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Chinese Journal of Chemical Engineering 2024年第5期69卷 13-22页

作者： Tong Liu Hao Sun Xiangqiong Wang Jie Li Zhanquan Zhang Pei Wu Naixin Wang Quanfu An Beijing Key Laboratory for Green Catalysis and Separation Department of Chemical EngineeringCollege of Materials Science and EngineeringBeijing University of TechnologyBeijing 100124China Petrochemical Research Institute CNPCBeijing 102206China

The separation of aromatic/aliphatic hydrocarbon mixtures is crucial in the petrochemical industry.Pervaporation is regarded as a promising approach for the separation of aromatic compounds from alkanes. Developing membrane materials with efficient separation performance is still the main task since the membrane should provide chemical stability, high permeation flux, and selectivity. In this study, the hyperbranched polymer(HBP) was deposited on the outer surface of a polyvinylidene fluoride(PVDF)hollow-fiber ultrafiltration membrane by a facile dip-coating method. The dip-coating rate, HBP concentration, and thermal cross-linking temperature were regulated to optimize the membrane structure.The obtained HBP/PVDF hollow-fiber-composite membrane had a good separation performance for aromatic/aliphatic hydrocarbon mixtures. For the 50%/50%(mass) toluene/n-heptane mixture, the permeation flux of optimized composite membranes could reach 1766 g·m^(-2)·h^(-1), with a separation factor of 4.1 at 60℃. Therefore, the HBP/PVDF hollow-fiber-composite membrane has great application prospects in the pervaporation separation of aromatic/aliphatic hydrocarbon mixtures.

关键词： Aromatic/aliphatic hydrocarbons hyperbranched polymer Pervaporation Hollow fiber membrane Dip-coating

Carbon nanofibers membrane bridged with graphene nanosheet and hyperbranched polymer for high-performance osmotic energy harvesting

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Nano Research 2023年第1期16卷 1205-1211页

作者： Weijie Wang Jinlin Hao Qian Sun Minqi Zhao Huiyi Liu Chao Li Xin Sui College of Materials Science and Engineering Qingdao UniversityQingdao 266071China Laboratory of Bio-Inspired Smart Interfacial Science and Technology of Ministry of Education Key Laboratory of Beijing EnergySchool of Chemistry and EnvironmentBeihang UniversityBeijing 100191China

Reverse electrodialysis(RED),based on ion-selective membranes,is one of the most promising technologies for capturing osmotic energy.As key elements of the RED system,ion-selective membranes must meet the crucial demands of mechanical stability,anti-fouling characteristics,easy fabrication,and high power density;however,this still remains a challenge.In this study,we demonstrated a large-scale,mechanically stable,and high-porosity membrane obtained by combining carbon nanomaterials and hyperbranched polyethyleneimine(h-PEI),thereby achieving a high power density of 5.0 W·m−2 with seawater and river water.Carbon nanofibers(CNFs)were subsequently bridged with graphene and h-PEI to strengthen the interaction between the CNFs,reduce the channel size and increase the space charge density,mechanical strength,and toughness.The large-scale and mechanically stable membrane fabricated using the modified CNFs exhibited anion selectivity and high ionic conductivity,thereby achieving a high-performance osmotic energy conversion.Furthermore,the anti-fouling property of the membrane was confirmed by the stability of the osmotic energy conversion in a solution with algae,which can be attributed to the high porosity of carbon nanomaterials.This economic and convenient method for the ion-selective membrane preparation is believed to be promising for large-scale osmotic energy harvesting.

关键词： carbon nanofibers graphene nanosheet bridged structure hyperbranched polymer osmotic energy harvesting

Fluorescent traceable nanoparticles by co-self-assembly of carbon dot-drug conjugate and biodegradable hyperbranched polymer for diagnosis and therapy

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Particuology 2022年第3期20卷 79-87页

作者： Guoping Li Mingliang Pei Xinming Li Peng Liu State Key Laboratory of Applied Organic Chemistry College of Chemistry and Chemical EngineeringLanzhou UniversityLanzhou 730000China

Carbon dots(CDs)have attracted more interest in tumor theranostics,but they suffer from the rapid renal clearance due to small size and high hydrophilicity.To solve such problems,hydrophobic pH-triggered carbon dot-drug conjugate(CDs-Hy-DOX)with high doxorubicin(DOX)content of 48.23%were designed by covalent conjugation of DOX onto the CDs via acid-labile linkage with hydrazine(Hy)as bridge.Then the fluorescent traceable hybrid prodrug nanoparticles were fabricated via co-self-assembly with the CDs-Hy-DOX as pH-sensitive prodrug and a pH/reduction dual-triggered degradable hyperbranched polymer PEG-PO-Cy as polyethylene glycol(PEG)-based surfactant,as well as gatekeeper for pH/reduction dual-triggered DOX release.The hybrid prodrug nanoparticles with hydrodynamic diameter of 220 nm and DOX content of 22.99%were obtained with the optimized co-self-assembling condition.They could release 68.98%of DOX in the simulated tumor microenvironment within 3 days in a sustained release mode,with a premature drug leakage of 7.58%.After the acid-triggered DOX release from the CDs-Hy-DOX,which was accelerated by the pH/reduction dual-triggered degradation of the hyperbranched polymer,the strong fluorescence of CDs-Hy was recovered,demonstrating the promising potential in future tumor nanotheranostics.

关键词： Tumor nanotheranostics Carbon dots hyperbranched polymer Tumor-specific Fluorescent imaging

A hyperbranched polymer-based water-resistant adhesive:Durable underwater adhesion and primer for anchoring anti-fouling hydrogel coating

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Science China(Technological Sciences) 2022年第1期65卷 201-213页

作者： ZHANG YaHan CUI ChunYan SUN YaGe ZHANG XiaoPing YANG Rong YANG JianHai XIE Fei LIU WenGuang School of Materials Science and Engineering Tianjin UniversityTianjin 300350China Shandong Zhushi Pharmaceutical Group Co. Lid.Heze 274300China

Direct deployment of gluing and achieving durable robust adhesion in water is challenging due to difficulty in repelling interface water.This work reports a novel hyperbranched polymer-based water-resistant adhesive(HBPBA)based on Michael addition reaction of multi-vinyl monomers with dopamine and 3-aminophenylboronic acid.Upon encountering water,the HBPBA forms coacervates whose hydrophobic chains aggregate to displace interface water,and meanwhile the catechols exposing outwards contribute to underwater adhesion.The HBPBA can strongly glue diverse substrates including PTFE,PE,PET,ceramic,Ti and stainless steel.The HBPBA can maintain stable adhesion in different environments,such as tap water,simulated sea water,PBS,and a wide range of pH solutions(pH 2 to 10)for 3 months,supposedly due to the complexation of catechol with boronic acid.Intriguingly,HBPBA film can be bonded to the titanium surface as a primer,which firmly anchors the antifouling PNAGAPCBAA hydrogel coating through copolymerization of remaining double bonds in HBPBA and NAGA plus CBAA.The PNAGA-PCBAA hydrogel-modified titanium is biocompatible and shows outstanding antifouling ability both in vitro and in vivo.This work proposes a new strategy for creating underwater deployable and water-resistant adhesives that may find promising applications in engineering and biomedical fields.

关键词： hyperbranched polymer adhesive anti-fouling hydrogel underwater adhesion

hyperbranched polymer micelles with triple-stimuli backbone-breakable iminoboronate ester linkages

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Chinese Chemical Letters 2020年第7期31卷 1822-1826页

作者： Xuan Zhang Jushan Gao Xiaoye Zhao Zhaotie Liu Zhongwen Liu Ke Wang Guo Li Jinqiang Jiang Key Laboratory of Syngas Conversion of Shaanxi Province Key Laboratory of Applied Surface and Colloid ChemistryMinistry of EducationSchool of Chemistry and Chemical EngineeringShaanxi Normal UniversityXi'an 710062China School of Pharmacy Health Science CenterXi'an Jiaotong UniversityXi'an 710061China

hyperbranched polymers have attracted increasing interests due to their unique structure-related advantages and have been utilized as drug carriers for controlled delivery.However,it is still challenging to prepare multi stimuli-responsive hyperbranched polymers to sense and response the complex yet delicate changes in physiological environment.Herein,we propose a triple-stimuli backbone-breakable hyperbranched polymer(HBP(OEG-IB)),which is prepared via the convenient iminoboronate multicomponent reaction ofα,ω-di(1,2-diol)s oligo(ethylene glycol),tris(3-aminopropyl)amine and 2-formylphenylboronic acid.Upon the stimulation of CO2,lactic acid and glutathione,micelles formed by HBP(OEG-IB)could be disrupted via the dissociation of iminoboronate ester bond to subsequent release incorporated camptothecin(CPT).Cell experiments show that the HBP(OEG-IB)is non-toxic but can enhance the therapeutic effect of CPT thanks to the effect of the protonated tertiary amino groups.The demonstration made in this work can enrich the design of responsive HBPs and can be readily applied to other systems with tunable responsive properties and functions.

关键词： hyperbranched polymer Multi-stimuli responsiveness Iminoboronate esters CPT Drug delivery

hyperbranched polymer surfactant: synthesis, characterization and surface tension activity

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Journal of Leather Science and Engineering 2021年第1期3卷 82-92页

作者： Longfang Ren Zheng Tang Taotao Qiang Guoguo Zhang College of Bioresources and Materials Engineering Shaanxi University of Science&TechnologyXi’an 710021China National Demonstration Center for Experimental Light Chemistry Engineering Education(Shaanxi University of Science&Technology) Xi’an 710021China

A series of hyperbranched polymer surfactants(HBP-C8,HBP-C12 and HBP-C16)were synthesized by the reaction between hydroxyl-terminated hyperbranched polymers(HBP)and fatty acyl chloride.The structure of obtained hyperbranched polymer surfactant was characterized by FTIR,NMR and GPC.The results showed that the products have amphiphilic structure.The thermal property of the hyperbranched polymer surfactant investigated by DSC and TGA was strongly influenced by the length of end alkyl chain.Surface activity of hyperbranched polymer surfactant was analyzed by surface tension method and UV spectrophotometry,respectively.The results showed that hyperbranched polymer surfactant took on better surface activity,which can effectively reduce the surface tension of the water.The hyperbranched polymer surfactant has a lower critical micelle concentration(CMC)and displays single molecular micellar properties,which can package small hydrophilic molecules in relatively low concentration.

关键词： Fatty acid chloride hyperbranched polymer Surface tension CMC

SECOND-ORDER NONLINEAR OPTICAL hyperbranched polymer CONTAINING ISOLATION CHROMOPHORE MOIETIES DERIVED FROM BOTH “H”-TYPE AND STAR-TYPE CHROMOPHORES

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Chinese Journal of polymer Science 2013年第10期31卷 1415-1423页

作者： Wen-bo Wu Ying-jie Fu Can Wang Zhen Xu Cheng Ye Jin-gui Qin Zhen Li Department of Chemistry Hubei Key Lab on Organic and Polymeric Opto-Electronic MaterialsWuhan University Key Laboratory of Organic Solids Institute of Chemistry Chinese Academy of Sciences

An NLO hyperbranched polymer （HP1） derived from both ＂H＂-type and star-type chromophores was synthesized successfully for the first time with high yield via one-pot ＂A2 ＋ B3＂ Suzuki polymerization reaction. Isolation chromophore was also introduced to further improve its performance. Although under the test conditions, the films of HP1 could not be poled completely, it still demonstrated satisfactory macroscopic NLO effect with the second harmonic generation （SHG） coefficient d33 value of 36 pm/V.

关键词： hyperbranched polymer NLO Isolation chromophore ＂H＂-type chromophore Star-type chromophore.

A FUNCTIONAL CONJUGATED hyperbranched polymer DERIVED FROM TETRAPHENYLETHENE AND OXADIAZOLE MOIETIES:SYNTHESIS BY ONE-POT “A_4+B_2+C_2” polymerIZATION AND APPLICAION AS EXPLOSIVE CHEMOSENSOR AND PLED

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Chinese Journal of polymer Science 2013年第10期31卷 1432-1442页

作者： Wen-bo Wu Shang-hui Ye Li-jin Huang Gui Yu Yun-qi Liu Jin-gui Qin Zhen Lia Department of Chemistry Hubei Key Lab on Organic and Polymeric Opto-Electronic MaterialsWuhan University Key Laboratory of Organic Solids Institute of Chemistry Chinese Academy of Sciences

A new conjugated hyperbranched polymer （hb-TFO） containing tetraphenylethylene （TPE） units, a famous aggregation-induced emission （AIE） active group, as the core, was synthesized successfully with modest yield via one-pot Suzuki polymerization reaction. Thanks to the introduction of TPE moieties, hb-TFO exhibited aggregation-enhanced emission （AEE） property, and could work as explosive chemosensor with high sensitivity. The polymeric light-emitting diode （PLED） device was fabricated to investigate its electroluminescent property, and hb-TFO demonstrated a maximum luminance efficiency of 0.22 cd/A and a maximum brightness of 545 cd/m2 at 15.9 V.

关键词： hyperbranched polymer AEE TPE Explosive chemosensor PLED.

Enhancing the long-term Na-storage cyclability of conversion-type iron selenide composite by construction of 3D inherited hyperbranched polymer buffering matrix

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Nano Research 2021年第11期14卷 3952-3960页

作者： Hao Li Changchun Hu Yaping Xia Ting Li Daohong Zhang Fei Xu Key Laboratory of Catalysis and Energy Materials Chemistry of Ministry of Education&Hubei Key Laboratory of Catalysis and Materials Science Hubei R&D Center of Hyperbranched Polymers Synthesis and ApplicationsSchool of Chemistry and Materials ScienceSouth-Central University for NationalitiesWuhan430074China Key Laboratory of Hydraulic Machinery Transients Ministry of EducationSchool of Power and Mechanical EngineeringWuhan UniversityWuhan430072China

Electrochemical conversion reactions provide more selections for Na-storage materials, but the reaction suffers from low reversibility and poor cyclability. Introducing an electrochemically inactive component is a common strategy, but the effect is quite limited since it could not stabilize the structure during long-term cycling. In this study, a new approach is developed using an amino group-functioned hyperbranched polymer (AHP) as a template and electrode additive for the design of high-performance FeSe2-AHP composite with chemical interaction. The assembled FeSe2-AHP composite nanoneedles were prepared by the selenylation of FeS-AHP composite microflowers and entirely inherit the polymer network from the precursor. The amino groups of AHP in composite coordinate with iron cations to achieve uniform polymer dispersion in the composite, and maintain the molecular level mixed state during the long-term cycling. Moreover, the in-situ constructed uniform 3D elastic polymer network effectively accommodates volume expansion and alleviates nanoparticle aggregation during sodiation/de-sodiation. FeSe2-AHP composite provides a superior rate capability (584.8 mAh·g−1 at 20 A·g−1) and a remarkable cyclability with a capacity retention rate of 93.3% after 2,000 cycles. FeSe2-AHP composite shows a high pseudocapacitive behavior for the abundant nanometer interface established by AHP, enhancing the solid-state Na+ diffusion. The FeSe2-AHP anode is also compatible with Na3V2(PO4)3/C cathode in a full Na-ion battery, which provides a high-power performance (powering 51 LEDs). The work herein highlights an innovative and efficient strategy for conversion-type material design and demonstrates the function of chemical interaction of polymer additive in the enhancement of long-term cyclability for conversion electrode.

关键词： Na-ion batteries conversion materials hyperbranched polymer iron selenide chemical interaction

Convenient Synthesis and Enhanced Second-order Nonlinear Optical Property of a Novel hyperbranched polymer

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Chinese Journal of Chemistry 2007年第2期25卷 237-240页

作者：朱志超李忠安李倩倩曾琪李振叶成秦金贵 Hubei Key Laboratory on Organic and polymeric Opto-electronic Materials Department of Chemistry Wuhan University Wuhan Hubei 430072 China Organic Solids Laboratories Institute of Chemistry Chinese Academy of Sciences Beijing 100080 China

A novel hyperbranched polymer （3） was prepared by copolymerization of tri-aldehyde moieties with azo chromophores having two active methelene groups, from ＂A2＋B3＂ approach based on simple Kneovenagel reaction. For comparison, its analogue linear polymer （5） was also synthesized. The two polymers are soluble in common organic solvents, and exhibit good thermal stability. Interestingly, the hyperbranched polymer demonstrates dramatically enhanced second-order nonlinear optical property with comparison to its linear analogue.

关键词： hyperbranched polymer nonlinear optical material Kneovenagel reaction