Xinling Wang

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Name: 王新灵; XinLing Wang

Organization: Shanghai Jiao Tong University , China

Department: School of Chemistry and Chemical Engineering

Title: Professor(PhD)

TOPICS

Polymer

Inorganic Chemistry

Organic Chemistry

Rotaxane Diels Alder Reaction

Chemicals
References

A Facile Strategy to Prepare an Enzyme-Responsive Mussel Mimetic Coating for Drug Delivery Based on Mesoporous Silica Nanoparticles

Co-reporter:Chunlin Hu, Ping Huang, Zhen Zheng, Zhibiao Yang, and Xinling Wang

Langmuir June 6, 2017 Volume 33(Issue 22) pp:5511-5511

Publication Date(Web):May 9, 2017

DOI:10.1021/acs.langmuir.7b01316

Surface functional mesoporous silica nanoparticles (MSNs) have been widely used as promosing materials for drug delivery. Herein, we reported a facile strategy to construct MSNs coated by enzyme-resposive polylysine-dopamine (PLDA) films through self-polymerization of dopamine derivative lysine-dopamine, in which the drug could be loaded and delivered efficiently. In detail, RhB or DOX was used as a drug model and loaded in functional MSNs via a one-pot procedure among MSNs, drug, and lysine-dopamine (LDA) under basic conditions. Owing to the fact that the peptide bonds between lysine and dopamine can be cleaved under triggering by pepsin, the resulting RhB/DOX@PLDA-MSNs exibit enzyme-responsive characterization. After the DOX@PLDA-MSNs enter into the cancer cells, the drug can be released effectively through degradation of peptide bonds under the influence of enzyme in cancer cells, which shows marked anticancer activity in vitro. This facile strategy may provide a new platform to construct enzyme-responsive controlled drug delivery systems.

Mixed polycarbonate prodrug nanoparticles with reduction/pH dual-responsive and charge conversional properties

Co-reporter:Lin Yu, Songwei Tan, Zhao Li, Zhen Zheng, Linzhu Zhou, Yue Su, Xinling Wang

Reactive and Functional Polymers 2017 Volume 120(Volume 120) pp:

Publication Date(Web):1 November 2017

DOI:10.1016/j.reactfunctpolym.2017.09.009

To build a multifunctional and biodegradable drug delivery system, positively and negatively charged functional polycarbonates (PCs) were synthesized and then assembled into nanoparticles (NPs) in pH 7.4 PBS via electrostatic and hydrophobic interaction. Hydrazone linked doxorubicin (DOX) and disulfide functional groups were conjugated to the propargyl-functional PC to achieve the positive PC, PC(Arss-N(CH3)2-DOX). In pH 7.4 PBS, the positive PCs could form charged NPs with reduction/pH dual sensitive behaviors. The negative PCs, poly(ethylene glycol)-block-1,2-dicarboxylic-cyclohexene anhydride modified amino polycarbonate (PEG-PCDCA) and PCDCA, were used to modulate the size/size distribution of the prodrug NPs and strengthen the blood circulation ability of the NPs. The surface nature of NPs could change from negative in physical pH to positive at tumor extracellular pH (pHe). In vitro study showed that the NPs could exhibit effective cellular uptake, intracellular drug release, and obvious cytotoxicity against Hela tumor cells. All these indicated that the NPs would be a potential for the anti-tumor drug delivery system.

Bilayered polyurethane/dipole–dipole and H-bonding interaction reinforced hydrogels as thermo-responsive soft manipulators

Co-reporter:Haiyan Jia;Zhangjun Huang;Zhaofu Fei;Paul J. Dyson;Zhen Zheng

Journal of Materials Chemistry B 2017 vol. 5(Issue 41) pp:8193-8199

Publication Date(Web):2017/10/25

DOI:10.1039/C7TB02028G

Dipole–dipole and hydrogen-bonding interaction reinforced (DHIR) hydrogels that demonstrate both excellent thermo-responsive volume change and high mechanical strength have been developed. Their thermo-responsive volume change originates from the balance between the temperature-sensitive reversible dipole–dipole and H-bonding interaction and an embedded super-hydrophilic component. By integrating these thermal responsive DHIR hydrogels with non-swelling polyurethane (PU) hydrogels, bilayered (DHIR-PU) thermomorphic actuators capable of shape transformation have been fabricated. The hybrid DHIR-PU hydrogels have a wide temperature window allowing dual-responsive actuations to be achieved. The new hydrogel-based actuators are highly attractive materials for a range of transformative applications in soft robotics, medical devices and advanced manufacturing.

Unconventional Tough Double-Network Hydrogels with Rapid Mechanical Recovery, Self-Healing, and Self-Gluing Properties

Co-reporter:Haiyan Jia, Zhangjun Huang, Zhaofu Fei, Paul J. Dyson, Zhen Zheng, and Xinling Wang

ACS Applied Materials & Interfaces 2016 Volume 8(Issue 45) pp:31339

Publication Date(Web):October 26, 2016

DOI:10.1021/acsami.6b11241

Hydrogels are polymeric materials that have a relatively high capacity for holding water. Recently, a double network (DN) technique was developed to fabricate hydrogels with a toughness comparable to rubber. The mechanical properties of DN hydrogels may be attributed to the brittle sacrificial bonding network of one hydrogel, facilitating stress dispersion, combined with ductile polymer chains of a second hydrogel. Herein, we report a novel class of tunable DN hydrogels composed of a polyurethane hydrogel and a stronger, dipole–dipole and H-bonding interaction reinforced (DHIR) hydrogel. Compared to conventional DN hydrogels, these materials show remarkable improvements in mechanical recovery, modulus, and yielding, with excellent self-healing and self-gluing properties. In addition, the new DN hydrogels exhibit excellent tensile and compression strengths and possess shape-memory properties, which make them promising for applications in engineering, biomedicine, and other domains where load bearing is required.Keywords: double-networks; hydrogels; materials; mechanical recovery; polymers; self-gluing; self-healing; shape memory

One-pot synthesis of highly mechanical and redox-degradable polyurethane hydrogels based on tetra-PEG and disulfide/thiol chemistry

Co-reporter:Haiyan Jia, Zhangjun Huang, Zhao Li, Zhen Zheng and Xinling Wang

RSC Advances 2016 vol. 6(Issue 54) pp:48863-48869

Publication Date(Web):09 May 2016

DOI:10.1039/C6RA04320H

Highly mechanical hydrogels with stimuli degradability are promising scaffold materials for tissue engineering, due to their unique advantage of retaining mechanical strength in use, while being able to be readily removed by external stimuli after use. However, it has always been a big challenge to integrate both good mechanical properties and stimuli degradability into one single hydrogel. In this work, a series of tetra-PEG polyurethane hydrogels with tunable redox-degradability and a high compressive fracture strength has been synthesized by a one-pot method. The good mechanical properties are owed to an extremely uniform network of tetra-PEG, and the redox-degradability is realized using cystamine, which contains a highly DTT-sensitive disulfide bond. The mechanical strength of the as-prepared hydrogels reaches a megapascal range, and their complete degradation time can be flexibly adjusted from 4 to 22 days by controlling the proportion of cystamine. With the above properties, these hydrogels are believed to have potential bio-applications.

Slightly crosslinked polyurethane with DielsAlder adducts from trimethylolpropane

Co-reporter:Pengfei Du;Haiyan Jia;Qinghua Chen;Zhen Zheng;Denglong Chen

Journal of Applied Polymer Science 2016 Volume 133( Issue 39) pp:

Publication Date(Web):

DOI:10.1002/app.43971

ABSTRACT

Diels–Alder (DA) reactions between furan and maleimide have been widely applied in thermally remendable polymeric materials. Crosslinked polyurethane with DA adducts exhibited much better mechanical properties than linear polyurethane with DA adducts. However, the highly crosslinked polyurethane needs a higher temperature and a longer healing time. This will increase the possibility of side reactions proceeding during the healing procedure. In this paper, slightly crosslinked polyurethane with DA adducts was synthesized by incorporating trimethylolpropane into linear polyurethane with DA adducts. The structure of the intermediate and final products was characterized by Fourier transform infrared spectroscopy, ¹H-NMR, and differential scanning calorimetry, confirming that the synthesizing process proceeded successfully. The images from the polarizing optical microscope demonstrated that the final product with slight crosslinking needed less time and a lower healing temperature to complete the healing procedure. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43971.

Preparation of a High-Strength Hydrogel with Slidable and Tunable Potential Functionalization Sites

Co-reporter:Zhao Li, Zhen Zheng, Shan Su, Lin Yu, and Xinling Wang

Macromolecules 2016 Volume 49(Issue 1) pp:373-386

Publication Date(Web):December 31, 2015

DOI:10.1021/acs.macromol.5b02359

A hydrogel with tunable potential functionalization sites has been successfully prepared. As potential functionalization sites, (2-hydroxypropyl)-α-CDs (Hy-α-CDs) were introduced into the network of tetrahedron-like poly(ethylene glycol) (tetra-PEG) gel through supramolecular chemistry. In the stage of complexation, poly-pseudo-rotaxane consisting of tetra-PEG macromonomer and Hy-α-CD formed in pregel solution. The dynamic complexation process and the structure of the poly-pseudo-rotaxane were investigated by NMR experiment. In the stage of gelation, some cross-linking reactions were completed through click chemistry. The structures and mechanical properties of the resultant hydrogels were characterized by ATR-FTIR, XPS, SEM, and compression test in detail. The number of Hy-α-CD introduced into the hydrogel is related closely to the structure of the poly-pseudo-rotaxane and can be controlled easily by tuning the feed ratio. Anthracene as an example of function was introduced into the hydrogel through Hy-α-CD to preliminarily demonstrate the validity of the potential functionalization site in the last, and the hydrogel also has the capacity for further diverse functionalization.

Self-assembly of pH-responsive biodegradable mixed micelles based on anionic and cationic polycarbonates for doxorubicin delivery

Co-reporter:Lin Yu, Chengyu Lin, Zhen Zheng, Zhao Li, Xinling Wang

Colloids and Surfaces B: Biointerfaces 2016 Volume 145() pp:392-400

Publication Date(Web):1 September 2016

DOI:10.1016/j.colsurfb.2016.05.029

•Micelle is prepared by self-assembly of anionic and cationic polycarbonates.•The ionic mixed micelle can withstand high ionic strength.•The decrease of pH value causes the disassembly of mixed micelle.•The micellar surface nature can be converted from negative to positive in acidic condition.•The mixed micelle is biocompatible.Poly(5-propyl-1,3-dioxan-2-one)-b-dimethylamine modified polycarbonate (PC(MPpC-MMA)) and poly(ethylene glycol)-b-carboxylated polycarbonate (PEG-PCCOOH) diblock copolymers were prepared to construct a pH responsive, highly stable and biodegradable mixed micelle. The two copolymers self-assembled into the mixed micelle in pH 7.4 PBS driven by electrostatic and hydrophobic interactions. PC(MPpC-MMA) with hydrophobic inner core was used for carrying drug and the dimethylamine part was designed as a trigger to disassemble the mixed micelle. PEG-PCCOOH could shield the positive character of the micelle which might show disadvantage to normal tissue. In addition, the free carboxyl groups could further increase the loading efficiency of positive charged drugs. The size and zeta potential of the micelle gradually decreased with increasing the molar ratio of PEG-PCCOOH to PC(MPpC-MMA). These mixed micelles could withstand high ionic strength of plasma and were rather stable for long time storage. However, via decrease of pH value from 7.4 to 5.0, they could undergo dissociation into smaller nanoparticles which were in a diameter of 20 nm and showed positive surface nature. In vitro drug delivery studies showed a faster release rate at pH 5.0 than that at pH 7.4. The MTT assays demonstrated potent cytotoxic activity against HepG2 cells. All these results indicate that the newly mixed polycarbonate micelle can show great potential in biomedical field.

Synthesis and properties of tunable thermoresponsive aliphatic polycarbonate copolymers with oligo ethylene glycol containing thioether and/or sulphone groups

Co-reporter:Lin Yu, Zhen Zheng, Yuan Liu, Zhao Li and Xinling Wang

RSC Advances 2015 vol. 5(Issue 80) pp:64832-64840

Publication Date(Web):22 Jul 2015

DOI:10.1039/C5RA10486F

A series of novel thermoresponsive copolycarbonates were constructed by cyclic trimethylene carbonate (MTC) monomers bearing oligo ethylene glycol (OEG) and with thioether or/and sulphone linkages. They were initiated by 1,4-benzenedimethanol with N-(3,5-trifluoromethyl)phenyl-N′-cyclohexylthiourea (TU)/1,8-diazabicyclo[5,4,0]undec-7-ene (DBU) as the organic catalyst. The lower critical solution temperature (LCST) properties of the polycarbonates with thioether or sulphone linkage were studied and discussed with regard to molecular weight, salt concentration and polymer concentration. By using monomers of different OEG chain lengths and thioether and/or sulphone linkages, the LCSTs of biodegradable and thermoresponsive polycarbonate copolymers can be easily tuned within a wide temperature window from 0 °C to 46 °C (3 g L−1 in aqueous solution). In addition, block polycarbonates with two tunable LCSTs were further synthesized and investigated. Results showed that LCST1 was constructed by polycarbonate with a hydrophobic thioether linkage, while the LCST2 was achieved by a polycarbonate containing hydrophilic sulphone linkage.

Tannin as a gatekeeper of pH-responsive mesoporous silica nanoparticles for drug delivery

Co-reporter:Chunlin Hu, Lingxue Yu, Zhen Zheng, Jing Wang, Yuan Liu, Yifeng Jiang, Guangzhi Tong, Yanjun Zhou and Xinling Wang

RSC Advances 2015 vol. 5(Issue 104) pp:85436-85441

Publication Date(Web):28 Sep 2015

DOI:10.1039/C5RA12009H

Tannin grafted on mesoporous silica nanoparticles (tannin-MSNs) was synthesized by the amidation reaction of carboxyl benzyl borate with amino group modified MSN. Tannin-MSNs were an MCM-41 type of mesoporous material with a uniform diameter of about 150 nm. The XRD and N2 adsorption/desorption isotherm results demonstrated that the rhodamine was effectively loaded and the pores of MSN were blocked by tannin. Rhodamine as a model cargo was used to evaluate the loading and releasing behaviors of tannin-MSNs. The drug release rate of tannin-MSNs was pH dependent. An in vitro cellular cytotoxicity test indicated that tannin-MSNs were highly biocompatible and suitable to be used as drug carriers. The cellular uptake was investigated by confocal laser scan microscopy. The results showed that tannin-MSNs are promising platforms to construct a pH-responsive controlled drug delivery system for cancer and stomach therapy.

Silver-releasing and antibacterial activities of polyphenol-based polyurethanes

Co-reporter:Jia Chen;Ying Peng;Zhen Zheng;Peiyu Sun

Journal of Applied Polymer Science 2015 Volume 132( Issue 4) pp:

Publication Date(Web):

DOI:10.1002/app.41349

ABSTRACT

Inspired by mussel adhesive proteins, catechol functional groups play an important role in the ability of the mussel to adhere to organic and inorganic surfaces. A novel functional polyurethane (PU) based on hydrolysable tannins that contain a number of catechol groups was successfully synthesized and characterized. These catechol groups were used as a reducer for Ag (I) to form Ag (0), and to prepare polyurethane/silver nanoparticles composites. These kinds of polyurethane containing Ag nanoparticles showed obvious inhibition of bacterial growth because of the conjunct actions of the well-known antibacterial property of silver and the antifouling property of PEG. It is possible for these materials to be applied widely into antibacterial adhesive coatings for surface modification due to their low cost and the material-independent adhesive property of catechol groups in tannins. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41349.

Facile Preparation of Mussel-Inspired Polyurethane Hydrogel and Its Rapid Curing Behavior

Co-reporter:Peiyu Sun, Jing Wang, Xiong Yao, Ying Peng, Xiaoxiong Tu, Pengfei Du, Zhen Zheng, and Xinling Wang

ACS Applied Materials & Interfaces 2014 Volume 6(Issue 15) pp:12495

Publication Date(Web):July 14, 2014

DOI:10.1021/am502106e

A facile method was found to incorporate a mussel-inspired adhesive moiety into synthetic polymers, and mussel mimetic polyurethanes were developed as adhesive hydrogels. In these polymers, a urethane backbone was substituted for the polyamide chain of mussel adhesive proteins, and dopamine was appended to mimic the adhesive moiety of adhesive proteins. A series of mussel mimetic polyurethanes were created through a step-growth polymerization based on hexamethylene diisocyanate as a hard segment, PEG having different molecular weights as a soft segment, and lysine-dopamine as a chain extender. Upon a treatment with Fe3+, the aqueous mussel mimetic polyurethane solutions can be triggered by pH adjustment to form adhesive hydrogels instantaneously; these materials can be used as injectable adhesive hydrogels. Upon a treatment with NaIO4, the mussel mimetic polyurethane solutions can be cured in a controllable period of time. The successful combination of the unique mussel-inspired adhesive moiety with a tunable polyurethane structure can result in a new kind of mussel-inspired adhesive polymers.Keywords: adhesive hydrogel; dopamine; gelation time; mussel mimetic; polyurethane

Synthesis of linear polyurethane bearing pendant furan and cross-linked healable polyurethane containing Diels–Alder bonds

Co-reporter:Pengfei Du, Meiyin Wu, Xuanxuan Liu, Zhen Zheng, Xinling Wang, Peiyu Sun, Thomas Joncheray and Yuefan Zhang

New Journal of Chemistry 2014 vol. 38(Issue 2) pp:770-776

Publication Date(Web):13 Nov 2013

DOI:10.1039/C3NJ01245J

Primary mono-amine (furfuryl amine) is functionalized as a chain extender to obtain linear polyurethane bearing pendant furan groups (L-PU-Furan), unlike the previous research (furanic diols as chain extender). Furfuryl amine can functionalize as a chain extender due to the reactivity between the resultant urea group and NCO group at higher temperatures. Pendant cross-linked polyurethane containing a DA bond (C-PU-DA) is obtained from the cross-linking of L-PU-Furan and a bismaleimide (BMI) via a Diels–Alder reaction. L-PU-Furan and C-PU-DA are characterized by 1H NMR, FTIR, DSC and TGA. The results of 1H NMR and gel–solution–gel experiments demonstrate that the C-PU-DA exhibits excellent thermal reversibility. C-PU-DA exhibits good healable properties as evidenced by the evolution of a crack versus temperature observed under polarizing optical microscopy. C-PU-DA exhibits good mechanical properties and healing efficiency, determined by breaking (tensile) strength measurements.

Mesoporous SBA-15 end-capped by PEG via l-cystine based linker for redox responsive controlled release

Co-reporter:Liang Chen, Zhen Zheng, Jing Wang, Xinling Wang

Microporous and Mesoporous Materials 2014 Volume 185() pp:7-15

Publication Date(Web):1 February 2014

DOI:10.1016/j.micromeso.2013.10.025

•A novel redox-responsive controlled release system based on SBA-15 was fabricated.•The SBA-SS-mPEG showed good controlled release property responsive to glutathione.•The SBA-15 based system showed a distinctive slow releasing behavior.•L-cystine based linker and PEG gatekeepers will improve the biocompatibility.A unique redox responsive system for glutathione (GSH) triggered controlled release was prepared by modifying the mesoporous SBA-15 with l-cystine ester linked mPEG chains, in which the former was served as the nanoreservoir of guest molecules and the latter was applied as gatekeepers to block the mesopores. The disulfide bond in l-cystine ester can be effectively cleaved by redox reaction under glutathione of cancer cell level, and then resulting in the release of guests encapsulated in the pores. Fluorescein dye as the model drug was loaded into the mesoporous silica nanoparticles (MSNs) and released in PBS with 10 mM GSH and without GSH respectively to test the controlled release properties of the MSNs using UV–Vis spectra as the detector. The results showed that fluorescein dye in PBS with 10 mM GSH was released much more rapidly. Compared with such a controlled release system based on MCM-41, the SBA-15 based system showed a distinctive release behavior. The MSNs synthesized from SBA-15 can be used as an effective drug controlled release system for biomedical applications, especially for long-term drug delivery.

DielsAlder-based crosslinked self-healing polyurethane/urea from polymeric methylene diphenyl diisocyanate

Co-reporter:Pengfei Du;Meiyin Wu;Xuanxuan Liu;Zhen Zheng;Thomas Joncheray;Yuefan Zhang

Journal of Applied Polymer Science 2014 Volume 131( Issue 9) pp:

Publication Date(Web):

DOI:10.1002/app.40234

ABSTRACT

Crosslinked self-healing polyurethane/urea based on a Diels–Alder reaction (C-PMPU–DA) was synthesized from a multiple-furan monomer and a commercial bismaleimide. The multiple-furan monomer (PMPU–furan) was obtained from a functionalized prepolymer (polymeric MDI: PBA-2000 = 2:1) by furfuryl amine. The structures of both the PMPU–furan and C-PMPU–DA were characterized by attenuated total reflectance (ATR)–Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry, thermogravimetric analysis, and ¹H-NMR. The Diels–Alder bonds enabled C-PMPU–DA thermal reversibility, which was investigated by ATR–FTIR spectroscopy, ¹H-NMR, gel–solution–gel experiments, and viscosity tests. Meanwhile, the self-healing properties of C-PMPU–DA were also investigated by the recovery of the mechanical properties. The results showed that C-PMPU–DA exhibited good thermal reversibility and self-healing properties. C-PMPU–DA exhibited thermosetting properties at room temperature, although it exhibited thermoplastic properties at higher temperatures and may find applications in self-healing materials, recyclable materials, or removable materials. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40234.

Trypsin-inspired poly(urea-urethane)s containing phenylalanine-lysine ethyl ester-phenylalanine units

Co-reporter:Fangjie Wang, Zhen Zheng, Wei Wang, Zhenqian Gu, Jing Wang, Xinling Wang

Polymer Degradation and Stability 2014 100() pp: 86-92

Publication Date(Web):

DOI:10.1016/j.polymdegradstab.2013.12.007

Lotus-like paper/paperboard packaging prepared with nano-modified overprint varnish

Co-reporter:Wenting Chen, Xinling Wang, Qingsheng Tao, Jinfang Wang, Zhen Zheng, Xiaoliang Wang

Applied Surface Science 2013 Volume 266() pp:319-325

Publication Date(Web):1 February 2013

DOI:10.1016/j.apsusc.2012.12.018

Abstract

Paper/paperboard has great advantages over plastics as packaging material in terms of cost and sustainability. However, the application of paper/paperboard packaging is limited due to their inferior water resistance performance. Here we report a functional overprint varnish prepared with the aim to significantly abate the wettability of the printed packaging. The prominent water repellency of the varnish is rendered by its unique nano-structured morphology, a technology bio-mimicking lotus surface. The frost formation on the applied packaging is also inhibited. Moreover, the transparency and the application process of the varnish are retained. We expect such varnish has high potential for expanding the application field of paper/paperboard packaging, especially for uses requiring a strict standard of water resistance.

Synthesis and characterization of linear self-healing polyurethane based on thermally reversible Diels–Alder reaction

Co-reporter:Pengfei Du, Xuanxuan Liu, Zhen Zheng, Xinling Wang, Thomas Joncheray and Yuefan Zhang

RSC Advances 2013 vol. 3(Issue 35) pp:15475-15482

Publication Date(Web):27 Jun 2013

DOI:10.1039/C3RA42278J

New linear polyurethane was synthesized via a Diels–Alder (DA) reaction between a polyurethane prepolymer end-capped with furan groups (MPF) and bismaleimide (BMI). The structure of the linear polyurethane with DA bonds was characterized by 1H NMR, ATI-FTIR, TGA and AFM. The introduction of DA bonds enables the polyurethane thermal reversibility, which was studied thoroughly by 1H NMR, DSC and GPC. Besides, the new linear polyurethane with DA bonds also exhibits self-healing properties under heat treatment, which was observed by polarized optical microscope. The self-healing efficiency determined by the recovery of breaking tensile strength after being damaged and healed can reach up to 80%.

Synthesis and characterization of polyphenol-based polyurethane

Co-reporter:Ying Peng, Zhen Zheng, Peiyu Sun, Xinling Wang and Tingke Zhang

New Journal of Chemistry 2013 vol. 37(Issue 3) pp:729-734

Publication Date(Web):14 Dec 2012

DOI:10.1039/C2NJ41079F

A novel adhering polyurethane (PU), based on hydrolysable tannins that contain a number of active sites, was successfully synthesized and characterized. The active sites were catechol groups in the hydrolysable tannins, which were used as a substitute for dopamine. This efficient, universal, and low cost coating based on hydrolysable tannins was cured by adding FeCl3, and was evaluated by nuclear magnetic resonance (1H-NMR), Fourier transform infrared (FTIR), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and UV-Visible spectrophotometry (UV/Vis). The polyurethane coating containing tannins showed improved coating adhesion and an accelerated curing rate on the substrate, both of which were similar those of dopamine based PU coatings. The TGA and UV/Vis results indicated that the characteristics of the tannin-containing polyurethane were deeply related to the concentration of the tannins.

Pore/bead membrane for rechargeable lithium ion batteries

Co-reporter:Yuezeng Su;Feng Shan;Zhiming Li

Journal of Applied Polymer Science 2013 Volume 127( Issue 5) pp:3485-3490

Publication Date(Web):

DOI:10.1002/app.37625

Abstract

A special “pore/bead” membrane was prepared with a mesoporous inorganic filler (MCM-41) and a P(VDF-HFP) binder. The special “pore/bead” structure of the MCM-41 filler not only enhanced the puncture strength of the membrane but also improved its ionic conductivity. The puncture strength of the dried “pore/bead” membrane (MCM-41 : P(VDF-HFP) = 1 : 1.5) was 18 N, and showed a slight decrease (16 N) after the membrane was wetted by liquid electrolyte. Additionally, the composite membrane showed excellent thermal dimensional stability. The composite membrane could be activated by adding 1M LiClO₄-EC/DMC (1 : 1 by volume). The activated membrane displayed a high ionic conductivity about 3.4 × 10⁻³ S cm⁻¹ at room temperature. Its electrochemical stability window was up to 5.3 V vs. Li/Li⁺, indicating that it was very suitable for lithium-ion battery application. The battery assembled using the composite electrolyte also showed reasonably good high-rate performance. The approach of preparing a “pore/bead” membrane provides a new avenue for improving both the conductivity and the mechanical strength of polymer electrolytes for lithium batteries. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013

Synthesis and characterization of biodegradable polyurethanes based on L-cystine/cysteine and poly(-caprolactone)

Co-reporter:Jing Wang;Zhen Zheng;Quan Wang;Pengfei Du;Jinjun Shi

Journal of Applied Polymer Science 2013 Volume 128( Issue 6) pp:

Publication Date(Web):

DOI:10.1002/app.38613

Abstract

Tunable biodegradable polyurethanes (PUs) with favorable mechanical properties were synthesized from 1,6-hexamelthylene diisocyanate (HDI) as the hard segment, poly(ϵ-caprolactone) (PCL) as the soft segment, and L-cystine ester as chain extender. The structure of PUs was confirmed by FTIR and ¹H-NMR. The results of differential scanning calorimeter, thermogravimetric analysis, dynamic mechanical analysis, and tensile test revealed that the thermal and mechanical properties of PUs were strongly influenced by the molecular weight of soft segment PCL. In the presence of glutathione, the disulfide group cleaved into thiols, realizing the PUs degraded and the molecular weight decreased. For PU [550], it remained only 50% of the original M_w. Evaluation of cell viability demonstrated the nontoxicity of the PUs, which facilitated their potential in biomedical applications. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013

Kinetic study of Diels–Alder reaction involving in maleimide–furan compounds and linear polyurethane

Co-reporter:Xuanxuan Liu;Pengfei Du;Li Liu;Zhen Zheng

Polymer Bulletin 2013 Volume 70( Issue 8) pp:2319-2335

Publication Date(Web):2013 August

DOI:10.1007/s00289-013-0954-8

Linear polyurethane was synthesized by Diels–Alder (DA) reaction between a polyurethane prepolymer end-capped with furan rings (MPF) and bismaleimide (BMI). The polymerization kinetics were studied following a preliminary kinetic study of the DA reaction between furfuryl alcohol (FA) and BMI compounds by attenuated total reflection infrared, ultraviolet–visible and in situ 1H NMR spectroscopies, where in situ 1H NMR spectroscopy was selected as the analytical method of choice to study the DA reaction between MPF and BMI. The results showed that the reaction followed second-order kinetics, and the most beneficial experimental conditions to maximize conversion were identified.

Facile and universal immobilization of L-lysine inspired by mussels

Co-reporter:Peiyu Sun, Haoxiang Lu, Xiong Yao, Xiaoxiong Tu, Zhen Zheng and Xinling Wang

Journal of Materials Chemistry A 2012 vol. 22(Issue 19) pp:10035-10041

Publication Date(Web):13 Apr 2012

DOI:10.1039/C2JM16598H

A novel functional molecule lysine-dopamine (LDA) was successfully synthesized and explored as a universal modifier for different types of surfaces, inspired by mussel adhesive moiety dopamine and bio-functional moiety L-lysine. The universal, robust, and efficient surface modification based on LDA was achieved through a facile and cost-effective dip-coating process, confirmed by Fourier transform infrared spectroscopy (FTIR), contact angle, X-ray photoelectron spectroscopy (XPS) and scanning electron microscope-energy dispersive spectroscopy (SEM-EDS) measurements. Meanwhile, LDA modification improved cell adhesion, promoted cell growth, and accelerated endothelialization on the substrate surface and provided plasma clot lysis activity. The results indicated that the surface biocompatibility was obviously improved by the one-step modification method for the immobilized L-lysine.

Pepsin-inspired polyurethanes containing a tyrosine–fumaric acid–tyrosine segment

Co-reporter:Haoxiang Lu, Wei Wang, Zhen Zheng, Peiyu Sun, Xinling Wang and Feng-Chih Chang

Polymer Chemistry 2012 vol. 3(Issue 2) pp:498-503

Publication Date(Web):15 Dec 2011

DOI:10.1039/C2PY00481J

Two kinds of novel peptide mimetic pepsin-inspired degradable polyurethanes were synthesized and characterized. A synthetic pseudo tripeptide acted as chain extender and provided active sites for pepsin biodegradation. In vitrodegradation behavior was investigated in simulated gastric fluid containing pepsin, and assessed by 1H NMR, mass loss and SEM. The results indicated that the pseudo peptide bonds in polyurethanes were effectively digested by the action of pepsin. Furthermore, the rate and degree of pepsin-inspired polyurethanes in simulated gastric fluid containing pepsin could be controlled by alteration of the soft segments and activity of pepsin. The influence of the polymers on human umbilical vein endothelial cells was evaluated by WST-1 assay. The results indicated that the polymers sustained much higher cell viability than the controls.

Glutathione-responsive biodegradable polyurethanes based on dithiodiundecanol

Co-reporter:Jing Wang, Peiyu Sun, Zhen Zheng, Fangjie Wang, Xinling Wang

Polymer Degradation and Stability 2012 Volume 97(Issue 11) pp:2294-2300

Publication Date(Web):November 2012

DOI:10.1016/j.polymdegradstab.2012.07.041

Biodegradable polyurethanes were prepared from 11,11′-dithiodiundecanol employed as soft segment incorporating hexamethylene diisocyanate (HDI) and 1,4-butanediol (BDO) serving as hard segment. The disulfide bonds in dithiodiundecanol could be cleaved into thiols in the presence of glutathione (GSH) through disulfide-thiol exchange reaction, which fulfilled the polyurethanes with responsive biodegradability. In vitro degradation test in PBS buffer at 37 °C, the molecular weight of polyurethanes substantially decreased and the surface morphology was significantly eroded after 8 days. The degradation reaction constants were calculated and kinetic equations were established.

Reduction-sensitive rapid degradable poly(urethane-urea)s based on cystine

Co-reporter:Haoxiang Lu, Peiyu Sun, Zhen Zheng, Xiong Yao, Xinling Wang, Feng-Chih Chang

Polymer Degradation and Stability 2012 Volume 97(Issue 4) pp:661-669

Publication Date(Web):April 2012

DOI:10.1016/j.polymdegradstab.2011.12.023

Two kinds of novel reduction-sensitive rapid degradable poly(urethane-urea)s were synthesized and characterized based on a cystine derivative chain extender which provided active sites for reductive degradation. In vitro degradation study was carried out under physiological conditions mediated by glutathione and dithiothreitol respectively, and was assessed by 1H NMR, GPC and SEM. The results indicated that the disulfide bonds in poly(urethane-urea)s were effectively cleaved while the structures of urethane groups and soft segments remained almost unaffected. Still, the rate and degree of reductive degradation could be controlled by the structures of the polymers. The influence of the poly(urethane-urea)s on human umbilical vein endothelial cells was investigated by WST-1 assay. The results indicated that the polymers sustained much higher cell viability than the controls. It is possible that the poly(urethane-urea)s can be potentially applied for temporary biomaterials such as wound closure devices, cell scaffolds and sophisticated drug delivery systems.

Thermoreversible supramolecular polyurethanes with self-complementary quadruple hydrogen-bonded end groups

Co-reporter:Bo Zhu;Zhicheng Feng;Zhen Zheng

Journal of Applied Polymer Science 2012 Volume 123( Issue 3) pp:1755-1763

Publication Date(Web):

DOI:10.1002/app.34638

Abstract

In this article, a new type of strongly dimerizing 2-ureido-4-[1H]-pyrimidinone (UPy) with amine group is synthesized and then used as end-group to prepare a novel series of supramolecular polyurethanes (PUs). The effects of strong and well-defined hydrogen bonding on material properties of PUs are studied. In these PUs, the UPy groups consequently serve as thermoreversible associations or the “hard blocks” and the bi-functional PU chains act as the “monomers.” This theoretical hypothesis is proved by the results of dynamic mechanical thermal analysis (DMTA) and rheological test. Thermal analysis shows that the strong hydrogen bonds from end groups restrict the formation of their microcrystalline domains. The supramolecular PUs exhibit good mechanical performance and their self-assemble mechanism is discussed. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

Effect of oxidation progress of tributylborane on the grafting of polyolefins

Co-reporter:Shujuan Liu;Zhen Zheng;Minrui Li

Journal of Applied Polymer Science 2012 Volume 125( Issue 5) pp:3335-3344

Publication Date(Web):

DOI:10.1002/app.34232

Abstract

Effect of the oxidation progress of tributylborane on the grafting reaction of PMMA onto high-density polyethylene (HDPE) and isotropic polypropylene (iPP) surface with tributylborane as initiator was studied in detail. The oxidation of tributylborane was triggered by the slow diffused oxygen or exposed contact to oxygen, so that the oxidation progress of tributylborane would be different. The grafted polyolefin surfaces were characterized by attenuated total reflection infrared (ATR-IR) spectroscopy, X-ray photoelectron spectroscopic (XPS), scanning electron microscope (SEM) and so on. The results of ATR-IR spectroscopy and XPS analysis suggested that PMMA could be grafted onto polyolefin surfaces successfully through these two ways, but the grafting degrees were varied due to the different oxidation progresses of tributylborane. The surface morphologies of the polyolefin indicated the different grafting degrees as a result of different oxidation progress of tributylborane. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

Study of the radical chemistry promoted by tributylborane

Co-reporter:Shujuan Liu;Zhen Zheng;Minrui Li

Research on Chemical Intermediates 2012 Volume 38( Issue 8) pp:1893-1907

Publication Date(Web):2012 October

DOI:10.1007/s11164-012-0512-2

The structures of radicals generated in the oxidation process of trialkylborane were detected based on ultra-high performance liquid chromatography-quadrupole-time-of-flight mass spectrometry (UPLC/Q-ToF MS) combined with the spin trapping method. Structural identification of the spin adducts produced by 5,5-dimethyl-1-pyrroline-1-oxide with radicals could be carried out unambiguously by combining the data obtained by UPLC/Q-ToF MS analyses. Then the oxidation mechanism was described. To specify the inter-relationships between the oxidation process of trialkylborane and the concomitant radical chemistry, four kinds of alkanes providing different H-abstraction reactivity to alkoxy radical were chosen as radical capturers. The final oxidation products of trialkylborane were characterized by GC–MS and 11B-NMR. The results indicted that the radical content was not only affected by the oxidation degree of trialkylborane, but also done by the activity of alkane. Especially the hydrogen atom abstraction by n-butoxy radical played an important role in the oxidation process of tributylborane, which would promote the oxidizability of tributylborane and deepen the oxidation degree of tributylborane.

Mechanism of adhesion of low surface energy materials treated with trialkylborane

Co-reporter:Minrui Li, Zhen Zheng, Shujuan Liu, Wei Wei, Xinling Wang

International Journal of Adhesion and Adhesives 2011 Volume 31(Issue 1) pp:36-42

Publication Date(Web):January 2011

DOI:10.1016/j.ijadhadh.2010.09.003

Excellent adhesion to low surface energy materials without surface pretreatment was obtained by acrylates polymerization initiated by trialkylborane at room temperature. The adhesion mechanism was elucidated by electron spin resonance (ESR) and gas chromatography–mass spectroscopy (GC–MS) analysis based on model compound and chain transferring agent technologies. On the other hand, polypropylene (as one kind of low energy surface materials) was treated with trialkylborane and its effects were also studied by attenuated total reflection Fourier transform infrared spectroscopy (FTIR-ATR) and Raman spectroscopy, static contact angle measurements. The result provided further supports the elucidated mechanism.The results showed the adhesion resulted from the monomer’s graft on the surface of low surface energy materials. The graft resulted from the hydrogen abstraction reaction of materials (not less than three hydrogen sites) by alkoxyl and other radicals. These radicals came from oxidation of trialkylborane through the cleavage of O−O bond of R2BOOR. The adhesion was caused neither by the materials’ surface energy improvement nor by the copolymerization of polymerizable monomers and unsaturated groups on the surface of materials.

Synthesis and properties of poly(acrylates-co-urethane) adhesives for low surface energy materials

Co-reporter:Minrui Li, Zhen Zheng, Shujuan Liu, Yuezeng Su, Wei Wei, Xinling Wang

International Journal of Adhesion and Adhesives 2011 Volume 31(Issue 6) pp:565-570

Publication Date(Web):September 2011

DOI:10.1016/j.ijadhadh.2011.05.006

The series of poly(acrylates-co-urethane) were synthesized based on the copolymerization between 2-hydroxyethyl acrylate terminated polyether (or polyester) urethane and acrylate monomers initiated by tri-n-butylborane (TBB). The effects of the soft segment of polyether (or polyester) urethane diacrylate on the copolymer properties were mainly discussed. Polyether (or polyester) urethane was relatively well dispersed in polyacrylate continuous phase, and was intended to aggregate with the increase of soft segment polarity and content. The adhesion to low surface energy materials and loss factor (tan δ) of copolymers were almost not influenced by the soft segment content, but decreased with the increase of soft segment polarity within the scope of the study. On the other hand, the working life of copolymers as adhesives was shortened with the increase of soft segment polarity, but prolonged with the increase of soft segment content. The copolymers with different structures of polyether (or polyester) urethane diacrylate were also shown to be good candidates as adhesives at room temperature.

Effect of nonsolvent on morphologies of polyamide 6 electrospun fibers

Co-reporter:Wei Wei;Jen-Taut Yeh;Peng Li;Min-Rui Li;Wei Li;Xin-Ling Wang

Journal of Applied Polymer Science 2010 Volume 118( Issue 5) pp:3005-3012

Publication Date(Web):

DOI:10.1002/app.32704

Abstract

The effect of nonsolvent on morphologies of electrospun polyamide 6 (PA6) fibers was reported in this study. An investigation of electrospinning PA6 / formic acid (FA) / dichloromethane (DCM) solutions was conducted, wherein FA was used as solvent and DCM was used as nonsolvent for PA6. It is interesting to note that PA6 pellets could dissolve in FA/DCM mixtures with various volume ratios faster than in pure FA. Moreover, the addition of DCM to PA6/FA solution modified the solution properties, that is, conductivity, surface tension, and viscosity. It is found that at any fixed PA6 concentration, the conductivity values and surface tensions values of PA6/FA/DCM solution reduce significantly, whereas the viscosity values of PA6/FA/DCM solution increase significantly, as the volume fraction of DCM in FA/DCM increase. The influences of mixed solvents component on morphological appearance and sizes of the resulting PA6 electrospun fibers were also investigated. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010

Effect of prepolyurethane on the performances of poly(acrylates-co-urethane) copolymer

Co-reporter:Minrui Li;Zhen Zheng;Shujuan Liu;Wei Wei

Journal of Applied Polymer Science 2010 Volume 118( Issue 6) pp:3203-3210

Publication Date(Web):

DOI:10.1002/app.32761

Abstract

Poly(acrylates-co-urethane) copolymers were synthesized by the polymerization of acrylates and 2-hydroxyethyl acrylate terminated polyurethane (prepolyurethane) at room temperature. The polymerization was initiated by the radicals, which were produced by the oxidation of tri-n-butylborane (TBB) from the mixing of TBB/hexamethylene diamine complex and diisocyanate decomplexer. The effects of prepolyurethane on the performances of copolymers were discussed. The results indicated that the damping property and flexibility of copolymers were obviously higher than that of pure polyacrylates. Dynamic mechanical analysis and transmission electron microscope results showed that PU was dispersed in polyacrylates phase very well. The copolymers were found to bond well to low surface energy materials because of introduction of PU. The lap shearing strength of copolymer bonding polypropylene or polyethylene both had the trend of first increase followed by decrease with the prepolyurethane content increase. The copolymers as adhesives were also shown to have a long working life and be suitable for utilization at low temperature especially at room temperature. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010

Preparation and properties of polythiourethane/ZnS nanocomposites with high refractive index

Co-reporter:Li Liu;Zhen Zheng

Journal of Applied Polymer Science 2010 Volume 117( Issue 4) pp:1978-1983

Publication Date(Web):

DOI:10.1002/app.32009

Abstract

The inorganic–organic crosslinking polythiourethane/ZnS (PTU/ZnS) nanocomposites with high refractive index and transmittance were successfully prepared. The thiol-capped ZnS nanoparticles with a diameter of about 5 nm were fabricated into the molecular chains of PTU via the formed covalent bonds between the capped ZnS and the matrix. The investigations demonstrated the ZnS nanoparticles were uniformly dispersed in the PTU matrix even at high contents. The optical studies showed the refractive index of the highly transparent nanocomposite films linearly increased from 1.643 to 1.792 with the increase of the ZnS content. The structure, morphology, and other properties were also characterized by FTIR, NMR, AFM, XRD, DSC, TGA, etc. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010

The preparation of biodegradable polyurethane/carbon nanotube composite based on in situ cross-linking

Co-reporter:Wen-Hui Song;Qiu-Ping Ni;Zhen Zheng;Li-Ying Tian ;Xin-Ling Wang

Polymers for Advanced Technologies 2009 Volume 20( Issue 3) pp:327-331

Publication Date(Web):

DOI:10.1002/pat.1271

Abstract

A biodegradable polyurethane (PU)/carbon nanotube (CNT) composite was prepared by bulk polymerization based on in situ cross-linking of hydroxyl-terminated polylactic acid functionalized CNTs. As parallel experiments, PU/CNT blend and pure PU were prepared. The obtained products were characterized by Fourier transform infrared (FTIR), thermogravimetric analyses (TGA) and differential scanning calorimetry (DSC), hydrogen nuclear magnetic resonance (¹H NMR) and field emission scanning electron microscopy (FESEM). The properties and morphology of composites were discussed including both blending and cross-linking composites. The results showed that the functionalized CNTs were dispersed well in the PU matrix, and its initial thermal decomposition temperature was higher than that of the blend. Copyright © 2008 John Wiley & Sons, Ltd.

Moisture-cured polyurethane/polysiloxane copolymers: Effects of the structure of polyester diol and NCO/OH ratio

Co-reporter:Hongmei Jiang;Zhen Zheng;Wenhui Song

Journal of Applied Polymer Science 2008 Volume 108( Issue 6) pp:3644-3651

Publication Date(Web):

DOI:10.1002/app.27343

Abstract

Moisture-cured polyurethane is one of the commercially important polymers, which is widely used in sealants, coatings, and reactive hot-melt adhesives. A series of moisture-cured polyurethane/polysiloxane (PUSR) copolymers were successfully prepared using a two-step solution polymerization procedure. Both amine-terminated polysiloxane (PDMS) and polyester diol were together used as mixed soft segments to react with 4,4′-diphenlymethane diisocyanate (MDI), and the alkoxysilane was used as end-capping agents. The effects of structure variation of building blocks such as the polyester diol structure and NCO/OH ratio on the properties and morphology of PUSR copolymers were studied. The tensile properties, dielectric behavior, thermal stability, surface, and water-repellency properties were investigated. The results showed that the properties and morphology of PUSR copolymers were greatly affected by the variations in molecular architecture. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008

Kinetic study of methyltriethoxysilane (MTES) hydrolysis by FTIR spectroscopy under different temperatures and solvents

Co-reporter:Hongmei Jiang, Zhen Zheng, Xinling Wang

Vibrational Spectroscopy 2008 Volume 46(Issue 1) pp:1-7

Publication Date(Web):16 January 2008

DOI:10.1016/j.vibspec.2007.07.002

Fourier transform infrared (FTIR) spectroscopy was employed to study the hydrolysis reaction of methyltriethoxysilane (MTES) in an acid-catalyzed system. The compound is greatly important in the preparation of adhesives and moisture-curing inorganic–organic hybrid materials. The kinetic behavior of the hydrolysis reaction as a function of temperature and solvent was investigated by the systematic changes of MTES characteristic bands. The results showed that the hydrolysis reactions of MTES under acid conditions were greatly influenced by the reaction temperature and solvents, and the hydrolysis process followed a first-order reaction. The hydrolysis rate constants, activation energy, and Arrhenius frequency factor were achieved by linear regression analysis for MTES hydrolysis in the acid system. The solvent effects were explained as “hydrophobic interaction”.

Novel network polymer electrolytes containing fluorine and sulfonic acid lithium prepared by ultraviolet polymerization

Co-reporter:Zhiming Li;Liwen Chen;Jiangong Wei;Jun Yang

Journal of Applied Polymer Science 2008 Volume 108( Issue 4) pp:2509-2514

Publication Date(Web):

DOI:10.1002/app.27911

Abstract

Novel gel network polymer electrolytes containing fluorine and sulfonic acid lithium were prepared by the ultraviolet polymerization of poly(ethylene glycol) dimethyl acrylate, 2-acrylamido-2-methyl propanesulfonic acid, and trifluoroethyl methacrylate. The network polymer was activated with 1.0M LiPF₆/ethylene carbonate/dimethyl carbonate solutions (ethylene carbonate/dimethyl carbonate = 1 : 1 v/v) to prepare gel network polymer electrolytes. The characteristics of the polymer networks, including the gel fractions, thermal stability, liquid electrolyte uptake, and electrochemical properties, were studied. When the poly(ethylene glycol) dimethylacrylate/2-acrylamido-2-methyl propanesulfonic acid/trifluoroethyl methacrylate weight ratio was 60 : 35 : 5, the network polymer electrolytes showed the highest liquid electrolyte uptake (144%) and ionic conductivity (ca. 10⁻³ S/cm) at room temperature (25°C). The network polymer electrolytes were electrochemically stable up to 5.0 V versus Li⁺/Li. The excellent performances of the network polymer electrolytes suggest that they are suitable for application in high-performance lithium-ion batteries. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008

Incorporation of Multi-Walled Carbon Nanotubes into Biodegradable Telechelic Prepolymers

Co-reporter:Wenhui Song;Zhen Zheng;Haoxiang Lu

Macromolecular Chemistry and Physics 2008 Volume 209( Issue 3) pp:315-321

Publication Date(Web):

DOI:10.1002/macp.200700362

PVDF/PMMA brushes membrane for lithium-ion rechargeable batteries prepared via preirradiation grafting technique

Co-reporter:Zhiming Li;Jiangong Wei;Feng Shan;Jun Yang

Journal of Polymer Science Part B: Polymer Physics 2008 Volume 46( Issue 7) pp:751-758

Publication Date(Web):

DOI:10.1002/polb.21408

Abstract

Poly(methyl methacrylate) (PMMA) was anchored to multiporous poly(vinylidine fluoride) (PVDF) surface via electron beam preirradiation grafting technique to prepare PVDF/PMMA brushes. The conformation of the PVDF/PMMA brushes was verified through Attenuated total reflection-Fourier transform infra red spectroscopy (ATR-FTIR), energy dispersive X-ray spectroscopy (EDX), and scanning electron microscopy (SEM). Thermal stability of PVDF/PMMA brushes was characterized by thermo gravimetric analysis (TGA). The degradation of PVDF/PMMA brushes showed a two-step pattern. PVDF/PMMA brushes membrane could be used as polymer electrolyte in lithium-ion rechargeable batteries after it was activated by uptaking 1 M LiPF₆/EC-DMC (ethylene carbonate/dimethyl carbonate; EC:DMC = 1:1 by volume) electrolyte solution. The activated membrane showed high ionic conductivity, 6.1 × 10⁻³ S cm⁻¹ at room temperature, and a good electrochemical stability up to 5.0 V. The excellent performances of multiporous PVDF-g-PMMA membranes suggest that they are suitable for application in high-performance lithium-ion batteries. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 751–758, 2008

High ionic conductive PVDF-based fibrous electrolytes

Co-reporter:Zhiming Li;Feng Shan;Jiangong Wei;Jun Yang

Journal of Solid State Electrochemistry 2008 Volume 12( Issue 12) pp:1629-1635

Publication Date(Web):2008 December

DOI:10.1007/s10008-008-0540-4

The high ionic conductive polymer electrolytes were prepared based on poly(vinylidenefluoride) (PVDF) fibers modified via preirradiation grafting poly(methyl methacrylate) (PMMA). In these polymer electrolytes, the PVDF fibers served as the supporting phase providing dimensional stability, and PMMA acted as the gel phase helping for the trapping liquid electrolyte and substituting the nonconductive PVDF phase to provide contact with electrodes well thus increasing conductive area. The modified PVDF fibrous membranes were used as a polymer electrolyte in lithium ion battery after they were activated by uptaking 1 M LiPF6/ethylene carbonate–dimethyl carbonate (1:1 vol) liquid electrolyte, which showed a much higher room-temperature ionic conductivity than the pristine PVDF fibrous membrane. The LiCoO2-mesocarbon microbead coin cells containing the dual-phase fibrous membrane (degree of graft, 111.8%) demonstrated excellent rate performance, and the cell still retained about 86% of discharge capacity at 4C rate, as compared to that at 0.1C rate. The prototype cell showed good cycle performance.

Preparation, morphology, and properties of polyurethane–urea elastomers derived from sulphone-containing aromatic diamine

Co-reporter:XiuMin Qin;XiaoHui Yang;JiaWen Xiong;Zhen Zheng

Journal of Applied Polymer Science 2007 Volume 104(Issue 6) pp:3554-3561

Publication Date(Web):22 MAR 2007

DOI:10.1002/app.25672

An aromatic diamine containing both sulfone and diphenyl ether groups, bis[4-(4-aminophenoxy)phenyl]sulfone, was synthesized in a two-step way, whose structure was confirmed through Fourier transform infrared spectrometry, nuclear magnetic resonance, and elemental analysis. Then, the obtained BAPS was used as the chain-extender to prepare a polyurethane–urea elastomer, whose morphology, thermal stability and mechanical properties were examined by means of attenuated total reflection, DSC, thermogravimetric analysis, dynamic mechanical thermal analysis, and stress–strain measurements. The results showed that the PUU elastomer based on BAPS showed good heat-resistance and mechanical properties. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3554–3561, 2007

Alkoxysilane Functionalized Polyurethane/Polysiloxane Copolymers: Synthesis and the Effect of End-Capping Agent

Co-reporter:Hongmei Jiang;Zhen Zheng;Wenhui Song;Zhiming Li

Polymer Bulletin 2007 Volume 59( Issue 1) pp:53-63

Publication Date(Web):2007/06/01

DOI:10.1007/s00289-007-0748-y

A series of moisture curable polyurethane/polysiloxane (PUSR) copolymers with different end-capping agents were prepared based on amine terminated polysiloxane (PDMS), poly-1,4-butylene adipate glycol (PBA), 4,4′-diphenylmethane diisocyanate (MDI). The copolymers were characterized by Fourier transform infrared (FT-IR) spectroscopy, thermogarvimetric (TGA), X-ray diffraction (XRD), dynamic mechanical thermal analysis (DMTA), X-ray photoelectron spectroscopy (XPS), surface contact angle and stress–strain measurement. Compared with conventional moisture curable PU the PUSR copolymer showed the better thermal stability and surface properties due to the forming of Si-O-Si crosslinking network and the enrichment of siloxane chains on the surface of films , and the tensile strength was not obviously damaged. DMTA results suggested that micro-phase separation was formed in the PUSR copolymer. It was found that the PUSR copolymer with mixed alkoxysilanes as end-capping agents showed better compromised properties than that with single alkoxysilane.

The thermal and mechanical properties of a polyurethane/multi-walled carbon nanotube composite

Co-reporter:Jiawen Xiong, Zhen Zheng, Xiumin Qin, Ming Li, Huiqing Li, Xinling Wang

Carbon 2006 Volume 44(Issue 13) pp:2701-2707

Publication Date(Web):November 2006

DOI:10.1016/j.carbon.2006.04.005

A polyurethane/multi-walled carbon nanotube elastomer composite was synthesized. The microstructure of the composite was examined by field-emission scanning electron microscopy and transmission electron microscopy. The thermal and mechanical properties of the composite were characterized by dynamic mechanical thermal analysis, thermogravimetric analysis and tensile testing. The chemical linkage of carbon nanotubes with polyurethane matrix was confirmed by Fourier transform infrared spectra. The study on the structure of the composite showed that carbon nanotubes could be dispersed in the polymer matrix well apart from a few of clusters. The results from thermal analysis indicated that the glass transition temperature of the composite was increased by about 10 °C and its thermal stability was obviously improved, in comparison with pure polyurethane. The investigation on the mechanical properties showed that the modulus and tensile strength could be obviously increased by adding 2 wt% (by weight) CNT to the matrix.

Synthesis and characterization of polyurethane urea based on fluorine-containing bisphenoxydiamine

Co-reporter:Xiu-Min Qin;Fang Fang;Xiao-Hui Yang;Xin-Ling Wang;Zhen Zheng

Journal of Applied Polymer Science 2006 Volume 102(Issue 2) pp:1863-1869

Publication Date(Web):28 JUL 2006

DOI:10.1002/app.24138

A fluorine-containing bisphenoxydiamine, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (BAPF₆P), was synthesized and characterized by means of Fourier transform infrared spectrometry (FTIR), NMR, and elemental analysis. The obtained BAPF₆P was used as a chain extender to prepare polyurethane urea (PUU), whose morphology and properties were measured through FTIR, differential scanning calorimetry, thermogravimetric analysis, tensile measurements, and atomic force microscopy. The results show that the PUU elastomers based on BAPF₆P exhibited good mechanical properties and thermal stability. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1863–1869, 2006

Synthesis and characterization of new hyperbranched polymers with only inner functional groups modified

Co-reporter:Ming Li;Xiaohui Yang;Yunhang Liu

Journal of Applied Polymer Science 2006 Volume 101(Issue 1) pp:317-322

Publication Date(Web):25 APR 2006

DOI:10.1002/app.23638

The novel core-shell polymers were synthesized based on the perfluoroalkyls grafting onto the inner hydroxyl groups of hyperbranched polyglycidol while the outer hydroxyl groups remained unaffected. The samples were characterized with FTIR, NMR, element analysis, and liquid chromatography/mass spectrometry. The various results obtained by different measurements are in good agreements. The conversion ratio of inner hydroxyl groups is about 0.3 and most functionalizations took place in linear 1,4-units (L_1–4). Differential Scanning Calorimetry results suggest the samples are amorphous within the experiment range. Their inner lipophilicity and outer hydrophilism resulted from their unique structures are expected to gain promising applications. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 317–322, 2006

Perfluoroalkyl-terminated star polymer electrolyte

Co-reporter:Shao Jiajia;Yang Xiaohui;Liu Yunhang;Wang Xinling

Journal of Applied Polymer Science 2005 Volume 98(Issue 1) pp:238-242

Publication Date(Web):12 JUL 2005

DOI:10.1002/app.22069

A perfluoroalkyl-terminated multiarm star polymer (perfluoroalkyl-terminated hyperbranched polyglycerol) was synthesized and characterized on the basis of perfluorooctanoyl chloride grafting on hyperbranched polyglycerol. The conductivity of a blend of the perfluoroalkyl-terminated star polymer and linear poly(ether urethane) was studied. The results indicated that this blend had better solvating capability in salt and higher ionic conductivity. The conductivity of the blend was 2.5 × 10⁻⁴ S cm⁻¹ at 60°C when the concentration of the perfluoroalkyl-terminated hyperbranched polyglycerol was 30 wt % and the ethylene oxide (EO)/Li ratio was 4 in the blend. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 238–242, 2005

Synthesis and characterization of poly(imide-urethane) based on novel chain-extender containing both imide and sulphone functions

Co-reporter:XiuMin Qin;XiaoHui Yang;MingJun Wang

Journal of Polymer Science Part A: Polymer Chemistry 2005 Volume 43(Issue 19) pp:4469-4477

Publication Date(Web):15 AUG 2005

DOI:10.1002/pola.20920

Several new glycols containing both imide and sulfone groups, sulfonyl bisimide glycol (SBIG), were prepared from primary aromatic diamine, trimellitic anhydride and excess low molecular glycols. Then these SBIGs were used as chain extender to prepare a series of thermoplastic poly(imide-urethane) (PIU), which introduced imide rings into the backbones. Compared to conventional linear polyurethane (PU), these PIUs exhibited better thermal stabilities because of the presence of the sulfone and built-in imide groups. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4469–4477, 2005

Thermal and mechanical properties of polyurethane/montmorillonite nanocomposites based on a novel reactive modifier

Co-reporter:Jiawen Xiong, Yunhang Liu, Xiaohui Yang, Xinling Wang

Polymer Degradation and Stability 2004 Volume 86(Issue 3) pp:549-555

Publication Date(Web):December 2004

DOI:10.1016/j.polymdegradstab.2004.07.001

Polyurethane/montmorillonite (PU/MMT) nanocomposites based on thermally stable, aromatic amine modifier containing active groups (methylene-bis-ortho-chloroanilline, MOCA) were synthesized by intercalative polymerisation. The cured hybrid exhibited higher thermal stability and better mechanical strength than pure polyurethane or polyurethane/cetyltrimethyl-ammonium-bromide (CTAB)-modified MMT (PU/C16-MMT). The moduli and the onset degradation temperature for the PU were obviously increased by addition of MMT treated with the MOCA (MO-MMT), and the mechanical strength was dramatically increased by about 600% for the MO-MMT only increased by about 450% for the C16-MMT at the point of 5 wt% organically modified MMT content. Surprisingly, the glass transition temperature of the PU/organic-MMT nanocomposites was lower than that of the PU.

Synthesis and characterization of a multiarm star polymer

Co-reporter:Sun Xiaoying;Yang Xiaohui;Liu Yunhang;Wang Xinling

Journal of Polymer Science Part A: Polymer Chemistry 2004 Volume 42(Issue 10) pp:2356-2364

Publication Date(Web):2 APR 2004

DOI:10.1002/pola.20083

A multiarm star polymer was synthesized through the grafting of oligo polyglycol with urethane chain end units onto the core of hyperbranched polyglycerol (HPG), which was obtained through the cationic ring-opening polymerization of glycidol. Samples were characterized with ¹³C NMR, liquid chromatography/mass spectrometry, vapor pressure osmometry, and Raman spectroscopy. The degree of branching of HPG was 0.54, and the number of arms grafting onto HPG was 4. The urethane of the arms mainly reacted with the terminal hydroxy groups of HPG. The differences between the spin–spin relaxation times indicated that the terminal segments of the star were more flexible than those of the core. Grafting polyglycol polyurethane (soft segments of polyurethane is polyglycol) onto HPG improved its dimensional stability. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2356–2364, 2004

Study of hyperbranched poly(glycidol) sulfate electrolyte

Co-reporter:Yang Xiaohui;Sun Xiaoying;Liu Yunhang;Wang Xinling;Chen Jianjun

Journal of Applied Polymer Science 2003 Volume 90(Issue 5) pp:1185-1190

Publication Date(Web):27 AUG 2003

DOI:10.1002/app.12531

Hyperbranched poly(glycidol) alkali sulfate (SHPG-M) was prepared based on hyperbranched poly(glycidol). Polyurethane–hyperbranched poly(glycidol) (PU–SHPG-M) sulfate electrolyte is a kind of single ionic or cationic conducting polymer electrolyte. Such a single ionic polymer electrolyte can obviously reduce the polarization and has little decay of direct current (DC) conductivity. SHPG-M was characterized by Fourier transform infrared (FTIR), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), atomic force microscopy (AFM) and impedance analysis. The optimum conductivity is ∼3 × 10⁻⁶ S·cm⁻¹, with 30–40% SHPG-M in the polymer electrolyte at room temperature. The species of cation greatly effects the ionic conductivity of the polymer electrolyte; that is, σ_SHPG-Li > σ_SHPG-Na > σ_SHPG-K, with same SHPG-M content in the polymer electrolyte. The ionic conductivity increases with an increase of temperature, and the dependence of ionic conductivity on temperature fits the Arrhenius equation well. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1185–1190, 2003

Facile and universal immobilization of L-lysine inspired by mussels

Co-reporter:Peiyu Sun;Haoxiang Lu;Xiong Yao;Xiaoxiong Tu;Zhen Zheng

Journal of Materials Chemistry A 2012 - vol. 22(Issue 19) pp:

Publication Date(Web):2012/04/24

DOI:10.1039/C2JM16598H

Facile construction of near-monodisperse and dual responsive polycarbonate mixed micelles with the ability of pH-induced charge reversal for intracellular delivery of antitumor drugs

Co-reporter:Lin Yu, Mengmeng Xie, Zhao Li, Chengyu Lin, Zhen Zheng, Linzhu Zhou, Yue Su and Xinling Wang

Journal of Materials Chemistry A 2016 - vol. 4(Issue 36) pp:NaN6093-6093

Publication Date(Web):2016/08/17

DOI:10.1039/C6TB01865C

A mixed strategy was used to construct size-adjustable, pH and redox dual-responsive, near-monodisperse and charge-conversional core–shell polycarbonate carriers. First, two kinds of random polycarbonates (PC(Arss-N2CH3)) with different ratios of hydrophobic disulfide (Arss) and hydrophilic dimethylamine functional groups (N2CH3) (relatively hydrophobic polycarbonate (BPC) with more disulfide groups and relatively hydrophilic polycarbonate (LPC) with more dimethylamine groups) were used to construct near-monodisperse core micelles in pH 7.4 PBS. Then, a negatively charged shell polymer, poly(ethylene glycol)-b-1,2-dicarboxylic-cyclohexene anhydride modified amino polycarbonate (PEG-PCDCA), bearing acid-labile β-carboxylic amides, was added to the core micelle solution to get the desired mixed micelle. The assembly process, pH induced charge-reversal, and dual-response abilities of the resultant mixed micelles were thoroughly studied using zeta potential and dynamic light scattering (DLS). Two model drugs, Nile red (NR) and doxorubicin (DOX), were successfully loaded into the micelle and could be released in response to dithiothreitol (DTT) and acidic conditions. Confocal microscopy indicated that the micelle system could achieve effective cellular uptake and DOX release in Hela cells. Moreover, the blank micelle and the drug-loaded mixed micelle showed slight and great cytotoxicity against Hela cells, respectively, indicating their significant potential in cancer therapy.