PHYSICAL CHEMISTRY CHEMICAL PHYSICS
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2025
·
IF 2.9
Chunyu Song,Xuan Zhang,Chenglong Qiu,Yong Yang
Polyacetylenes (PDAs) with superior thermochromic properties serve as effective safeguards against equipment overheating and personal safety hazards. However, their responsiveness to medium-to-high temperature ranges still poses a significant challenge. In this study, a series of thermochromic bis-polyacetylene (Bis-PDA-1, Bis-PDA-2, Bis-PDA-3) linked with symmetric aromatic amides consisted of benzene, biphenyl and bipyridine at the center have been developed. These polymers can undergo multi-step color transitions in response to thermal stimulation ranged from 80 °C to 110 °C, and after multiple heating and cooling cycles, the samples still show reversible thermochromic characteristics. The thermochromic Bis-PDAs exhibit exceptional sensitivity with instantaneous color transitions (<1 s) at 110°C. The temperature-dependent high-contrast chromatic variations significantly improve visual discernibility in practical applications. In particular, Bis-PDA-1 displays thermochromic behavior when heated up to 110 °C, which presents a higher color transition temperature than Bis-PDA-2 and Bis-PDA-3. This is attributed to the low steric hindrance of Bis-PDA-1 at the molecular center, which enhances the intermolecular hydrogen bonding. These Bis-PDAs designed in this work present superior practicability in the field of thermal management, which also provide a guideline for the tuning of color-transition behaviors of thermochromic materials.
研究领域:
材料科学
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高分子化学
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热致变色
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传感器
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纳米技术
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产品关联
DOI
PubMed
高影响因子
JOURNAL OF APPLIED POLYMER SCIENCE
·
2020
·Vol. 137
·期 39
·49167
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IF 2.52
Jiaqi Shang,Song Mei,Danyu Zhao,Jianping Deng
Optically active hybrid particles consisting of chiral organic component and inorganic component integrate the individual advantages of the components in one entity. This article reports a new type of optically active hybrid particles constructed by helical substituted polyacetylene and octavinyl polyhedral oligomeric silsesquioxane (OvPOSS). The hybrid particles were prepared in a two-step process. First, helical substituted polyacetylene with pendent vinyl groups was synthesized and named as macromonomer (MM). Then, hybrid particles were prepared from MM and OvPOSS by free radical suspension polymerization, in which OvPOSS acted simultaneously as comonomer and crosslinking agent. OvPOSS and MM together constituted a crosslinked network and formed spherical, porous hybrid particles. The resulting hybrid particles exhibited the desired optical activity, according to circular dichroism spectroscopy measurement. As an organic/inorganic hybrid molecule itself, OvPOSS moderately improved the thermostability of the organic component and meanwhile increased the porosity of the hybrid particles. It also helped to tune the surface morphology of the hybrid particles. The present study provides a novel class of optically active hybrid particles, and the preparation strategy may further work as a versatile platform for developing novel chiral hybrid materials.
研究领域:
材料科学
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有机化学
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DOI
高影响因子
CHINESE JOURNAL OF POLYMER SCIENCE
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2014
·Vol. 32
·期 7
·931-940
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IF 1.42
Liu Rui-yuan,Zhang Tong,Yang Xiao-dong,Yan Yi-chen,Qu Jin-qing
A novel phenylacetylene derivative containing urea groups was synthesized and polymerized with a Rh catalyst to give the corresponding polymer, poly( 1 ) with moderate number-average molecular weights. The poly( 1 ) was soluble in toluene, CHCl 3 , CH 2 Cl 2 , THF, DMF, and DMSO, but insoluble in hexane, diethyl ether and MeOH. The specific rotation and circular dichroism (CD) spectroscopic studies revealed that poly( 1 ) took predominantly one-handed helical structures. The presence of intramolecular hydrogen bonding was confirmed by liquid-state IR spectroscopy. The helicity of poly( 1 ) could be tuned by temperature and anion. The helical conformation of the polymer was stable against Br- but susceptible to F − .
研究领域:
有机化学
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高分子化学
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产品关联
DOI
高影响因子
RSC Advances
·
2015
·Vol. 5
·期 33
·26236-26245
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IF 3.84
Huajun Huang,Wantai Yang,Jianping Deng
Microparticles simultaneously showing optical activity and fluorescence were prepared based on fluorescent, optically active helical polymers. Chiral and fluorescent substituted acetylene monomers (L- and D-CFM) were synthesized and then underwent precipitation polymerization in a solvent mixture of CHCl3/n-heptane in the presence of a Rh catalyst at room temperature. The CHCl3/n-heptane mixture at a suitable ratio provided spherical microparticles (L- and D-CFMPs) with uniform diameters of 910 nm in a high yield (ca. 90 wt%). The microparticles were comprised of polymer chains (number-average molecular weight, 8700 g mol−1) that were found to adopt chiral helical structures, according to circular dichroism and UV-vis absorption spectroscopy. The fluorescence property was measured using fluorescent microscopy and spectroscopy. Remarkably, the novel microparticles exhibited enantioselective recognition ability towards alanine and phenylethylamine enantiomers. However, L- and D-CFMPs behaved differently in the enantioselective recognition processes. Possible mechanisms were proposed for the observed enantioselective recognition.
研究领域:
材料科学
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化学
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产品关联
DOI
高影响因子
REACTIVE & FUNCTIONAL POLYMERS
·
2015
·
IF 2.515
Chunyu Zhang,Yu Zhang,Hexin Zhang,Yanming Hu,Xuequan Zhang,Toshio Masuda
Acetylenic monomers containing salicylidene Schiff-base groups ( 1a and 1b ) as well as Schiff-base and hydroxy groups ( 1c ) were synthesized and polymerized with [(nbd)RhCl] 2 /Et 3 N catalyst to afford the corresponding polymers 2a – c with high molecular weights ( M n = 2.6–7.2 × 10 5 ) in high yields (75–97%). Polarimetric, circular dichroism (CD), and UV–vis spectroscopic analyses indicated that the polymers formed helical structures with a predominantly one-handed screw sense. The addition of metal ions to salicylidene Schiff-base-containing polymers 2a and 2b produced insoluble polymer/metal complexes through ionic cross-linking as a result of salicylaldimine–metal ion complexation. Polymers 2b and 2c underwent a helix–coil transition upon the addition of HSO 4 − , whereas these polymers did not exhibit responsiveness to other anions, such as F − , Cl − , and Br − .
研究领域:
高分子化学
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材料科学
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有机化学
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产品关联
DOI
高影响因子
Nanoscale Advances
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2020
·Vol. 2
·期 3
·1301-1308
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IF 0
Jiali Yang,Pengpeng Li,Biao Zhao,Kai Pan,Jianping Deng
Chirality is ubiquitous in nature and closely related to the pharmacological effects of chiral drugs. Therefore, chiral recognition of molecular enantiomers becomes an important research theme. Fluorescence detection is highly sensitive and fast but has achieved only limited success in enantiomeric detection due to the lack of powerful chiral fluorescence detection materials. In this paper, a novel chiral fluorescent probe material, i.e. a chiral fluorescent nanofiber membrane, is prepared from chiral helical substituted polyacetylene by the electrospinning technique. The SEM images demonstrate the success in fabricating continuous, uniform nanofibers with a diameter of about 100 nm. Circular dichroism spectra show that the nanofibers exhibit fascinating optical activity. One of the enantiomeric chiral fluorescent membranes has chiral fluorescence recognition effects towards alanine and chiral phenylethylamine, while the other enantiomeric membrane does not. The prepared chiral fluorescent nano-materials are expected to find various applications in chirality-related fields due to their advantages such as chirality, fluorescence, and a high specific surface area. The established preparation approach also promises a potent and versatile platform for developing advanced nanofiber materials from conjugated polymers.
研究领域:
材料科学
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光学
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生物化学
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DOI
PubMed
REACTIVE & FUNCTIONAL POLYMERS
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2015
·
IF 2.515
Jiexuan Song,Haiyang Zhang,Jianping Deng
This article reports on the preparation of a novel category of optically active magnetic microspheres (OAMMPs) consisting of Fe 3 O 4 nanoparticles and helical substituted polyacetylene bearing pendent prolineamide groups and the use of them for asymmetric direct Aldol reactions. The microspheres (200–300 μm in diameter) were prepared by using chiral acetylenic monomer and alkynyl-Fe 3 O 4 nanoparticles via suspension polymerization approach. They were obtained in high yield (> 99%) with regular spheric morphology and exhibited noticeable optical activity, according to circular dichroism spectra and specific optical rotation measurements. The microspheres further served as chiral catalyst for performing direct Aldol reactions between acetone and p -nitrobenzaldehyde, providing the product in moderate yield (68%) and ee (75%). The magnetic microspheres can be easily recycled and reused. Mechanism for the asymmetric catalysis of Aldol reaction was further proposed.
研究领域:
材料科学
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有机化学
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催化化学
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产品关联
DOI
高影响因子
REACTIVE & FUNCTIONAL POLYMERS
·
2014
·
IF 2.822
Xiaohai Bu,Yuming Zhou,Zhenjie Chen,Man He,Tao Zhang
Chiral amino acid-based monosubstituted acetylene monomers [ N - tert -butoxy-carbonyl- l -phenylalanine- N ′-propargylamide (LP), and N - tert -butoxycarbonyl- l -serine- N ′-propargylamide (LS)] were (co)polymerized with rhodium zwitterion catalyst in THF to afford helical polyacetylenes (PAs) with moderate molecular weights (4400–14,800) in good yields. The optically active PA copolymers were soluble in common organic solvents and proven to adopt predominately single-handed helical conformations according to their intense Cotton effect and large specific rotations. Various contents of amino acid units in side chains facilitated controllable helical secondary structure while the helix was primarily stabilized by hydrogen bonding and steric repulsion between the substituents. Intramolecular hydrogen bonds constructed between hydroxyl and amide groups, in particular, played a significant role in adjusting the helicity and orderliness of the helix. The infrared emissivity values of the PAs at wavelength of 8–14 μm were measured and the correlation between helical conformations and their effect on infrared emission were systematically investigated. The results showed that more well-ordered and compact screw-sense could enhance the performance of organic polymers in lowering their infrared emissivity. Among all the as-prepared PAs, poly(LP 50 - co -LS 50 ) exhibited the lowest infrared emissivity value ( ε 25 = 0.632) and possessed excellent resistance against heat.
研究领域:
高分子化学
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材料科学
·
光学
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产品关联
DOI
高影响因子
JOURNAL OF APPLIED POLYMER SCIENCE
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2014
·Vol. 132
·期 1
·
IF 1.64
Xiaohai Bu,Yuming Zhou,Tao Zhang,Man He,Yongjuan Wang
Serine-based monosubstituted acetylene monomers were synthesized and polymerized with rhodium zwitterion catalyst in THF to afford optically active polyacetylene derivatives (LPA and DPA) and corresponding racemic polyacetylenes (RPA) with moderate molecular weights in good yields. All of the substituted polyacetylenes (SPA) were characterized by FT-IR, NMR, GPC, UV-Vis spectroscopy, circular dichroism (CD) spectroscopy, and TGA. LPA and DPA were soluble in common organic solvents and possessed single-handed helical conformation according to their intense Cotton effect and large specific rotations, while RPA presented random coiled polymer chain. The characterization results showed that helical structure of these SPAs was stabilized by intra- and intermolecular hydrogen bonding between the substituents which played a significant role in creating and maintaining the helix. Further, the infrared emissivity properties of them at wavelength of 8 to 14 μm were investigated at room temperature. Consequently, the LPA and DPA exhibited lower infrared emissivity values than RPA, which came down to 0.632 and 0.616. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132 , 41210.
研究领域:
有机化学
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材料科学
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光谱学
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DOI
高影响因子
JOURNAL OF MATERIALS SCIENCE
·
2019
·Vol. 54
·期 22
·14243-14254
·
IF 3.442
Wu Wenting,Zhou Yuming,Xu Ran,Hu Saichun,Wu Yangjin,He Qiang,He Man,Bu Xiaohai,Nan Qiuli,Yang Xiaoming
The first snail shell-shaped helical polyacetylenes (SHPAs) were synthesized from the copolymerization between l -serine-grafted propargylamine (LSA) and propargylamine (PA). The novel structure was obtained at the monomer input proportion of 50%. The monomer (LSA) and copolymers (poly(LSA m - co -PA n )) were characterized by 1 H nuclear magnetic resonance, Fourier transform infrared spectroscopy, ultraviolet visible spectroscopy, circular dichroism and transmission electron microscopy. The infrared emissivity of poly(LSA 50 - co -PA 50 ) investigated at 8–14 μm was 0.451, which was much lower than the other copolymers. This was because the poly(LSA 50 - co -PA 50 ) could form the obvious intramolecular interaction and self-assembled to a snail-shell shape by intermolecular hydrogen bonding in MeOH solution. Meanwhile, the conjugation performance of the main chain was enhanced. Consequently, the abundant hydrogen bonds formed through N–H and C=O bonding and the strong conjugate properties both could decrease the unsaturation degree, as well as change the heat conduction mode in the molecules, thereby reducing the infrared emissivity. This strategy provided a new direction to achieve the controllable infrared stealth.
研究领域:
材料科学
·
化学
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产品关联
DOI
高影响因子
RSC Advances
·
2019
·Vol. 9
·期 21
·11986-11995
·
IF 3.049
Tianhang Luo,Xuebing Xu,Maoqiang Jiang,Ying-zhou Lu,Hong Meng,Chun-xi Li
Polyacetylene (PA) was synthesized for the first time under mild conditions via polymerization of acetylene in n-octane with AlCl3 as a catalyst, whereby a series of PA-derived carbon materials were obtained. Their composition and structure were characterized and their electrochemical performance was evaluated systematically. It is found that acetylene gas at 1 MPa can polymerize explosively at room temperature under catalysis of AlCl3, forming acetylene black-like PA and a great amount of H2, while in the presence of n-octane solvent, acetylene polymerizes smoothly at higher temperature (30 to 300 °C), forming PA with a H(CHCH)nH structure. A series of PA-derived carbon materials are obtained by treating PA with KOH at 800 °C. The as-synthesizzed PA-100–KOH exhibits a high specific surface area (∼2500 m2 g−1), high specific capacitance (241 F g−1 at a current density of 0.1 A g−1 and 143 F g−1 at 5 A g−1), low AC resistance, and good cycling stability with 91.7% maintenance of capacity after 2000 cycles at a current density of 2 A g−1. This paper provides a new method for the facile synthesis of PA and a novel carbon source for supercapacitor electrode materials with excellent electrochemical performance and practical application.
研究领域:
材料科学
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电化学
·
能源存储
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产品关联
DOI
PubMed
高影响因子
JOURNAL OF SOLID STATE CHEMISTRY
·
2014
·
IF 2.2
Xiaohai Bu,Yuming Zhou,Tao Zhang,Yongjuan Wang,Zewu Zhang,Man He
Optically active substituted polyacetylene@multiwalled carbon nanotubes (SPA@MWCNTs) nanohybrids were fabricated by wrapping helical SPA copolymers onto the surface of modified nanotubes through ester bonding linkage. SPA copolymer based on chiral phenylalanine and serine was pre-polymerized by a rhodium zwitterion catalyst in THF , and evidently proved to possess strong optical activity and adopt a predominately one-handed helical conformation. Various characterizations including Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and transmission electron microscopy (TEM) demonstrated that the SPA had been covalently grafted onto the nanotubes without destroying their original graphite structure. The wrapped SPA was found to exhibit an enhancement in thermal stability and still maintained considerable optical activity after grafting. The infrared emissivity property of the nanohybrids at 8–14 μm was investigated in addition. The results indicated that the SPA@MWCNTs hybrid matrix could possess a much lower infrared emissivity value ( ε =0.707) than raw MWCNTs, which might be due to synergistic effect of the unique helical conformation of optically active SPA and strengthened interfacial interaction between the organic polymers and inorganic nanoparticles .
研究领域:
材料科学
·
高分子化学
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产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）