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1.
Functional materials derived from synthetic helical polymers are attracting increasing interest. Helically substituted polyacetylenes (HSPAs) are especially interesting as typical artificial helical polymers. In recent years, we designed and prepared a series of functional materials based on HSPAs and inorganic materials. The target is to establish some novel hybrid materials that combine the superior properties of both. The examined inorganic materials include silica, graphene, and magnetic Fe3O4 nanoparticles. Such new functional materials hold great promise and are expected to find practical applications, for instance, as chiral absorbents, chiral sensors, chiral selectors for inducing enantioselective crystallization, chiral catalysts towards asymmetric catalysis, and chiral carriers for enantioselective release. The Personal Account summarizes our major achievements in preparing optically active hybrid materials. We hope it will speed up progress in chiral‐related research areas.  相似文献   

2.
This review mainly describes the asymmetric synthesis of optically active polymers with helical conformation. Bulky methacrylates such as triphenylmethyl methacrylate and 1-phenyldibenzosuberyl methacrylate give one-handed helical and optically active polymers with almost perfectly isotactic main chain conformation by polymerization with chiral anionic initiators. The radical polymerization and copolymerization of these monomers under chiral conditions also afford optically active polymers with prevailing one-handed helicity. N, N-Disubstituted acrylamides also give optically active, helical polymers in the asymmetric anionic polymerization. Optically active polyisocyanates with a prevailing one-handed helical structure have been prepared in the copolymerization of an achiral isocyanate with a small amount of an optically active isocyanate and also in the polymerization of alkyl and aromatic isocyanates with optically active lithium alkoxide or amide compounds. The existence of a stable helical structure for polychloral has been successfully proved with the helical oligomers of chloral. One-handed helical polyisocyanides have been prepared by helix-sense-selective polymerization of bulky isocyanides and also by the cyclopolymerization of a 1, 2-diisocyanobenzene derivative with the Pd complex of a one-handed helical oligomer.  相似文献   

3.
The methods used for the separation and analytical determination of individual isomers are based on interactions with substances exhibiting optical activity. The currently used methods for the analysis of optically active compounds are primarily high-performance separation methods, such as gas and liquid chromatography using chiral stationary phases or chiral selectors in the mobile phase, and highly efficient electromigration techniques, such as capillary electrophoresis using chiral selectors. Chemical sensors and biosensors may also be designed for the analysis of optically active compounds.  相似文献   

4.
Editorial     
Abstract

Asymmetric syntheses of optically active polymethacrylate, polyacrylate, polyacrylamide, and polyisocyanate with helical conformation and their chiral recognition abilities are described. 1-Phenyldibenzosuberyl methacrylate (PDBSMA) gave a purely onehanded-helical, optically active polymer ([α]365 +1670 ~ +1780º) with almost perfectly isotactic structure by anionic polymerization using optically active initiators. Radical polymerizations of PDBSMA using chiral initiators, chain transfer agents, and additives also afforded optically active polymers with a prevailing onehanded helicity. Triphenylmethyl acrylate yielded an optically active, helical polymer ([α]365 +102º) having a dyad isotacticity of 70% using an optically active anionic initiator. Although the polyacrylate demonstrated chiral recognition ability as a chiral stationary phase for HPLC, the ability was low mainly because of the low degree of one-handedness. N-(3-Chlorophenyl)-N-phenylacrylamide gave an optically active, helical polymer ([α]365–343º) in the asymmetric anionic polymerization; the polymer had a dyad tacticity of 77%. Optically active polyisocyanates with a predominantly one-handed helical conformation were prepared in homo-and co-polymerization of optically active phenyl isocyanate derivative. These polyisocyanates showed the ability to discriminate enantiomers in solution.  相似文献   

5.
We successfully synthesized optically active polymers by using a chiral bisphosphine, (S,S)‐1,2‐bis[boranato(t‐butyl)methylphosphino]ethane, as a key building block. Their structures were characterized with 1H, 13C, and 31P NMR spectra. The obtained polymers exhibited different glass‐transition temperatures depending on the structure of each comonomer, whereas a model compound had a melting point. According to circular dichroism spectra, the difference in the stereochemistry of the comonomers yielded the different higher‐ordered structures of the polymers induced by chiral phosphine units. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 866–872, 2007  相似文献   

6.
Optically active poly(m‐phenylene)s substituted with chiral oxazoline derivatives have been synthesized by the nickel‐catalyzed Yamamoto coupling reaction of optically active (S)‐4‐benzyl‐2‐(3,5‐dihalidephenyl)oxazoline derivatives (X = Br or I). The structures and chiroptical properties of the polymers were characterized by spectroscopic methods and thermal gravimetric analyses. The polymers showed higher absolute optical specific rotation values than their corresponding monomer, and showed a Cotton effect at transition region of conjugated main chain. The optical activities of the polymers should be attributed to the higher order structure such as helical conformations. Moreover, the helical conformation could be induced by addition of metal salts into polymer solutions. The polymers showed good thermal stabilities, which was attributable to the oxazoline side chains. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013  相似文献   

7.
Novel poly(biphenylylacetylene) derivatives carrying different types of pyridine N‐oxide units with a bulky or less‐bulky substituent at a different position as the functional pendant groups (poly‐ 2a and poly‐ 2b ) were synthesized by the rhodium‐catalyzed polymerization of the corresponding monomers. The influence of the steric environment around the catalytically active pyridine N‐oxide sites on the helicity induction and its static memory as well as the asymmetric catalytic activities of the resulting helical polymers with a macromolecular helicity memory was investigated. The polyacetylenes formed an excess one‐handed helical conformation upon noncovalent interactions with optically active alcohols and the induced macromolecular helicities of the polyacetylenes were efficiently memorized after the removal of the chiral inducers. Poly‐ 2b with the macromolecular helicity memory showed an enantioselectivity for the catalytic asymmetric allylation of benzaldehydes, producing optically active allyl alcohols, although their enantioselectivities were low. On the other hand, poly‐ 2a exhibited a negligible catalytic activity probably due to the bulky substituent at the o‐position of the pyridine N‐oxide residues, while poly‐ 2a underwent a unique helix‐inversion with the increasing concentration of chiral alcohols and the opposite helicity of poly‐ 2a was further successfully memorized. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 2481–2490  相似文献   

8.
A new class of chiral and potentially biodegradable poly(ester-imide)s (PEI)s as pseudo-poly(amino acid)s (PAA)s bearing natural amino acids in the main chain was synthesized. In this investigation, N,N′-(pyromellitoyl)-bis-(L-tyrosine dimethyl ester) as a biodegradable optically active diphenol and synthesized trimellitic anhydride-derived dicarboxylic acids containing different natural amino acids such as S-valine, L-methionine, L-leucine, L-isoleucine, and L-phenylalanine were used for direct polyesterification. With the aim of tosyl chloride/pyridine/N,N′-dimethylformamide system as a condensing agent, the new optically active PEIs were obtained in good yields and moderate inherent viscosity up to 0.42 dL/g. The obtained polymers were characterized with FT-IR, 1H-NMR, X-ray diffraction (XRD), field emission scanning electron microscopy, elemental, and thermogravimetric analysis techniques. These polymers show high solubility in organic solvents, such as N,N′-dimethyl acetamide, N-methyl-2-pyrrolidone, and sulfuric acid at room temperature, and are insoluble in solvents, such as methylene chloride, cyclohexane, and water. Morphology probes showed these pseudo-poly(amino acid)s were noncrystalline and nanostructured polymers. On the basis of thermogravimetric analysis data, such PAAs are thermally stable and can be classified as self-extinguishing polymers. In addition due to the existence of amino acids in the polymer backbones these pseudo-PAAs not only are optically active but also are expected to be biodegradable and therefore could be classified under eco-friendly polymers.  相似文献   

9.
The resolution of stereoisomers of C21‐alkylated nickel(II) complexes of N‐confused porphyrin (NCP) was performed by means of chiral‐phase HPLC with an effectiveness of above 90 % molar ratio for each isomer. The reverse signs of the Cotton effects in the circular dichroism (CD) spectra of the separated fractions are indicative of the pair of enantiomers. The application of low‐temperature 2D NMR methods to the separated diastereomers of the system comprising a chiral 2‐(S)‐methylbutyl substituent, in connection with the CD spectra and relative HPLC migration rates, allowed the assignment of the absolute configuration of the chiral C21‐substituted complexes of NCP. The assignment was confirmed by time‐dependent DFT (TDDFT) calculations of CD spectra for the C21‐methylated nickel(II) complex. The system remains chiral after removal of the metal ion from the macrocyclic crevice, despite the fact that this demetalation is connected with a change of the C21 hybridization from pyramidal to trigonal. The retention of chirality was established by means of CD spectra and confirmed by TDDFT calculations for a C21‐methylated NCP free base. Stereoisomers were also separated for three covalently linked bis(NCP) systems with bridges involving one or two C21 carbon atoms. The occurrence of a pair of enantiomers was established for nonsymmetrical dimers comprising only one stereogenic center. In the case of the 21,21′‐(o‐xylene)‐linked dimer, three stereoisomers, that is, a pair of enantiomers and an optically inactive meso‐form, were separated and analyzed by CD and 1H NMR spectroscopy. The stereoisomers of a diastereoselectively formed nonsymmetrical chloroplatinum(II)‐linked dimer, consisting of heterochiral C21‐alkylated NCP nickel(II) subunits, after separation displayed a strong optical activity, which can be ascribed to the rigid helical structure of the complex.  相似文献   

10.
Optically active polymers bearing chiral units at the side chain were prepared via reversible addition‐fragmentation chain transfer (RAFT) polymerization in the presence of 2,2′‐azobisisobutyronitrile (AIBN)/benzyl dithiobenzoate (BDB), using a synthesized 6‐Op‐vinylbenzyl‐1,2:3,4‐Di‐O‐isopropylidene‐D ‐galactopyranose (VBPG) as the monomer. The experimental results suggested that the polymerization of the monomer proceeded in a living fashion, providing chiral group polymers with narrow molecular weight distributions. The optically active nature of the obtained poly (6‐Op‐vinylbenzyl‐1,2:3,4‐Di‐O‐isopropylidene‐D ‐galactopyranose) (PVBPG) was studied by investigating the dependence of specific rotation on the molecular weight of PVBPG and the concentration of PVBPG in tetrahydrofuran (THF). The results showed the specific rotation of PVBPG increased greatly with the decrease of the concentration of the PVBPG homopolymer. In addition, the effect of block copolymers of PVBPG on the optically active nature was also investigated by preparing a series of diblock copolymers of poly(methyl methacrylate) (PMMA)‐b‐PVBPG, polystyrene (PS)‐b‐PVBPG, and poly(methyl acrylate) (PMA)‐b‐PVBPG. It was found that both the homopolymer and the diblock copolymers possessed specific rotations. Finally, the ability of chiral recognition of the PVBPG homopolymer was investigated via an enantiomer‐selective adsorption experiment. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3788–3797, 2007  相似文献   

11.
Two novel phenylacetylene derivatives bearing diethylaminomethyl groups at the meta position on phenyl groups [3‐(N,N‐diethylaminomethyl)phenyl]acetylene ( 1 ) and [3,5‐bis(N,N‐diethylaminomethyl)phenyl]acetylene ( 2 ) were synthesized and polymerized with [Rh(nbd)Cl]2 (nbd: norbornadiene). Both monomers gave highly cis–transoidal stereoregular polymers that exhibited an induced circular dichroism (ICD) in the UV–visible region, probably because of a prevailing one‐handed helical conformation upon complexation with optically active carboxylic acids such as mandelic acid and lactic acid. The sign of the Cotton effects reflected the absolute configuration of the chiral acids. Therefore, these polymers can be used as a novel probe for determining the configuration of chiral acids. The polymers were stable in the presence of chiral acids in solution. The poly‐ 1 complexed with chiral acids exhibited a split‐type ICD, whereas the poly‐ 2 complexed with chiral acids showed a different, non‐split‐type ICD. The ICD pattern of the poly‐ 1 /chiral acids complexes dramatically changed with an increase in the concentration of the chiral acids, thus showing a non‐split‐type ICD similar to those of the poly‐ 2 /chiral acid complexes. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3180–3189, 2001  相似文献   

12.
Helical polymers have attracted a great deal of attention and been extensively investigated due to their various applications.One of the most important applications of helical polymers is chiral recognition and resolution of enantiomers for the reason that a pair of enantiomers is commonly with different physiological and toxicological behaviors in biological systems.Helical polymers usually present unexpected high chiral recognition ability to a variety of racemic compounds.What's more,the chiral recognition and resolution abilities of the system are dependent on the highly ordered helical structures of the helical polymers.This mini review mainly focuses on the recent progress in chiral recognition and resolution based on helical polymers.The synthetic methodology for helical polymers is firstly discussed briefly.Then recent advances of chiral recognition and resolution systems based on helical polymers,especially polyacetylenes and polyisocyanides,are described.We hope this mini review will inspire more interest in developing helical polymers and encourage further advances in chiral-related disciplines.  相似文献   

13.
Two optically active solvents were synthesised, (S)‐(–)‐2‐methyl‐1‐propoxybutane and (S)‐(–)‐(2‐methylbutoxymethyl)benzene. The main chain conformations of poly(methylphenylsilane) and poly(hexylmethylsilane) in these solvents were investigated using optical UV‐visible and circular dichroism spectroscopy. It was observed that dissolving these inherently achiral polysilanes in optically active solvents induces the polymer chains to adopt preferred helical screw senses. This is the first example of induction of optical activity in conjugated polymers through chiral solvation.  相似文献   

14.
Optically active homopolymers and copolymers, bearing chiral units at the side chain and end chain, were prepared via atom transfer radical polymerization (ATRP) techniques. The well‐defined optically active polymers were obtained via the ATRP of pregnenolone methacrylate (PR‐MA), β‐cholestanol acrylate (CH‐A), and 20‐(hydroxymethyl)‐pregna‐1,4‐dien‐3‐one acrylate (HPD‐A) with ethyl 2‐bromopropionate as the initiator and CuBr/N,N,N′,N″,N″‐pentamethyldiethylenetriamine as the catalytic system. The experimental results showed that the polymerizations of PR‐MA, CH‐A, and HPD‐A proceeded in a living fashion, providing pendent chiral group polymers with low molecular weight distributions and predetermined molecular weights that increased linearly with the monomer conversion. Furthermore, the copolymers poly(pregnenolone methacrylate)‐b‐poly[(dimethylamino)ethyl methacrylate] and poly(pregnenolone methacrylate‐co‐methyl methacrylate) were synthesized and characterized with 1H NMR, transmission electron microscopy, and polarimetric analysis. In addition, when optically active initiators estrone 2‐bromopropionate and 20‐(hydroxymethyl)‐pregna‐1,4‐dien‐3‐one 2‐bromopropionate were used for ATRPs of methyl methacrylate and styrene, terminal optically active poly(methyl methacrylate) and polystyrene were obtained. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1502–1513, 2006  相似文献   

15.
The chiral ferroelectric smectic C (SmC*) phase, characterized by a helical superstructure, has been well exploited in developing high‐resolution microdisplays that have been effectively employed in the fabrication of a wide varieties of portable devices. Although, an overwhelming number of optically active (chiral) liquid crystals (LCs) exhibiting a SmC* phase have been designed and synthesized, the search for new systems continues so as to realize mesogens capable of meeting technical necessities and specifications for their end‐use. In continuation of our research work in this direction, herein we report the design, synthesis, and thermal behavior of twenty new optically active, three‐ring calamitic LCs belonging to four series. The first two series comprise five pairs of enantiomeric Schiff bases whereas the other two series are composed of five pairs of enantiomeric salicylaldimines. In each pair of optical isomers, the configuration of a chiral center in one stereoisomer is opposite to that of the analogous center in the other isomer as they are derived from (3 S)‐3,7‐dimethyloctyloxy and (3 R)‐3,7‐dimethyloctyloxy tails. To probe the structure–property correlations in each series, the length of the n‐alkoxy tail situated at the other end of the mesogens has been varied from n‐octyloxy to n‐dodecyloxy. The measurement of optical activity of these chiral mesogens was carried out by recording their specific rotations. As expected, enantiomers rotate plane polarized light in the opposite direction but by the same magnitude. The thermal behavior of the compounds was established by using a combination of optical polarizing microscopy, differential scanning calorimetry, and powder X‐ray diffraction. These complementary techniques demonstrate the existence of the expected, thermodynamically stable, chiral smectic C (SmC*) LC phase besides blue phase I/II (BPI or BPII) and chiral nematic (N*) phase. However, as noted in our previous analogous study, the vast majority of the Schiff bases show an additional metastable, unfamiliar smectic (SmX) phase just below the SmC* phase. Notably, the SmC* phase persists over the temperature range ≈80–115 °C. Two mesogens chosen each from Schiff bases and salicylaldimines were investigated for their electrical switching behavior. The study reveals the ferroelectric switching characteristics of the SmC* phase featuring the spontaneous polarization (PS) in the range 69–96 nC cm?2. The helical twist sense of the SmC* phase as well as the N* phase formed by a pair of enantiomeric Schiff bases and salicylaldimines has been established with the help of circular dichroism (CD) spectroscopic technique. As expected, the SmC* and the N* phase of a pair of enantiomers showed mirror image CD signals. Most importantly, the reversal of helical handedness from left to right and vice versa has been evidenced during the N* to SmC* phase transition, implying that the screw sense of the helical array of the N* phase and the SmC* phase of an enantiomer is opposite.  相似文献   

16.
The need for new optically active monomers and polymers is conducive to the setting up of stereospecific synthesis routes starting from chiral precursors. The biomass can be considered as a major source for extracting such biomolecules aimed at chemoenzymatic transformation and further polymerization. Due to its versatility, ß-methylaspartate ammonia-lyase, from cell-free extracts of Clostridium tetanomorphum, has been used in the bioconversion of alkylfumarates into optically active pure 3-alkylaspartic acids with alkyl=methyl, ethyl, isopropyl. These amino acids have been transformed in several steps into optically active benzyl 3-alkylmalolactonates leading to semi-crystalline polyesters. 3-Methylaspartic acid includes two chiral centers and the racemic compound containing the four stereoisomers can be prepared by a multiple step synthesis. The ability of ß-methylaspartase to catalyse both syn- and anti-elimination of ammonia from natural 3-methylaspartic acid has been expressed to retain one stereoisomer and this bioconversion is a preparative method for obtaining unnatural stereoisomers. Moreover, the catalytic hydrogenolysis of the benzyl α,ß-substituted ß-lactone yields stable 3-alkylmalolactonic acid which can be coupled with functional alcohols and copolymerized. At last the introduction of (2S)-3,3-dimethyl-2-butanol, using Rhodotorula glutinis as microorganism in a biological synthesis step, as chiral ester pendant group, has conducted to optically active polyesters with very high melting transition temperatures. The combination of bioconversion and chemical synthesis is a very useful tool for building hydrolyzable functionalized polyesters required for temporary applications.  相似文献   

17.
<正>A potential biodegradable and optically active bulky chiral aromatic amide-imidic diacid monomer,(2S,3S)-5-(3- methyl-2-phthalimidylpentanoylarnino)isophthalic acid(7),containing a rigid phthalimide and flexible L-isoleucine pendant group was synthesized in three steps.New aromatic polyamides including pendant phthalimido groups and flexible side spacers have been synthesized by direct polycondensation reaction of equimolar amounts of different aromatic diamines with an optically active diacid 7,using N-methyl-2-pyrrolidone(NMP) as a solvent and triphenyl phosphite/CaCl_2/pyridine as a condensing agent.These polyamides were characterized by FTIR,~1H-NMR spectroscopy,specific rotation, thermogravimetric and elemental analysis.The resulting polymers have inherent viscosities in the range of 0.21-0.45 dL/g. Amino acid existence in this backbone results in optically active polymers.Due to introduction of bulky and flexible groups in these polyamides,they show improved solubility in polar aprotic solvents such as NMP and dimethylacetamide and also good thermal stability(10%weight loss temperatures in excess of 330℃,and char yields at 600℃in nitrogen higher than 62%).  相似文献   

18.
To develop better polymeric materials for optical-resolution membranes, we synthesized nine chiral phenylacetylenes containing pinanyl groups. We used them to investigate the effects of chemical structures, including the number and position of the chiral groups in the monomers, on the induction of chirality in the main chain during polymerization and on the degree of enantioselectivity in the permeation of the polymeric membranes. The monomers included six new chiral p-(oligomethylpinanylsiloxanyl)phenylacetylenes. The homopolymerizations of these nine monomers with a Rh complex produced high-molecular-weight polymers (molecular weight = 105–106). Of the five polymers with a chiral pinanyl group at the 1-position of each oligosiloxanyl group, all except for two polymers showed high molar ellipticity in the main-chain region in the circular dichroism spectra. This finding indicated that these polymers had a chiral helical main chain. The membranes fabricated from all the polymers synthesized in this study were high-quality, except for two polymers. All these membranes showed enantioselective permeabilities for two amino acids and an alcohol. The membranes from the polymers with a chiral helical backbone, a high content of pinanyl groups, no oligodimethylsiloxane moieties, or a combination of these showed good enantioselectivities (= 1.7–640) in permeation. We propose that the sense of the main-chain helicity determined the selectivity. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4502–4517, 2004  相似文献   

19.
A cholesteryloxyallene (1) bearing chiral cholesteryl pendant group was designed and synthesized. Living polymerization of this monomer with an allylnickel complex as a catalyst give poly(cholesteryloxyallene)s (poly‐ 1 ms) in high yields with controllable molecular weights and narrow molecular weight distributions. These polymers were found to possess a dynamic helical conformation with a preferred handedness in n‐hexane as confirmed by circular dichroism and absorption spectra as well as optical ratios. The helical conformation of the polymers was revealed to stabilize as the number of repeat units increased until the degree of polymerization reached 100. The helical conformation of poly‐ 1 100 could be controlled by altering the temperature of solutions. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2227–2233  相似文献   

20.
杨光  何晨露  邹纲 《高分子学报》2017,(11):1725-1738
手性是自然界中普遍存在的有趣现象之一,在生命体中手性大分子特有的不对称结构在维持生命过程、新陈代谢和进化等面均起着决定性作用.受此启发,合成具有新型结构的光学活性聚合物,研究其独特的物理化学性质和功能已成为当今高分子领域研究的热点.左旋和右旋的圆偏振光已被广泛应用于氨基酸衍生物的不对称光合成、光分解和去消旋化反应,以及诱导含有偶氮苯或三苯胺等特定功能基团的超分子组装体或无机纳米粒子形成稳定螺旋结构.本文详细地介绍了圆偏振光辐照在手性聚合物合成与螺旋结构调控中的应用,初步揭示了圆偏振光的作用机制以及优势,归纳总结了已取得的研究进展,并对圆偏振光在手性聚合物合成与结构调控中的应用及发展进行了简单的评述和展望.  相似文献   

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