerized using KOH as an initiator. The molecular weight of the poly(3-(9-alkylfluoren-9-yl)propene oxide)s is larger than that of poly(4,4,4-triphenyl-1-butene oxide), which had been proved to take stable helical conformation in solution, and their molecular weight distributions were narrower (M_w/M_n = 1.02 to 1.09) than poly(4,4,4-triphenyl-1-butene oxide). By investigating of chiroptical properties of a series of polymers derived from optically active epoxide, it is suggested that the poly(3-(9-alkylfluoren-9-yl)propene oxide)s keep one-handed helical conformation in solution.     

Tailoring of chiroptical properties of substituted polyanilines by controlling steric hindrance

Optically active polyorthoanisidine, polyorthotoluidine, polyorthoethylaniline and polyorthochloroaniline were synthesized with chemical polymerization of corresponding monomers in aqueous medium by using d- or l-camphorsulfonic acid (d- or l-CSA) as chiral dopant, ammonium persulfate as oxidant, and diaminodiphenylamine as initiator. By circular dichroism spectroscopic measurements, it was found that PANI exhibited generally a reversed chirality in comparison with the used chiral dopant, but the substituted PANIs had the same one as the chiral dopant. This revealed that the substituent at ortho position caused helical inversion of conformation in comparison with the parent PANI. Such effect was further confirmed by the influence of the copolymerization of aniline and its derivatives on the chirality of the copolymers. The effect of the substituent on the chirality of the copolymers was increased with the increase of the steric hindrance of the ortho substituent. A mechanism was proposed to explain the effects of steric hindrance on the chirality of PANIs. The clarified relationship between the steric hindrance and the chirality of the polymer can enable us to tailor the chiroptical properties of functional polymer materials for future application.     

Preparation and Applications of Chiral Polymeric Particles

Chiral polymeric particles (CPPs) have been gathering increasing interest as typical functional polymeric particles in recent decades. This article presents a review on the preparation and applications of CPPs. The methods for preparing CPPs are classified into two major groups: The first one is the direct polymerization of monomers and the other is the post-treatment of preformed polymers. CPPs have been explored as a unique type of chiral materials in various fields like asymmetric catalysis, enantioselective release, enantioselective crystallization, and enantioseparation. This review article is expected to accelerate the progress of scientific research dealing with CPPs and their applications in chirality-related fields.     

Solid polymerization and supramolecular chirality formation of azobenzene substituted diacetylene Langmuir–Blodgett films

An azobenzene mesogen-substituted diacetylene (NADA) monolayer has been transferred onto the solid substrate by the traditional Langmuir–Blodgett (LB) method. Solid-state polymerization of NADA LB films can be sensitized in visible light region. In situ UV–vis absorption measurement enables us to study polymerization kinetics of NADA LB films. The polymerization process can be described as a first order rate equation and polymerization rate constants are characterized in detail. Furthermore, achiral NADA molecules can form chiral LB films through overcrowded packing of the azobenzene moiety.     

Chirality-enriched semiconducting carbon nanotubes synthesized on high surface area MgO-supported catalyst

Single-walled carbon nanotubes (SWCNTs) with a narrow diameter distribution were synthesized by radio frequency-Catalytic Chemical Vapor Deposition (RF-CCVD) through the pyrolysis of CH4. Fe-Co bimetallic catalytic nanoclusters were supported on high-surface area MgO nanopowders and used in the nanotube synthesis process. Nanolog absorption fluorescence analysis was used to characterize the chiralities of the as-produced SWCNTs over this nanostructural catalyst. In the final SWCNT sample, the (7,5) semiconducting carbon nanotube species were found to be dominant, with a low chirality variation.     

单层和双层手征介质球域中并矢格林函数理论及其应用研究

本文应用散射迭加法，首先给出了单层和双层手征介质球域中的并矢格林函数，分析了点偶极天线分别位于手征介质球心和球罩内任意位置处的辐射场特性，并组给出辐射阻抗随手征介质球尺寸的变化规律，特别考虑了手征导纳的影响；研究表明，通过改变手征介质球罩的厚度和波长之比，可以任意调节罩外辐射场的极化状态，因此，手征介质在天线工程中有广阔的应用前景。     

Optical isomers of 3,13-dimethylheptadecane: Sex pheromone components of the western false hemlock looper,Nepytia freemani (Lepidoptera: Geometridae)

(3S, 13R)-3, 13-Dimethylheptadecane [(3S, 13R)-3, 13-dime-17Hy] is the major pheromone component of the western false hemlock looper (WFHL),Nepytia freemani. In comparative gas chromotographic-electroantennographic detection (GC-EAD) analyses of stereoselectively synthesized isomers, 1 pg of (3S, 13R)-dime-17Hy elicited significantly stronger electrophysiological responses by male WFHL antennae than did 1 pg of separately injected (3R, 13R)-, (3R, 13S)- or (3S, 13S)-3, 13-dime-17Hy. In field experiments with individually tested stereoisomers. (3S, 13R)-3, 13-dime-17Hy was the only stereoisomer to attract males, but the four-stereoisomer blend was 3.6 times more attractive. Quaternary and all binary combinations of (3S, 13R)-3, 13-dime-17Hy with the other stereoisomers were equally attractive, suggesting that synergisytic behavioral activity in WFHL resided with either one of (3R, 13R)-, (3R, 13S)-, or (3S, 13S)-3, 13-dime-17Hy. Because optical isomers of (di)methylhydrocarbons do not separate on currently available columns, it remains unknown whether female WFHL also produce a four-stereoisomer pheromone blend. Substitutionality of pheromone stereoisomers without loss of behavioural activity has not previously been reported, but favorably compares with the concept of pheromone redundancy that was first suggested for the multiple pheromone component blend of the cabbage looper moth,Trichoplusia ni.     

频域分波法研究涂覆于金属表面的手征介质层的电磁反射特性

本文利用频域分波法研究了平面电磁波入射的涂覆于金属表面的无限大层状手征介质了反射特性。频域分波法是电磁场领域新近发展起来的一种计算方法，其特点是在频域内通过数学物理变换把平面电磁波分为前行波和后行波，从而清晰地了解介质中电磁波的传输特性。本文通过理论推导和数值计算，得出了一些有用的结论，为设计防电磁反射涂层提供了理论指导。     

Circularly polarized luminescence of enantiopure carboline-based europium cryptates under visible light excitation

The enantiomers of carboline-based cryptates were successfully resolved by chiral HPLC.These complexes show high configurational stability under harsh conditions and their absolute configuration was determined by comparing theoretical and expe rimental electronic circular dichroism spectra.The e nantiopure cryptates exhibit strong circularly polarized luminescence with a maximum dissymmetry factor g_(lum)=0.25 for the f-f transition ~5 D_0 →~7 F_1(λ=594 nm) under visible light excitation at λ_(gx)=400 nm.     

The fabrication and enhanced nonlinear optical properties of electrostatic self-assembled film containing water-soluble chiral polymers

An ultra-thin film containing a water-soluble chiral PPV derivative and oligo-thiophene derivative was fabricated through the electrostatic self-assembly technique. The PPV and thiophene derivatives are poly{(2,5-bis(3-bromotrimethylammoniopropoxy)-phenylene-1,4-divinylene)-alt-1,4-(2,5-bis((3-hydroxy-2-(S)-methyl)propoxy)phenylenevinylene) (BHP-PPV) and 4′,3″-dipentyl-5,2′:5′,2″:5″,2″′-quaterthiophene-2,5″′-dicarboxylic acid (QTDA), respectively. The circular dichroism (CD) spectrum of BHP-PPV cast film on quartz substrate proved the chirality of BHP-PPV. The UV–vis spectra showed a continuous deposition process of BHP-PPV and QTDA. The film structure was characterized by small angle X-ray diffraction (XRD) measurement and atomic force microscopy (AFM) images. The nonlinear optical (NLO) properties of BHP-PPV/QTDA ultra-thin film with different number of bilayers were investigated by the Z-scan technique with 8 ns laser pulse at 532 nm. The Z-scan experimental data were analyzed with the double-sided film Z-scan theory. The BHP-PPV/QTDA film exhibits enhanced reverse saturable absorption (RSA) and self-defocusing effects, which may be attributed to the conjugated strength, chirality and well-ordered film structure. The chirality may lead to the RSA of BHP-PPV/QTDA film contrary to the SA of the other electrostatic self-assembled films without chiral units. The self-defocusing effect should be due to the thermal effect.