Co-reporter:Xiuyan Wang, Husheng Yan
Materials Science and Engineering: C 2017 Volume 78(Volume 78) pp:
Publication Date(Web):1 September 2017
DOI:10.1016/j.msec.2017.04.136
•Drug-adsorbed porous polymeric adsorbents as oral sustained release formulations.•The adsorption (load) is performed in water medium without use of organic solvents.•The formulations show both sustained release and high oral bioavailability.•The release rate can be controlled by pore size of the adsorbents.Methotrexate as a model drug with poor aqueous solubility was adsorbed into porous polymeric adsorbents, which was used as oral sustained release formulations. In vitro release assay in simulated gastrointestinal fluids showed that the methotrexate-loaded adsorbents showed distinct sustained release performance. The release rate increased with increase in pore size of the adsorbents. In vivo pharmacokinetic study showed that the maximal plasma methotrexate concentrations after oral administration of free methotrexate and methotrexate-loaded DA201-H (a commercial porous polymeric adsorbent) to rats occurred at 40 min and 5 h post-dose, respectively; and the plasma concentrations decreased to 22% after 5 h for free methotrexate and 44% after 24 h for methotrexate-loaded DA201-H, respectively. The load of methotrexate into the porous polymeric adsorbents not only resulted in obvious sustained release, but also enhanced the oral bioavailability of methotrexate. The areas under the curve, AUC0–24 and AUC0-inf, for methotrexate-loaded DA201-H increased 3.3 and 7.7 times, respectively, compared to those for free methotrexate.Download high-res image (127KB)Download full-size image
Co-reporter:Liang Xu, Tao Zhang, Huajin Dong, Dazheng Cai, Han Han, Qingbin Meng, Yongjia Tang, Qingguo Meng, Zehui Gong, Tianhong Zhang, Zhenqing Zhang, Husheng Yan and Keliang Liu
Journal of Materials Chemistry A 2016 vol. 4(Issue 23) pp:4147-4155
Publication Date(Web):06 May 2016
DOI:10.1039/C6TB00235H
Addition polymerization usually results in polymers with long carbon–carbon main chains. Cyanoacrylate (CA) is arguably an important example of such polymerization and has gained widespread acceptance as an all-purpose adhesive. However, CA-based medical adhesives have never been approved by the U.S. Federal Drug Administration for use below the skin, mainly due to the low biodegradability and biocompatibility of their solid glue after polymerization. In this research, a cross-linking strategy involving the combination of alkyl-CA and the cross-linking agent poly(ethylene glycol)–di(cyanoacrylate) (CA–PEG–CA) to form a copolymeric network was used to synthesize a new generation of biodegradable CA medical adhesives. The degradability could be modulated by adjusting the ratio of CA–PEG–CA to alkyl-CA and the length of PEG. An optimal composite adhesive, LKJ11, was shown to have excellent biodegradability, adhesive capability, and biocompatibility. Importantly, the molecular weight of polycyanoacrylate chains in the polymerized LKJ11 was greatly reduced compared to those polymerized from pure butyl-CA. Thus, the degradation product could be readily extracted. The results showed that LKJ11 represents a new generation of CA-based biodegradable medical adhesives. This advance also provides a general strategy to facilitate the conversion of other polymers with long carbon–carbon main chains to a biodegradable form, thereby expanding the novel applications available for traditional polymeric materials.
Co-reporter:Xiaoju Wang, Cuiping Yang, Chenhong Wang, Leijia Guo, Tianhong Zhang, Zhenqing Zhang, Husheng Yan, Keliang Liu
Materials Science and Engineering: C 2016 Volume 59() pp:766-772
Publication Date(Web):1 February 2016
DOI:10.1016/j.msec.2015.10.084
•Polymeric micelles with α-glutamyl-PEG shells show low protein adsorption.•Polymeric micelles with α-glutamyl-PEG shells have good stealth property.•Polymeric micelles with α-glutamyl-PEG shells show prolonged blood circulation.Although PEG remains the gold standard for stealth functionalization in drug delivery field up to date, complete inhibition of protein corona formation on PEG-coated nanoparticles remains a challenge. To improve the stealth property of PEG, herein an α-glutamyl group was conjugated to the end of PEG and polymeric micelles with α-glutamyl-terminated PEG shells were prepared. After incubation with bovine serum albumin or in fetal calf serum, the size of the micelles changed slightly, while the size of the micelles of similar diblock copolymer but without α-glutamyl group increased markedly. These results indicated that the micelles with α-glutamyl-terminated PEG shells showed low non-specific protein adsorption. In vivo blood clearance kinetics assay showed that the micelles with α-glutamyl-terminated PEG shells exhibited a longer in vivo blood circulation time compared with similar micelles but without α-glutamyl groups. The better stealth property of the micelles with α-glutamyl-terminated PEG shells was presumably attributed to the zwitterionic property of the α-glutamyl groups.
Co-reporter:Leijia Guo, Chenhong Wang, Cuiping Yang, Xiuyan Wang, Tianhong Zhang, Zhenqing Zhang, Husheng Yan, Keliang Liu
Polymer 2016 Volume 84() pp:189-197
Publication Date(Web):10 February 2016
DOI:10.1016/j.polymer.2015.12.056
•Morpholino-terminated PAMAM shows tumor-pH triggered cellular uptake.•Modification of dendrimer with morpholino groups prolongs blood circulation time.•The dendrimer can penetrate deeply to tumors, while remaining long circulation.Short circulation is a disadvantage of dendrimers as drug delivery carriers due to their small size. In this work, pH-sensitive morpholino-terminated generation 5 poly(amido amine) (PAMAM) is prepared. At neutral pH, the dendrimer has a hydrophilic neutral surface and thereby stealth property. Under tumor acidic environments, the dendrimer develops positive charges due to protonation of the morpholino groups, and cellular uptake of the dendrimer is subsequently enhanced. The dendrimer is predicted to penetrate deeper within the tumor due to its small size (∼9 nm), and thereby the pH-sensitive function can be efficiently achieved because the microenvironment in the deeper sites is more acidic. Moreover, the morpholino-terminated PAMAM exhibited longer in vivo circulation time compared to PAMAM and hydroxyl-terminated PAMAM, partly compensating for the disadvantage of short circulation of dendrimers. Furthermore, the morpholino-terminated PAMAM also showed lower cytotoxicity than PAMAM and hydroxyl-terminated PAMAM.
Co-reporter:Liang Luan, Qingbin Meng, Liang Xu, Zhao Meng, Husheng Yan and Keliang Liu
Journal of Materials Chemistry A 2015 vol. 3(Issue 6) pp:1068-1078
Publication Date(Web):04 Dec 2014
DOI:10.1039/C4TB01353K
To overcome barriers associated with gene delivery, a series of peptides consisting of multifunctional fragments, including a cationic amphiphilic α-helical antimicrobial peptide (AMP), a cell penetrating peptide (CPP), TAT, a stearyl moiety, and cysteine residues, were designed and synthesized for evaluation as non-viral gene vectors. TAT and AMP segments were utilized to mediate cellular uptake and endosomal escape, respectively. Stearyl moieties provide an intramolecular hydrophobic environment to promote AMPs to form an α-helical conformation in PBS, and this is beneficial for DNA binding, cellular uptake, and endosomal escape. The α-helical content of the peptides, as well as the particle size, zeta potential, and morphology of the peptide/DNA complexes, was characterized. Fluorescence activated cell sorting (FACS) and confocal microscopy data showed that the peptides were able to efficiently translocate a pGL3 control plasmid across the plasma membrane via endocytosis, and then they successfully evaded endosomal entrapment and possible metabolic degradation. Moreover, one of the peptide vectors exhibited a high transfection efficiency similar to that of Lipofectamine 2000, concomitant with lower cytotoxicity. Overall, a combination of the four functional segments tested was used to generate a non-viral gene vector that synergistically promoted cellular uptake, endosomal escape, and gene expression.
Co-reporter:Jiawei Lu, Huiyan Jia, Leijia Guo, Genghui Zhang, Youjia Cao, Husheng Yan, Keliang Liu
European Polymer Journal 2015 Volume 66() pp:376-385
Publication Date(Web):May 2015
DOI:10.1016/j.eurpolymj.2015.02.041
•Slightly negatively charged and zwitterionic micelles at blood pH.•Positively charged micelles at tumor acidic pH.•Tumor-extracellular pH-triggered positive charge generation.To achieve a good stealth property and to enhance the uptake by tumor cells, polymeric micelles containing a slightly negatively charged and zwitterionic corona at pH 7.4 (i.e., blood pH) and a positively charged surface at a slightly acidic pH (i.e., tumor extracellular pH) were prepared. The amphiphilic diblock copolymer which was used to prepare the polymeric micelles contains a hydrophilic block comprised of nonionic hydrophilic groups, negatively charged groups (carboxyl groups) and pH-triggered positive charge-generation groups (morpholino groups). The zeta potential of the micelles was found to increase as the pH decreased over the pH range covering the blood and tumor tissue pH ranges, and the corona of the micelles should contain zwitterionic groups. This could be due to that, in the pH range studied, more morpholino groups become protonated as the pH decreased, whereas the carboxyl groups were almost completely deprotonated to form carboxylate anions. Furthermore, by adjusting the molar ratio of morpholino to carboxyl groups, the zeta potential of the polymeric micelles was controlled to achieve a slightly negative value at pH 7.4. Thus, the combination of a slightly negatively charged surface and a zwitterionic corona suggests that these micelles would possess good stealth property. When the pH decreased from 7.4 to 6.8 or 6.5, the zeta potential value of the micelles became positive due to increased protonation of the morpholino groups. Correspondingly, the cellular uptake of the micelles by HeLa cells was enhanced.
Co-reporter:Yan Zhang, Chenhong Wang, Yunxiao Huang, Husheng Yan, Keliang Liu
European Polymer Journal 2015 Volume 68() pp:104-114
Publication Date(Web):July 2015
DOI:10.1016/j.eurpolymj.2015.04.033
•Drug load driven by a combination of ionic bonding and hydrophobic effects.•High stability upon extensive dilution due to the core-crosslinking.•High loading capacity and low premature release.•Rapid release upon entry into the target cells.Polymeric micelles containing a poly(ethylene glycol) shell and a disulfide-crosslinked core with a hydrophobic moiety and carboxylic acid groups were prepared. The loading of doxorubicin into the core was achieved with a combination of ionic bonding and hydrophobic effects. The cooperativity of these effects enabled doxorubicin to bind tightly to the core, thereby endowing the system with a high loading capacity and a low rate of premature release in the bloodstream. Disulfide crosslinkages prevented the dissociation of the micelles into unimers upon extensive dilution. Under intracellular-like conditions (e.g., pH 5 with the presence of glutathione), the payload was released at a high rate from the micelles. The release was attributed to cleavage of the disulfide crosslinkages by glutathione and disruption of the ionic bonds at a lower pH due to protonation of the carboxylate anions in the core. Intracellular doxorubicin release was found to positively correlate with intracellular glutathione levels.
Co-reporter:Chenhong Wang;Lei Qiao;Keliang Liu
Journal of Applied Polymer Science 2014 Volume 131( Issue 12) pp:
Publication Date(Web):
DOI:10.1002/app.40405
ABSTRACT
A one-pot synthesis is developed for PEG600-b-poly(glycerol monoacrylate) (PEG600-b-PGA), by which folate and superparamagnetic iron oxide nanoparticles (SPIONs) are assembled to form folic acid-conjugated magnetic nanoparticles (FA-MNPs) as a tumor targeting system. The synthesis consists of a “click” reaction and atom transfer radical polymerization (ATRP) to obtain the well-defined furan-protected maleimido-terminated PEG600-b-poly(solketal acrylate) (PEG600-b-PSA) copolymer. After deprotection, the key copolymer N-maleimido-terminated PEG600-b-PGA is successfully conjugated with thiol derivatives of folate and FITC, respectively. FA-MNPs are developed by assembling of the resulting polymer FA-PEG600-b-PGA with SPIONs, and characterized for their size, surface charge, and superparamagnetic properties. To investigate the cellular uptake of the nanoparticles by Hela cells and φ2 cells using fluoresce technique, FA-FITC-MNPs are also obtained by assembling of FA-PEG600-b-PGA, FITC-PEG600-b-PGA with SPIONs. Qualitative and quantitative determinations of FA-FITC-MNPs show that the particles specifically internalized to Hela cells. No significant cytotoxicity is observed for these two kinds of cell lines. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40405.
Co-reporter:Yan Zhang;Xiao-ju Wang;Miao Guo;Hu-sheng Yan 阎虎生
Chinese Journal of Polymer Science 2014 Volume 32( Issue 10) pp:1329-1337
Publication Date(Web):2014 October
DOI:10.1007/s10118-014-1510-1
Multifunctional nanocarriers with multilayer core-shell architecture were prepared by coating superparamagnetic Fe3O4 nanoparticles with diblock copolymer folate-poly(ethylene glycol)-b-poly(glycerol monomethacrylate) (FA-PEG-b-PGMA), and triblock copolymer methoxy poly(ethylene glycol)-b-poly(2-(dimethylamino) ethyl methacrylate)-b-poly(glycerol monomethacrylate) (MPEG-b-PDMA-b-PGMA). The PGMA segment was attached to the surfaces of Fe3O4 nanoparticles, and the outer PEG shell imparted biocompatibility. In addition, folate was conjugated onto the surfaces of the nanocarriers. Cisplatin was then loaded into the nanocarrier by coordination between the Pt atom in cisplatin and the amine groups in the inner shell of the multilayer architecture. The loaded cisplatin showed pH-responsive release: slower release at pH 7.4 (i.e. mimicking the blood environment) and faster release at more acidic pH (i.e. mimicking endosome/lysosome conditions). All of the cisplatin-loaded nanoparticles showed concentration-dependent cytotoxicity in HeLa cells. However, the folate-conjugated cisplatin-loaded carriers exhibited higher cytotoxicity in HeLa cells than non-folate conjugated cisplatin-loaded carriers.
Co-reporter:Yan Zhang, Chenhong Wang, Chuang Xu, Cuiping Yang, Zhenqing Zhang, Husheng Yan and Keliang Liu
Chemical Communications 2013 vol. 49(Issue 66) pp:7286-7288
Publication Date(Web):24 Jun 2013
DOI:10.1039/C3CC43334J
Micelles with surface morpholino groups were stealthy at blood and normal tissue pH (7.4) due to the unprotonated hydrophilic morpholino groups on the surfaces. At tumor pH (<7), the micelle surfaces were positively charged because of the protonation of the morpholino groups, which promoted the cellular uptake of the micelles.
Co-reporter:Yong Zhang;Jia-jia Chen;Geng-hui Zhang
Chinese Journal of Polymer Science 2013 Volume 31( Issue 2) pp:294-301
Publication Date(Web):2013 February
DOI:10.1007/s10118-013-1190-2
Single-hole hollow polymer nanospheres were fabricated by raspberry-like template method using “graft-from” strategy through atom transfer radical polymerization (ATRP). Nanometer-sized silica spheres were covalently attached onto the surfaces of micrometer-sized silica spheres. Crosslinked polymer shells on the nano-sized spheres outside the attached area were formed by “graft-from” strategy through ATRP. After removal of the silica cores, single-hole hollow crosslinked polymer nanospheres were obtained. In this strategy, most of ATRP monomers may be used and thus many functional groups can be easily incorporated into the single-hole hollow crosslinked polymer nanospheres.
Co-reporter:Zhenhua Xu, Miao Guo, Husheng Yan, Keliang Liu
Reactive and Functional Polymers 2013 73(3) pp: 564-572
Publication Date(Web):March 2013
DOI:10.1016/j.reactfunctpolym.2012.12.012
Co-reporter:Chan Yang, Husheng Yan
Materials Letters 2012 Volume 73() pp:129-132
Publication Date(Web):15 April 2012
DOI:10.1016/j.matlet.2012.01.031
Magnetite nanoparticles with tunable sizes and morphologies were synthesized by heating an aqueous solution of Fe2+/Fe3+ (1/2, molar ratio) and urea without or with additives at 85 °C. Polyhedral magnetite nanocrystals with an average size of ~ 300 nm were prepared without any additive. When poly(vinyl alcohol) (PVA) was used as an additive, microspherical magnetite particles composed of clustered nanocrystals were got. The diameters of the microspheres can be tuned from ~ 100 to ~ 280 nm by changing the concentration of PVA. Larger and looser (porous) microspheres were obtained with acetic acid as the secondary additive in addition to PVA. Magnetite nanorods or flowerlike particles were got with poly(acrylic acid) as the additive. The as-synthesized products showed high saturation magnetization and low coercivity or remanence.Highlights► Magnetite nanoparticles with tunable sizes and morphologies. ► Heating Fe2+/Fe3+/urea/H2O (85 °C) gets polyhedral magnetite nanocrystals. ► Heating Fe2+/Fe3+/urea/HAc/poly(vinyl alcohol)/H2O (85 °C) gets porous microspheres. ► Heating Fe2+/Fe3+/urea/poly(acrylic acid)/H2O (85 °C) gets rods or flowers.
Co-reporter:Yong Zhang, Jiajia Chen, Genghui Zhang, Jiawei Lu, Husheng Yan, Keliang Liu
Reactive and Functional Polymers 2012 72(6) pp: 359-364
Publication Date(Web):June 2012
DOI:10.1016/j.reactfunctpolym.2012.03.010
Co-reporter:Quan Zhang, Liang Luan, Siliang Feng, Husheng Yan, Keliang Liu
Reactive and Functional Polymers 2012 72(3) pp: 198-205
Publication Date(Web):March 2012
DOI:10.1016/j.reactfunctpolym.2012.01.003
Co-reporter:Yanqiang Wang;Junjuan Xu;Yueheng Zhang;Keliang Liu
Macromolecular Bioscience 2011 Volume 11( Issue 11) pp:1499-1504
Publication Date(Web):
DOI:10.1002/mabi.201100196
Co-reporter:Xiutao Li, Yan Liu, Zhenhua Xu, Husheng Yan
European Polymer Journal 2011 Volume 47(Issue 10) pp:1877-1884
Publication Date(Web):October 2011
DOI:10.1016/j.eurpolymj.2011.07.010
Narrow-disperse magnetic microspheres were prepared by alkaline coprecipitation of Fe2+ and Fe3+ ions within poly(acrylic acid–divinylbenzene) microspheres that were prepared by distillation–precipitation copolymerization. Magnetic microspheres with polymer brushes that contain epoxy groups were prepared by graft copolymerization of glycidyl methacrylate and glycerol monomethacrylate via atom transfer radical polymerization (ATRP) from the magnetic microsphere surfaces. Subsequently, magnetic microspheres with thiol-containing polymer brushes were prepared by treating the epoxy group-containing magnetic microspheres with sodium hydrosulfide. Gold nanoparticles were immobilized in the brush layer of the thiol-containing magnetic microspheres through Au–S coordination. The catalytic activity of the gold nanoparticle-immobilized magnetic microspheres was investigated using the reduction of 4-nitrophenol to 4-aminophenol with sodium borohydride as a model reaction. The catalyst could be reused for over 10 cycles without noticeable loss of catalytic activity.Graphical abstractHighlights► Crosslinked polymer microspheres with embedded magnetite nanoparticles. ► Magnetic microspheres with polymeric brushes containing thiol groups. ► Magnetic microspheres with polymeric brushes containing gold nanoparticles. ► Gold nanoparticle-immobilized magnetic microspheres as a catalyst.
Co-reporter:Yan Liu, Husheng Yan
Materials Letters 2011 Volume 65(Issue 7) pp:1063-1065
Publication Date(Web):15 April 2011
DOI:10.1016/j.matlet.2011.01.032
Narrow-size disperse porous carbon microspheres with embedded magnetite nanoparticles were prepared by annealing Fe(III)-containing microspheres composed of a copolymer of acrylic acid and divinylbenzene at 800 °C under inert atmosphere. The Fe(III)-containing microspheres were prepared by uptake of Fe2+ ions through ion exchange process by poly(acrylic acid-divinylbenzene) microspheres that were prepared by distillation–precipitation polymerization, followed by annealing at 250 °C at ambient atmosphere. The carbonization of the microspheres created micropores with a maximum pore diameter of about 0.38 nm and a BET surface area of ~ 200 m2/g. The saturation magnetization of the magnetic carbon microspheres was 31.5 emu/g with a low remnant magnetization and coercivity.
Co-reporter:Miao Guo, Chailu Que, Chenhong Wang, Xiaozhou Liu, Husheng Yan, Keliang Liu
Biomaterials 2011 32(1) pp: 185-194
Publication Date(Web):
DOI:10.1016/j.biomaterials.2010.09.077
Co-reporter:Quan Zhang, Chenhong Wang, Lei Qiao, Husheng Yan and Keliang Liu
Journal of Materials Chemistry A 2009 vol. 19(Issue 44) pp:8393-8402
Publication Date(Web):30 Sep 2009
DOI:10.1039/B910439A
Folate-functionalized magnetic fluids were prepared by direct chemisorption of a folate-tetra(ethylene glycol)-poly(glycerol monoacrylate) (FA-TEG-PGA) conjugate on Fe3O4nanoparticles. In the magnetic fluids, the PGA block of FA-TEG-PGA was chemisorbed onto the Fe3O4nanoparticle surface through its 1,2-diol groups, while the TEG chain conjugated with FA extended into the water matrix. Characterization by transmission electron microscopy, X-ray diffraction and a vibrating sample magnetometer indicated that the pure Fe3O4 superparamagnetic nanoparticles were formed and the coating process did not significantly affect the size and structure of Fe3O4nanoparticles. Fourier transform infrared spectroscopy, UV-vis spectroscopy, thermogravimetric analysis and X-ray photoelectron spectroscopy confirmed the successful coating of FA-TEG-PGA on the Fe3O4nanoparticles, suggested a coating mechanism for the FA-TEG-PGA, and revealed the maximum weight ratio of FA-TEG-PGA to Fe3O4. The dispersion of FA-TEG-PGA-coated Fe3O4nanoparticles possessed excellent stability over a wide range of pH and salt concentrations. Such folate-functionalized magnetic fluids are expected to be targeting contrast agents for magnetic resonance imaging (MRI) applications. This approach represents a new strategy to synthesize functionalized magnetic nanoparticles that form stable dispersions in water and facilitates potential biomedical applications of these magnetic nanoparticles.
Co-reporter:Junsheng Huang;Xiutao Li;Yanhui Zheng;Yong Zhang;Ruiying Zhao;Xicai Gao
Macromolecular Bioscience 2008 Volume 8( Issue 6) pp:508-515
Publication Date(Web):
DOI:10.1002/mabi.200700256
Co-reporter:Shourong Wan;Junsheng Huang;Miao Guo;Hongkai Zhang;Youjia Cao;Keliang Liu
Journal of Biomedical Materials Research Part A 2007 Volume 80A(Issue 4) pp:946-954
Publication Date(Web):2 NOV 2006
DOI:10.1002/jbm.a.31022
Methoxypoly(ethylene glycol)–oligo(aspartic acid) (MPEG–Aspn-NH2, n = 2–5) hybrid block copolymers were synthesized and used as stabilizers to prepare superparamagnetic Fe3O4 nanoparticles with magnetite as the inner core and and poly(ethylene glycol) as the hydrophilic outer shell. The aqueous dispersions of the nanoparticles were stable at pH 2–11 and in 1M NaCl solution, when repeat number, n, was 3 or more. Transmission electron microscopy showed that the nanoparticles, stabilized with MPEG–Asp3-NH2, were about 14 nm in diameter. Magnetic measurements indicated that MPEG–Asp3-NH2-coated iron oxide nanoparticles showed superparamagnetic behavior. Cell adhesion assay and in vitro cell viability/cytotoxicity studies showed that MPEG–Asp3-NH2-coated iron oxide nanoparticles had less effect on cell adhesion/viability and morphology, and less cytotoxicity compared with uncoated, poly (acrylic acid)-coated, and MPEG–poly(acrylic acid)-coated iron oxide nanoparticles. © 2006 Wiley Periodicals, Inc. J Biomed Mater Res, 2006
Co-reporter:Shourong Wan, Junsheng Huang, Husheng Yan and Keliang Liu
Journal of Materials Chemistry A 2006 vol. 16(Issue 3) pp:298-303
Publication Date(Web):08 Nov 2005
DOI:10.1039/B512605C
Stable aqueous iron oxide nanoparticle dispersions were prepared by coprecipitation of ferrous (Fe2+) and ferric (Fe3+) aqueous solution by a base in the presence of graft copolymers, poly(glycerol monoacrylate)-g-poly(PEG methyl ether acrylate) (PGA-g-PEG). PGA-g-PEG was prepared by acidic hydrolysis of poly(solktal acrylate)-g-poly(PEG methyl ether acrylate), which was synthesized by copolymerization of solktal acrylate and PEG methyl ether acrylate by atom transfer radical polymerization (ATRP). The size of the magnetite nanoparticles can be controlled from 4 nm to 18 nm by varying the graft density of the graft copolymers. Structural characterization using X-ray diffraction showed the presence of only the magnetite phase in the nanoparticles. Thermogravimetric analysis confirmed the presence of the graft copolymers on the magnetite surface. The magnetic characterization of the nanoparticles showed that they were superparamagnetic at room temperature.
Co-reporter:Shaoling Cheng;Haiyan Tang
Journal of Applied Polymer Science 2006 Volume 102(Issue 5) pp:4652-4658
Publication Date(Web):28 SEP 2006
DOI:10.1002/app.24702
To investigate the effects of multiple weak interactions on the binding of phenolic compounds by polymeric adsorbents, macroporous polystyrene (PS) resin and PS-based adsorbents with different hydrogen-bond acceptor atoms (PSCH2(OCH2CH2)nOCH3, n = 0, 1, 2, and 3, denoted as PS-EG0, PS-EG1, PS-EG2, and PS-EG3) were prepared. The phenol adsorption strength order on these adsorbents was PS/PS-EG0 < PS-EG1 < PS-EG2 < PS-EG3, indicating that the adsorption on PS and PS-EG0 was driven by hydrophobic and π–π interactions, and the adsorption on PS-EG1, PS-EG2, and PS-EG3 was driven by a hydrogen bond in addition to hydrophobic and π–π interactions. PS-EG2 may adsorb a second phenol molecule on each binding site and PS-EG3 may adsorb second and third ones. The adsorption strength of resorcinol increased in the order of PS, PS-EG1, and PS-EG2, indicating that the adsorption was driven by 0, 1, and 2 hydrogen bonds in addition to hydrophobic and π–π interactions. Similarly, the adsorption of phloroglucinol on PS, PS-EG1, PS-EG2, and PS-EG3 was driven by 0, 1, 2, and 3 hydrogen bonds in addition to hydrophobic and π–π interactions because the adsorption strength increased in this order. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4652–4658, 2006
Co-reporter:Shourong Wan, Yuee Zheng, Yuanqin Liu, Husheng Yan and Keliang Liu
Journal of Materials Chemistry A 2005 vol. 15(Issue 33) pp:3424-3430
Publication Date(Web):19 Jul 2005
DOI:10.1039/B504607F
Highly stable aqueous magnetic fluids were prepared by coating Fe3O4 nanoparticles with poly(glycerol monoacrylate), poly(glycerol monomethacrylate), or diblock copolymers, poly(acrylic acid)-b-poly(glycerol monoacrylate), poly[(N,N-dimethylamino)ethyl methacrylate]-b-poly(glycerol monomethacrylate) or poly(ethylene glycol) monomethyl ether-b-poly(glycerol monoacrylate). These homopolymers and block copolymers were synthesized by atom transfer radical polymerization. These dispersions were stable in 10% NaCl, 10% CaCl2, or in wide pH ranges. In these magnetic fluids, poly(glycerol monoacrylate) or poly(glycerol monomethacrylate) were chemisorbed onto the Fe3O4 nanoparticle surface through their 1,2-diol groups by forming five-membered chelate rings with the Fe atoms, while the other blocks in the cases of the block copolymers as the stabilizers extended into the water matrix. Thus the nanoparticles prepared with these three block copolymers mentioned above respectively contain negatively charged, positively charged or uncharged and biocompatible surfaces under physiological conditions. This procedure provided a good choice for preparing stable magnetic fluids with tailored surfaces and/or tailored functional groups on the surfaces of the magnetic nanoparticles.
Co-reporter:Yuee Zhen;Shourong Wan;Yuanqin Liu;Rongfu Shi;Chunhong Wang
Macromolecular Chemistry and Physics 2005 Volume 206(Issue 5) pp:
Publication Date(Web):28 FEB 2005
DOI:10.1002/macp.200400414
Summary: Solketal acrylate (SA) was homopolymerized by atom transfer radical polymerization (ATRP) using CuBr/N,N,N′,N″,N″-pentamethyldiethylenetriamine as the catalyst and cyclohexanone as the solvent with controlled molecular weights and low polydispersities. The prepared bromine-terminated homopolymers, PSA, were used as macroinitiators to initiate polymerization of tert-butyl acrylate (tBA) under similar ATRP conditions to produce diblock copolymers, PSA-b-PtBA, with controlled molecular weights and low polydispersities. ATRP of SA using bromine-terminated PtBA as the macroinitiator was also carried out and diblock copolymers, PtBA-b-PSA, were obtained. The PSA block was selectively hydrolyzed by stirring for 3 h in 6 N HCl/THF (1/9, v/v) at room temperature to form a poly(glycerol monoacrylate) block. Both blocks of PSA and PtBA were hydrolyzed by stirring in anhydrous trifluoroacetic acid (TFA)/dichloromethane for 4 h, then adding water to the system and stirring for another 3 h to form corresponding diblock copolymers of glycerol monoacrylate and acrylic acid.
Co-reporter:Ruiying Zhao, Yu Yan, Mingxian Li, Husheng Yan
Reactive and Functional Polymers (March 2008) Volume 68(Issue 3) pp:768-774
Publication Date(Web):March 2008
DOI:10.1016/j.reactfunctpolym.2007.11.016
Co-reporter:Yan Zhang, Chenhong Wang, Chuang Xu, Cuiping Yang, Zhenqing Zhang, Husheng Yan and Keliang Liu
Chemical Communications 2013 - vol. 49(Issue 66) pp:NaN7288-7288
Publication Date(Web):2013/06/24
DOI:10.1039/C3CC43334J
Micelles with surface morpholino groups were stealthy at blood and normal tissue pH (7.4) due to the unprotonated hydrophilic morpholino groups on the surfaces. At tumor pH (<7), the micelle surfaces were positively charged because of the protonation of the morpholino groups, which promoted the cellular uptake of the micelles.
Co-reporter:Liang Xu, Tao Zhang, Huajin Dong, Dazheng Cai, Han Han, Qingbin Meng, Yongjia Tang, Qingguo Meng, Zehui Gong, Tianhong Zhang, Zhenqing Zhang, Husheng Yan and Keliang Liu
Journal of Materials Chemistry A 2016 - vol. 4(Issue 23) pp:NaN4155-4155
Publication Date(Web):2016/05/06
DOI:10.1039/C6TB00235H
Addition polymerization usually results in polymers with long carbon–carbon main chains. Cyanoacrylate (CA) is arguably an important example of such polymerization and has gained widespread acceptance as an all-purpose adhesive. However, CA-based medical adhesives have never been approved by the U.S. Federal Drug Administration for use below the skin, mainly due to the low biodegradability and biocompatibility of their solid glue after polymerization. In this research, a cross-linking strategy involving the combination of alkyl-CA and the cross-linking agent poly(ethylene glycol)–di(cyanoacrylate) (CA–PEG–CA) to form a copolymeric network was used to synthesize a new generation of biodegradable CA medical adhesives. The degradability could be modulated by adjusting the ratio of CA–PEG–CA to alkyl-CA and the length of PEG. An optimal composite adhesive, LKJ11, was shown to have excellent biodegradability, adhesive capability, and biocompatibility. Importantly, the molecular weight of polycyanoacrylate chains in the polymerized LKJ11 was greatly reduced compared to those polymerized from pure butyl-CA. Thus, the degradation product could be readily extracted. The results showed that LKJ11 represents a new generation of CA-based biodegradable medical adhesives. This advance also provides a general strategy to facilitate the conversion of other polymers with long carbon–carbon main chains to a biodegradable form, thereby expanding the novel applications available for traditional polymeric materials.
Co-reporter:Liang Luan, Qingbin Meng, Liang Xu, Zhao Meng, Husheng Yan and Keliang Liu
Journal of Materials Chemistry A 2015 - vol. 3(Issue 6) pp:NaN1078-1078
Publication Date(Web):2014/12/04
DOI:10.1039/C4TB01353K
To overcome barriers associated with gene delivery, a series of peptides consisting of multifunctional fragments, including a cationic amphiphilic α-helical antimicrobial peptide (AMP), a cell penetrating peptide (CPP), TAT, a stearyl moiety, and cysteine residues, were designed and synthesized for evaluation as non-viral gene vectors. TAT and AMP segments were utilized to mediate cellular uptake and endosomal escape, respectively. Stearyl moieties provide an intramolecular hydrophobic environment to promote AMPs to form an α-helical conformation in PBS, and this is beneficial for DNA binding, cellular uptake, and endosomal escape. The α-helical content of the peptides, as well as the particle size, zeta potential, and morphology of the peptide/DNA complexes, was characterized. Fluorescence activated cell sorting (FACS) and confocal microscopy data showed that the peptides were able to efficiently translocate a pGL3 control plasmid across the plasma membrane via endocytosis, and then they successfully evaded endosomal entrapment and possible metabolic degradation. Moreover, one of the peptide vectors exhibited a high transfection efficiency similar to that of Lipofectamine 2000, concomitant with lower cytotoxicity. Overall, a combination of the four functional segments tested was used to generate a non-viral gene vector that synergistically promoted cellular uptake, endosomal escape, and gene expression.
Co-reporter:Quan Zhang, Chenhong Wang, Lei Qiao, Husheng Yan and Keliang Liu
Journal of Materials Chemistry A 2009 - vol. 19(Issue 44) pp:NaN8402-8402
Publication Date(Web):2009/09/30
DOI:10.1039/B910439A
Folate-functionalized magnetic fluids were prepared by direct chemisorption of a folate-tetra(ethylene glycol)-poly(glycerol monoacrylate) (FA-TEG-PGA) conjugate on Fe3O4nanoparticles. In the magnetic fluids, the PGA block of FA-TEG-PGA was chemisorbed onto the Fe3O4nanoparticle surface through its 1,2-diol groups, while the TEG chain conjugated with FA extended into the water matrix. Characterization by transmission electron microscopy, X-ray diffraction and a vibrating sample magnetometer indicated that the pure Fe3O4 superparamagnetic nanoparticles were formed and the coating process did not significantly affect the size and structure of Fe3O4nanoparticles. Fourier transform infrared spectroscopy, UV-vis spectroscopy, thermogravimetric analysis and X-ray photoelectron spectroscopy confirmed the successful coating of FA-TEG-PGA on the Fe3O4nanoparticles, suggested a coating mechanism for the FA-TEG-PGA, and revealed the maximum weight ratio of FA-TEG-PGA to Fe3O4. The dispersion of FA-TEG-PGA-coated Fe3O4nanoparticles possessed excellent stability over a wide range of pH and salt concentrations. Such folate-functionalized magnetic fluids are expected to be targeting contrast agents for magnetic resonance imaging (MRI) applications. This approach represents a new strategy to synthesize functionalized magnetic nanoparticles that form stable dispersions in water and facilitates potential biomedical applications of these magnetic nanoparticles.