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Journal of Materials Chemistry C · 2021 ·Vol. 10 ·期 3 ·1010-1016 · IF 7.393

Transforming polyethylene and polypropylene into nontraditional fluorescent polymers by thermal oxidation

Yaxin Zhao,Jiayu Long,Peifeng Zhuang,Ying Ji,Changcheng He,Huiliang Wang

Polyolefins like polyethylene (PE) and polypropylene (PP) without any conventional or nonconventional fluorescent chromophores have never been considered as raw materials for the preparation of fluorescent polymers. Here we report that PE and PP can be transformed into nontraditional luminescent polymers (NLPs) with strong fluorescence emissions by a simple thermal oxidation method. The maximum excitation and emission wavelengths of PE and PP oxidized products generally firstly increase with the increase of heating temperature and time, and then decrease. In addition, the oxidized products also exhibit significant excitation-dependent fluorescence (EDF) characteristics. Oxygen-containing nonconventional chromophores like hydroxyl, carbonyl and ester groups are proven to be formed in the PE and PP oxidized products. The formation of extended through-space n–π* and π–π* interactions among the nonconventional chromophores leads to the fluorescence emissions. Fluorescence emissions can also be introduced onto PE and PP surfaces by fast flame burning, and its application in anti-counterfeiting is demonstrated. This work is of great scientific importance in understanding the origin of fluorescence and will have an important impact on the development and practical applications of fluorescent materials.

CAS / MDL: 9003-07-0
研究领域: 材料科学 · 化学 · 光学材料
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PROGRESS IN ORGANIC COATINGS · 2021 · IF 5.161

Two hydrogen donor-containing naphthalimide benzyl thioether photoinitiators for LED photopolymerization

Xiaobing Ju,Xiuyuan Hu,Yanjing Gao,Jun Nie,Fang Sun

This work reports two hydrogen donor-containing naphthalimide benzyl thioether photoinitiators (NBT-HD1 and NBT-HD2), combining characters of one-component and two-component photoinitiators, for LED photopolymerization . They have good absorptions at emission wavelengths of LED and their ɛ max are more than or close to 1 × 10 4  M −1  cm −1 . Both photoinitiators can generate radicals having initiating ability through not only the cleavage of C S bonds, but also intermolecular hydrogen abstractions themselves under 405 nm LED irradiation. NBT-HD2 with acryloyl group presents an excellent capability of reducing oxygen inhibition. Moreover, NBT-HD1 or NBT-HD2/iodonium salt can trigger the cationic photopolymerization of the epoxide under 405 nm LED irradiation. More significantly, NBT-HD2 with acryloyl group exhibits a prominent migration stability in the polymer film and has broad application prospects in the field of food packaging and biomaterials.

CAS / MDL: 6258-60-2
研究领域: 材料科学 · 化学工程 · 高分子化学
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FIBERS AND POLYMERS · 2017 ·Vol. 18 ·期 9 ·1644-1651 · IF 1.113

Different photoinitiating ability and photobleaching efficiency of erythrosine B derivatives in radical/cationic photopolymerization

Nan Xuying,Huang Yi,Fan Qinguo,Shao Jianzhong,Yao Yuhua

A series of erythrosine B derivatives with a linked coinitiator on different position, combined with iodonium salt and/or tertiary amine were used to initiate free radical/cationic photopolymerization. Their photoinitiating ability and photobleaching behaviors were investigated and compared with those of the systems containing separated counterparts. The polymerization results showed that compared to the systems containing separated counterparts, the systems containing derivatives with a linked coinitiator on carboxyl group exhibited higher photoinitiating ability in radical photopolymerization, but had poorer one in cationic polymerization. Simultaneously, in free radical/cationic polymerizations, these linked derivatives could be photobleached more efficiently than the separated one, due to fast intramolecular reaction, which was especially significant for the industrial application. Besides, it was found that the investigated systems were photobleached more efficiently in cationic photopolymerization than in radical one. These results will provide useful information for designing effective photoinitiators for different polymerization.

CAS / MDL: 13048-33-4
研究领域: 高分子科学 · 光化学 · 材料科学
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COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS · 2024 · IF 4.9

Robust photopolymerized superoleophobic/superhydrophilic mesh for oil-water separation

Jian Wang,Feiran Li,Yunlu Pan,Fang Chen,Cong Huang,Xuezeng Zhao

Selective superwetting surfaces preserve the opposite superwetting properties of oil and water and have attracted considerable attention for their application in oil-water separation owing to their efficient surface energy since 2000. Among these surfaces, superoleophobic/superhydrophilic surfaces are considered remarkable because of their anti-oil properties. The coexistence of superoleophobicity and superhydrophilicity poses a challenge based on the traditional surface/interface theory. However, the fabrication of superoleophobic surfaces requires extremely low surface energy, which is achieved by introducing compounds with long fluorocarbon chains. However, these compounds are harmful to the environment. Herein, a mesh with superoleophobic/superhydrophilic properties was developed by coating a chemically etched copper mesh substrate with photopolymerized short fluorocarbon chains and water-insoluble hydrophilic monomers. This mesh can separate different types of oil-water mixtures with a separation efficiency of >99 %. The mesh demonstrated excellent underwater stability as well as chemical and mechanical durability. The water resistance and chemical durability of the mesh are stronger than those of the control copper mesh using metal ions and long fluorocarbon chains. Moreover, oil-water separation was achieved even after immersion in deionized water and salt, acid, and alkali solutions. In addition, the mesh preserves the ability of oil-water separation after being cleaned and reused for 10 times. The proposed superoleophobic/superhydrophilic mesh offers a solution for continuous oil-water separation and has prospects for developing anti-fouling/sweat-absorbing fabrics and self-cleaning surfaces.

研究领域: 材料科学 · 环境科学
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POLYMER ENGINEERING AND SCIENCE · 2018 ·Vol. 58 ·期 12 ·2185-2191 · IF 1.551

Co-initiating function of silk peptide in free radical photopolymerization

Xuying Nan,Yi Huang,Jianzhong Shao,Huiqiong Yan,Mingshu Wu,Yuhua Yao

Silk peptide used as a co-initiator in type 2 photo-initiator has not been known. In this study, the photoinitiation system is composed of the sensitizer, the synergist and silk peptide with low molecular weight (<3,500), which is used to initiate photopolymerization of common monomer. The same photopolymerization was performed to evaluate the co-initiating ability of four essential amino acids of silk peptide, and of four pentapeptides synthesized using them as substrates, respectively. It was suggested that the glycine residue and alanine residue on silk peptide might be mainly responsible for the co-initiating role. And the co-initiating function might be ascribed to the electron/hydrogen donation of silk peptide. Silk peptide combined with the sensitizer and iodonium salt could also efficiently initiate photo-curing of hydrogel precursors. And due to excellent water solubility of silk peptide, the water absorption of the formed hydrogel could be further improved. These studies will open an opportunity for the application of silk peptide as a biocompatible co-initiator. POLYM. ENG. SCI., 58:2185–2191, 2018. © 2018 Society of Plastics Engineers

研究领域: 材料科学 · 生物医学 · 高分子化学
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ANALYTICA CHIMICA ACTA · 2021 · IF 6.558

Flexible fabrication of lipophilic-hydrophilic micromotors by off-chip photopolymerization of three-phase immiscible flow induced Janus droplet templates

Kailiang Zhang,Yukun Ren,Tianyi Jiang,Hongyuan Jiang

Self-propelled microparticles are promising for lots of applications ranging from analytical detection to water treatment . Herein, we present an effective approach to fabricate lipophilic-hydrophilic micromotors via the photocuring of three-phase immiscible flow induced droplet templates. In the microfluidic system, two immiscible inner fluids, the lipophilic 1, 6-Hexanediol diacrylate (HDDA), and the hydrophilic poly (ethylene glycol) diacrylate (PEGDA), are simultaneously injected into a theta-shaped cylindrical capillary from two separate inlets, and they are emulsified into Janus drops when encountering the outer immiscible silicone oil. Because of the immiscible feature of droplet templates, off-chip photopolymerization strategy has been used, which can significantly decrease the blocking chance of microdevice. And also, the lipophilic-hydrophilic structure of droplets is convenient for the loading of cargos with different characteristics. More importantly, the size and configuration of droplet templates can be flexibly regulated by changing the flow rates of three different phases. Accordingly, multifunctional micromotors can be fabricated by adding different nanoparticles and materials into the HDDA or PEGDA phase first and then photocuring the droplets. Taking the bubble-propelled micromotors for example, we prepare microswimmers by loading Ag, TiO 2 and Fe 3 O 4 nanoparticles into the PEGDA phase. The swimming behaviors of micromotors in H 2 O 2 solution are systematically investigated, finding that the proportion of PEGDA phase and the concentration of H 2 O 2 both positively affect the moving speed. Furthermore, the applicability of motor particles on water treatment is successfully demonstrated by using neutral red solution as the model pollutant. And the micromotors can be recycled using magnets after the catalytic degradation process. Therefore, this micromotor generation technique and this kind of micromotor can be attractive for many applications.

研究领域: 材料科学 · 化学工程 · 环境科学
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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2013 · IF 3.172

Magnetic field induced formation of visually structural colored fiber in micro-space

Zhifu Liu,Qinghong Zhang,Hongzhi Wang,Yaogang Li

A new type of photonic crystal structural colored fiber was prepared by assembling superparamagnetic chains on the surface of a flexible fiber in a magnetic field under photopolymerization . In this system, fixed structural colors (blue, green, and red) were generated instantaneously. The fiber with multi-stopband can also be prepared by carefully controlling the size of the magnetic spheres in each photopolymerization procedure. This method would be fast and facile for the further study of structural color on the surface of the fiber, and the process may be used to simulate the conventional fiber coloration process.

CAS / MDL: 24650-42-8
研究领域: 材料科学 · 光学
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ACS Applied Materials & Interfaces · 2018 · IF 8.097

Coumarin-Based Oxime Esters: Photobleachable and Versatile Unimolecular Initiators for Acrylate and Thiol-Based Click Photopolymerization under Visible Light-Emitting Diode Light Irradiation

Zhiquan Li,Xiucheng Zou,Guigang Zhu,Xiaoya Liu,Ren Liu

Developing efficient unimolecular visible light-emitting diode (LED) light photoinitiators (PIs) with photobleaching capability, which are essential for various biomedical applications and photopolymerization of thick materials, remains a great challenge. Herein, we demonstrate the synthesis of a series of novel PIs, containing coumarin moieties as chromophores and oxime ester groups as initiation functionalities and explore their structure–activity relationship. The investigated oxime esters can effectively induce acrylates and thiol-based click photopolymerization under 450 nm visible LED light irradiation. The initiator O-3 exhibited excellent photobleaching capability and enabled photopolymerization of thick materials (∼4.8 mm). The efficient unimolecular photobleachable initiators show great potential in dental materials and 3D printings.

CAS / MDL: 68-12-2 7446-08-4
研究领域: 材料科学 · 化学 · 生物医学工程
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EUROPEAN POLYMER JOURNAL · 2021 · IF 4.598

Fully-water-soluble BODIPY containing fluorescent polymers prepared by RAFT method for the detection of Fe3+ ions

Suyan He,Li Xiao,Luminita Marin,Yike Bai,Xinjian Cheng

The development of water-soluble polymer dyes is of great practical and scientific significance. In this article, small fluorescent molecule boron-dipyrromethene (BODIPY) bearing C=C bond was synthesized first. And then, via Suzuki reaction, recognition groups were introduced into the 2, 6 positions of BODIPY. Thus polymerizable fluorescent monomers were prepared. Finally, methacrylic acid (MAA) was copolymerized with the as-prepared small molecular fluorescent monomers via reversible addition-fragmentation chain transfer (RAFT) polymerization methodology. Four fully-water-soluble polymer sensors with BODIPY moieties in the end of the polymer chain were obtained eventually. In the presence of long PMAA chain, and by the assistance of it, BODIPY could be dissolved totally in water. These polymer sensors exhibited sensitive and selective recognition ability to Fe 3+ . Even the content rate of BODIPY was as low as 0.5% of the polymer (calculated from element analysis), the detection limit could reach 1.2 μM. The sensors with two recognition groups in one BODIPY unit were more sensitive than that with one recognition groups in each BODIPY unit. The sensing mechanism was investigated as well. By endowing the water solubility to organic sensors, the application scope could be greatly enlarged in sensing metal ions in aqueous environments. This work provides a method to develop water soluble high performance polymer sensors.

研究领域: 材料科学 · 化学传感器 · 分析化学
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Additive Manufacturing · 2023 · IF 11

Influence of temperature field on the rheological properties and photopolymerization process of Mg2TiO4 microwave ceramic slurry during vat photopolymerization process

Fei Liu,Hanwei He,Lijin Cheng,Hao Li,Mohsen Abdel-Naeim Hassan Mohamed,Ning Hu,Shaojun Liu

Temperature-field-assisted vat photopolymerization has been applied to prepare Mg 2 TiO 4 ceramics with few defects and remarkably reduced dielectric loss . These excellent properties could be attributed to the significantly reduced viscosity and increased curing depth of the prepared ceramic slurry with a high solid loading when the photopolymerization temperature reaches 65 °С. Increasing the temperature helped to increase the kinetic energy of the resin molecules and reduce the viscosity of the ceramic slurry. This ensured a smooth spreading of the slurry and suppressed the formation of intra-layer defects during the printing process. Additionally, increasing the curing temperature enhanced the activation energy of the free radicals and accelerated the transfer of molecular chains , thereby increasing the polymerization rate and curing depth of the slurry. This reduced the interlayer pores of the Mg 2 TiO 4 green bodies. Thus, Mg 2 TiO 4 ceramic slurry with a high solid loading could be successfully printed by applying a temperature field. Significantly fewer defects were found in Mg 2 TiO 4 ceramics printed with 57.5 vol% solid loading than those in the samples printed with 50 vol% solid loading. The quality factor of Mg 2 TiO 4 ceramics sintered at 1550 °С for 4 h using ceramic slurries with 57.5 vol% solid loading could reach 150,000 GHz when printed at a curing temperature of 65 °С, this value is equivalent to that of dry-pressed ceramics.

CAS / MDL: 13463-67-7 1309-48-4
研究领域: 材料科学 · 化学工程
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Nature Communications · 2022 ·Vol. 13 ·期 1 ·1-10 · IF 17.694

Direct in situ photolithography of perovskite quantum dots based on photocatalysis of lead bromide complexes

Zhang Pingping,Yang Gaoling,Li Fei,Shi Jianbing,Zhong Haizheng

Photolithography has shown great potential in patterning solution-processed nanomaterials for integration into advanced optoelectronic devices. However, photolithography of perovskite quantum dots (PQDs) has so far been hindered by the incompatibility of perovskite with traditional optical lithography processes where lots of solvents and high-energy ultraviolet (UV) light exposure are required. Herein, we report a direct in situ photolithography technique to pattern PQDs based on the photopolymerization catalyzed by lead bromide complexes. By combining direct photolithography with in situ fabrication of PQDs, this method allows to directly photolithograph perovskite precursors, avoiding the complicated lift-off processes and the destruction of PQDs by solvents or high-energy UV light, as PQDs are produced after lithography exposure. We further demonstrate that the thiol-ene free-radical photopolymerization is catalyzed by lead bromide complexes in the perovskite precursor solution, while no external initiators or catalysts are needed. Using direct in situ photolithography, PQD patterns with high resolution up to 2450 pixels per inch (PPI), excellent fluorescence uniformity, and good stability, are successfully demonstrated. This work opens an avenue for non-destructive direct photolithography of high-efficiency light-emitting PQDs, and potentially expands their application in various integrated optoelectronic devices.

研究领域: 材料科学 · 光电技术 · 纳米技术
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POLYMER ENGINEERING AND SCIENCE · 2024 · IF 3.2

Synthesis of the fluorescent polymer containing pyrene and its application in the detection of tea polyphenol

Cuilian Yi,Chunyan Xu,Xiaoyan Zhao,Chenyi Wang,Hengxue Xiang

Tea polyphenol (TP) is used as a food additive to inhibit lipid peroxidation reactions and extend shelf life, but excessive intake can affect the human immune system. Therefore, developing effective TP detection is significant. Here, pyrene-based polyimide (Py-PI) was synthesized by one-step condensation copolymerization. This polyimide possessed excellent solubility and photoluminescence due to the introduction of pyrene-conjugated groups. It could be used as fluorescent probe for TP detection in solution. In addition, Py-PI fluorescent test paper with different morphology were prepared by electrospinning. As the concentration of the spinning solution was 15 wt%, the bead-like porous polymer electrospun membrane displayed excellent surface wettability which could make the water droplet completely penetrate into the sample within 6 min. The fluorescence enhancement phenomenon could be observed for 5 × 10 −6 mg/mL TP solution on Py-PI test paper. Furthermore, interference investigation of pH on test paper indicated that the sample exhibited a relatively stable fluorescence “turn-on” response in acidic conditions. This work provides a convenient and rapid detection of TP antioxidant in the future.

CAS / MDL: 125-20-2
研究领域: 材料科学 · 食品科学 · 分析化学
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