Co-reporter:Shanlong Li, Yinglin Zhang, Hong Liu, Chunyang Yu, Yongfeng Zhou, and Deyue Yan
Langmuir September 26, 2017 Volume 33(Issue 38) pp:10084-10084
Publication Date(Web):August 31, 2017
DOI:10.1021/acs.langmuir.7b02411
Asymmetric vesicles are valuable for understanding and mimicking cell and practical biomedicine applications. Recently, a very straightforward methodology for fabricating asymmetric polymersome was developed by Lodge’s group through the coassembly of polystyrene-b-poly(ethylene oxide) (PS-b-PEO) and polybutadiene-b-poly(ethylene oxide) (PB-b-PEO) block copolymers at the interface of a polystyrene/polybutadiene/chloroform (PS/PB/CHCl3) emulsion. However, the in-depth microscopic mechanism for the formation of asymmetric polymersomes remains unclear. To address this issue, in this article, the coassembly process for the formation of the asymmetric polymersomes in Asano’s experimental system was systematically investigated by employing a dissipative particle dynamics (DPD) simulation. Our results definitely demonstrate the formation of the asymmetric polymersomes such as that in the experiments and that the bilayer formed through the folding and crossing of the PEO blocks. Besides, from the microscopic view, three stages can be discerned in the formation process: (1) the formation of micelles, (2) the micelle diffusion to the interface, and (3) the micelle rearrangement at the interface to form an asymmetric polymersome. Meanwhile, the incompatibility among PS, PB, and PEO is proven to be the main driving force for asymmetric polymersome formation. Moreover, the effects of the order of addition of copolymers and the volume fraction of PEO blocks on the structure of the asymmetric polymersomes are also investigated. We find that the formation process is affected severely by the order of addition, and adding PS-b-PEO first can make the asymmetric bilayer more perfect. Not only that, but perfect asymmetric polymersomes can be formed only when the volume fraction of PEO (fPEO) is greater than 0.55. We believe the present work can extend the knowledge of the self-assembly of asymmetric polymersomes, especially with respect to the self-assembly mechanism.
Co-reporter:Chuanlong Li;Chuanshuang Chen;Shanlong Li;Tahir Rasheed;Ping Huang;Tong Huang;Yinglin Zhang;Wei Huang
Polymer Chemistry (2010-Present) 2017 vol. 8(Issue 32) pp:4688-4695
Publication Date(Web):2017/08/15
DOI:10.1039/C7PY00908A
This work reports on the preparation and functionalization of novel alternating copolymer vesicles. An amphiphilic alternating copolymer was synthesized first by the epoxy-thiol click reaction of 1,7-octadienediepoxide and 1,4-dithiothreitol. Then its self-assembly in selective solvents was studied through a simple injection method. The size and morphology of the self-assemblies were investigated by dynamic light scattering (DLS) and transmission electron microscope (TEM), scanning electron microscope (SEM), atomic force microscope (AFM) and cryogenic transmission electron microscope (cryo-TEM) measurements. The results showed that the abovementioned alternating copolymers could self-assemble into vesicles with a monolayer structure. Then a modular click reaction was employed to functionalize the obtained vesicles. Two kinds of functional groups, including the carboxyl group and the amino group, were successively introduced into the vesicles through the facile click-copolymerization of the alternating copolymers, indicating that the modular click reaction is quite potent in functionalizing these vesicles. The combined advantages of facile synthesis, self-assembly and functionalization offer a promising perspective for the application of such alternating copolymer vesicles.
Co-reporter:Haina Tan;Chunyang Yu;Zhongyuan Lu;Deyue Yan
Soft Matter (2005-Present) 2017 vol. 13(Issue 36) pp:6178-6188
Publication Date(Web):2017/09/20
DOI:10.1039/C7SM01170A
Self-assembly of amphiphilic hyperbranched multiarm copolymers (HMCs) has shown great potential for preparing all kinds of delicate supramolecular structures in all scales and dimensions in solution. However, theoretical studies on the influencing factors for the self-assembly of HMCs have been greatly lagging behind. The phase diagram of HMCs in selective solvents is very necessary but has not been disclosed up to now. Here, the self-assembly of HMCs with different hydrophilic fractions in various solvents was studied systematically by using dissipative particle dynamics (DPD) simulations. Three morphological phase diagrams are constructed and a rich variety of morphologies, ranging from spherical micelles, worm-like micelles, membranes, vesicles, vesosomes, small micellar aggregates (SMAs), and aggregates of spherical and worm-like micelles to helical micelles, are obtained. In addition, both the self-assembly mechanisms and the dynamic processes for the formation of these self-assemblies have been systematically investigated. The simulation results are consistent with available experimental observations. Besides, several novel structures, like aggregates of spherical and worm-like micelles, vesosomes and helical micelles, are firstly discovered for HMC self-assembly. We believe the current work will extend the knowledge on the self-assembly of HMCs, especially on the control of supramolecular structures and on fabricating novel self-assemblies.
Co-reporter:Lei Huang;Zuotao Lei;Tong Huang;Yongping Bai
Nanoscale (2009-Present) 2017 vol. 9(Issue 6) pp:2145-2149
Publication Date(Web):2017/02/09
DOI:10.1039/C6NR09379E
This paper reports the aqueous self-assembly of giant elliptical platelets over 20 μm in axial length, from a novel polyamide. Both the self-assembly pathway and mechanism were studied using morphology and X-ray characterizations. The polymer first self-organizes into small quadrangular frustum pyramid platelets, and then these small platelets can be further installed into giant elliptical platelets through an “installation art”-like hierarchical self-assembly process driven by crystallization. The as-prepared regular giant platelets can further aggregate together into multi-horned or flower-like superstructures.
Co-reporter:Tong Huang, Zhilin Hou, Qingsong Xu, Lei Huang, Chuanlong Li, and Yongfeng Zhou
Langmuir 2017 Volume 33(Issue 1) pp:
Publication Date(Web):December 6, 2016
DOI:10.1021/acs.langmuir.6b03869
This study reports the first polymer vesicle sensor for the visual detection of SO2 and its derivatives in water. A strong binding ability between tertiary alkanolamines and SO2 has been used as the driving force for the detection by the graft of tertiary amine alcohol (TAA) groups onto an amphiphilic hyperbranched multiarm polymer, which can self-assemble into vesicles with enriched TAA groups on the surface. The polymer vesicles will undergo proton exchange with cresol red (CR) to produce CR-immobilized vesicles (CR@vesicles). Subsequently, through competitive binding with the TAA groups between CR and SO2 or HSO3–, the CR@vesicles (purple) can quickly change into SO2@vesicles (colorless) with the release of protonated CR (yellow). Such a fast purple to yellow transition in the solution allows the visual detection of SO2 or its derivatives in water by the naked eye. A visual test paper for SO2 gas has also been demonstrated by the adsorption of CR@vesicles onto paper. Meanwhile, the detection limit of CR@vesicles for HSO3– is approximately 25 nM, which is improved by approximately 30 times when compared with that of small molecule-based sensors with a similar structure (0.83 μM). Such an enhanced detection sensitivity should be related to the enrichment of TAA groups as well as the CR in CR@vesicles. In addition, the CR@vesicle sensors also show selectivity and specificity for the detection of SO2 or HSO3– among anions such as F–, Br–, Cl–, SO42–, NO2–, C2O42–, S2O32–, SCN–, AcO–, SO32–, S2–, and HCO3–.
Co-reporter:Chunyang Yu, Li Ma, Ke Li, Shanlong Li, Yannan Liu, Lifen Liu, Yongfeng ZhouDeyue Yan
Langmuir 2017 Volume 33(Issue 1) pp:
Publication Date(Web):December 21, 2016
DOI:10.1021/acs.langmuir.6b03480
This paper investigates the pH-responsive self-assembly of an amphiphilic carboxyl-terminated polyester dendrimer, H20–COOH, in aqueous solution using the dissipative particle dynamics method. The electrostatic interactions were described by introducing the explicit interaction between the smeared charges on ionized polymer beads and the counterions. The results show that the self-assemblies could change from unimolecular micelles, microphase-separated small micelles, wormlike micelles, sheetlike micelles, and small vesicles to large vesicles with the decrease in the degree of ionization (α) of carboxylic acid groups. In addition, the detailed self-assembly mechanisms and the molecular packing models have also been disclosed for each self-assembly stages. Interestingly, the wormlike micelles are found to change from linear to branched when α decreases from 0.182 to 0.109. The current work might serve as a comprehensive understanding on the effect of carboxylic acid groups on the self-assembly behaviors of dendritic polymers.
Co-reporter:Chunyang Yu;Li Ma;Wei Huang;Jingui Qin
Science China Chemistry 2017 Volume 60( Issue 3) pp:377-384
Publication Date(Web):2017 March
DOI:10.1007/s11426-016-0431-1
In this work, all-atom molecular dynamics simulations were employed to study the influence of the side alkyl chain on glass transition behavior of several carbazole trimers (CT) in a temperature range from 423 to 183 K. The glass transition temperatures were obtained from the break in the slope of the volume-temperature curves and found to agree with the experimental values. The short time dynamics of four CT molecules were probed by using velocity autocorrelation functions and mean-square displacements. The current studies showed that the dynamics of CT systems can be easily interpreted through the cage effect. Furthermore, the investigation of the torsional autocorrelation function and P2-state/P3-state functions showed that the rotational barriers of side chains can slow down the conformational relaxation and lead to stronger temperature dependence of conformational relaxation. The relaxation time, characteristic time of P2-state(t) and P3-state(t) functions were all found to have Arrhenius-type temperature dependence.
Co-reporter:Lei Huang, Chunyang Yu, Tong Huang, Shuting Xu, Yongping Bai and Yongfeng Zhou
Nanoscale 2016 vol. 8(Issue 9) pp:4922-4926
Publication Date(Web):05 Feb 2016
DOI:10.1039/C5NR08596A
This study reports the self-assembly of novel polymer vesicles from an amphiphilic multiblock copolyamide, and the vesicles show a special structure with an ultrathin wall thickness of about 4.5 nm and a combined bilayer and monolayer packing model. Most interestingly, the vesicles are ultrasound-responsive and can release the encapsulated model drugs in response to ultrasonic irradiation.
Co-reporter:Yannan Liu, Shanlong Li, Ke Li, Yongli Zheng, Meng Zhang, Caiyun Cai, Chunyang Yu, Yongfeng Zhou and Deyue Yan
Chemical Communications 2016 vol. 52(Issue 60) pp:9394-9397
Publication Date(Web):13 Jun 2016
DOI:10.1039/C6CC03595G
A novel hybrid light-harvesting antenna with a srikaya-like structure of multi-graphene quantum dots (GQDs) as donors and one porphyrin unimolecular micelle as the acceptor was constructed through electrostatic self-assembly. The constructed antenna showed a high energy transfer efficiency of up to 93.6% and an antenna effect of 7.3 in an aqueous solution.
Co-reporter:Wenfeng Jiang, Yong Liu, Chunyang Yu, Shanlong Li, Yongjin Li and Yongfeng Zhou
Chemical Communications 2016 vol. 52(Issue 53) pp:8223-8226
Publication Date(Web):13 May 2016
DOI:10.1039/C6CC03445D
This study reports a new category of stimuli-responsive morphological transitions, i.e., from one morphology (e.g., vesicles) to another two different ones (e.g., nanosheets and nanofibers), by investigating the light-responsive self-assembly behaviour of a “latent double-amphiphilic” linear-hyperbranched supramolecular block copolymer.
Co-reporter:Chunyang Yu, Li Ma, Ke Li, Shanlong Li, Yannan Liu, Yongfeng Zhou and Deyue Yan
Physical Chemistry Chemical Physics 2016 vol. 18(Issue 32) pp:22446-22457
Publication Date(Web):19 Jul 2016
DOI:10.1039/C6CP03726G
Hyperbranched polyglycerol (HPG) is one of the most important hyperbranched polymers (HBPs) due to its interesting properties and applications. Herein, the conformation of HPGs depending on the degree of polymerization (DP) and the degree of branching (DB) is investigated explicitly by molecular dynamics simulations. This study shows that the radius of gyration (Rg) scales as Rg ∼ DP1/3, which is in close agreement with the result of the SANS experiment. For HPGs with the same DP, the radius of gyration, asphericities and solvent accessible surface area all monotonically decrease with the increase of DB; while for HPGs with the same DB, the molecular anisotropy decreases with the increase of DP. The radial density investigation discloses that the cavities are randomly distributed in the interior of the HPG core to support the “dendritic box effect”, which can be used to encapsulate the guest molecules. Interestingly, the terminal groups of HPGs with a high Wiener index (WI) are more favorable to fold back into the interiors than those with the low WI when in water. For the hyperbranched multi-arm copolymer with a HPG core and many polyethylene glycol (PEG) arms, drug encapsulation studies show that the PEG caps can not only effectively prevent tamoxifen from leaving the HPG core, but also encapsulate tamoxifen inside the PEG chains. These simulation results have provided more details for understanding the structure–property relationships of HPGs in water.
Co-reporter:Yunzhou Ni, Gangsheng Tong, Jie Wang, Huimei Li, Feng Chen, Chunyang Yu and Yongfeng Zhou
RSC Advances 2016 vol. 6(Issue 47) pp:40698-40705
Publication Date(Web):19 Apr 2016
DOI:10.1039/C6RA05902C
A pre-mixing and post-polymerization strategy has been developed for one-pot preparation of pomegranate-like polydopamine (PDA) stabilized small gold nanoparticles (AuNPs) with sizes smaller than 5 nm in aqueous media. Firstly, the pre-mixing of dopamine (DA) and HAuCl4 was used to generate the Au clusters as nucleating seeds. Secondly, the rapid self-polymerization of DA into polydopamine (PDA) and simultaneous Au redox reaction were initiated when the pH of the reaction system was tuned to 8 by the injection of a NaOH solution into the mixture, leading to the formation of the pomegranate-like PDA–AuNPs nanocomposites with small AuNPs well dispersed inside. The as-prepared nanocomposites exhibited superior stability in high saline conditions (500 mM NaCl) and were able to be coated onto a filter paper to form paper catalysts, which were used as recyclable catalysts for the reduction of high concentrated (50 mM) 4-nitrophenol (4-NP) with a TOF of 1006 h−1.
Co-reporter:Yannan Liu;Jiyang Jin;Hongping Deng;Ke Li;Dr. Yongli Zheng;Dr. Chunyang Yu ; Yongfeng Zhou
Angewandte Chemie International Edition 2016 Volume 55( Issue 28) pp:7952-7957
Publication Date(Web):
DOI:10.1002/anie.201601516
Abstract
A micelle-like hybrid natural–artificial light-harvesting nanosystem was prepared through protein-framed electrostatic self-assembly of phycocyanin and a four-armed porphyrin star polymer. The nanosystem has a special structure of pomegranate-like unimolecular micelle aggregate with one phycocyanin acceptor in the center and multiple porphyrin donors in the shell. It can inhibit donor self-quenching effectively and display efficient transfer of excitation energy (about 80.1 %) in water. Furthermore, the number of donors contributing to a single acceptor could reach as high as about 179 in this nanosystem.
Co-reporter:Yannan Liu;Jiyang Jin;Hongping Deng;Ke Li;Dr. Yongli Zheng;Dr. Chunyang Yu ; Yongfeng Zhou
Angewandte Chemie 2016 Volume 128( Issue 28) pp:8084-8089
Publication Date(Web):
DOI:10.1002/ange.201601516
Abstract
A micelle-like hybrid natural–artificial light-harvesting nanosystem was prepared through protein-framed electrostatic self-assembly of phycocyanin and a four-armed porphyrin star polymer. The nanosystem has a special structure of pomegranate-like unimolecular micelle aggregate with one phycocyanin acceptor in the center and multiple porphyrin donors in the shell. It can inhibit donor self-quenching effectively and display efficient transfer of excitation energy (about 80.1 %) in water. Furthermore, the number of donors contributing to a single acceptor could reach as high as about 179 in this nanosystem.
Co-reporter:Tong Huang, Huimei Li, Lei Huang, Shanlong Li, Ke Li, and Yongfeng Zhou
Langmuir 2016 Volume 32(Issue 4) pp:991-996
Publication Date(Web):January 14, 2016
DOI:10.1021/acs.langmuir.5b04478
This work reports on the facile preparation of hybrid polymer vesicles with alterable armors of metal nanoparticles by using a novel hyperbranched polymer vesicle as the templates. The vesicles were prepared through the aqueous self-assembly of a hyperbranched multiarm copolymers with many tertiary amino groups on the surface, which can electrostatically complexed or coordinated with metal ions like AuCl4–, PtCl62–, and Ag+ ions. Subsequently, the vesicles coated with metal ions can be in situ reduced into metal nanoparticles, through which a series of surface-engineered vesicles (Au@vesicles, Ag@vesicles, Pt@vesicles) with an advantage of fully covered metal nanoparticles on the surface could be readily prepared. The morphologies, structures, and formation mechanism of the as-prepared hybrid vesicles were carefully characterized, and the obtained hybrid vesicles also showed great potentials in catalysis and surface-enhanced Raman scattering (SERS) applications.
Co-reporter:Wenfeng Jiang, Yongfeng Zhou and Deyue Yan
Chemical Society Reviews 2015 vol. 44(Issue 12) pp:3874-3889
Publication Date(Web):22 Oct 2014
DOI:10.1039/C4CS00274A
Vesicles, including lipid vesicles, surfactant vesicles, as well as polymer vesicles, have been extensively investigated over the past fifty years. Among them, polymer vesicles have attracted more and more attention because of their low permeability, superior stability and toughness, in addition to the numerous possibilities for tailoring physical, chemical and biological properties. Polymer vesicles are generally fabricated through the self-assembly of amphiphilic polymers with a linear architecture. Recently, as representative polymers with a highly branched three-dimensional architecture, hyperbranched polymers have also exhibited great potential for preparing vesicles. The resultant hyperbranched polymer vesicles, defined as branched-polymersomes (BPs), have shown unique properties, such as giant and easily tuned vesicle sizes, facile functionalization, a special formation mechanism, and appealing solution behaviours. In this tutorial review, ten years of advances in BPs have been summarized since their first discovery in the year 2004, including the syntheses of vesicle-forming hyperbranched polymers, self-assembly methods, self-assembly mechanisms, as well as the special properties. In addition, the cytomimetic, biomedical and other initiatory applications of BPs are also included.
Co-reporter:Yujiao Fan, Dapeng Zhang, Jie Wang, Haibao Jin, Yongfeng Zhou and Deyue Yan
Chemical Communications 2015 vol. 51(Issue 33) pp:7234-7237
Publication Date(Web):19 Mar 2015
DOI:10.1039/C5CC01802A
This work reports the self-assembly of anion-exchangeable vesicles from an amphiphilic hyperbranched polymeric ionic liquid (HBPIL). By a simple one-step anion exchange with methyl orange, the obtained HBPILs could self-assemble into pH-indicative and colorful vesicles in water with color changes directly visible to the naked eye in response to solution pH. In addition, by another step of anion exchange with bovine serum albumin (BSA), the BSA-coated vesicles could also be readily prepared.
Co-reporter:Yun-Zhou Ni, Wen-Feng Jiang, Gang-Sheng Tong, Jian-Xin Chen, Jie Wang, Hui-Mei Li, Chun-Yang Yu, Xiao-hua Huang and Yong-Feng Zhou
Organic & Biomolecular Chemistry 2015 vol. 13(Issue 3) pp:686-690
Publication Date(Web):14 Nov 2014
DOI:10.1039/C4OB02080D
A miscible tetrahydrofuran–tris buffer mixture has been used to fabricate polydopamine hollow capsules with a size of 200 nm and with a shell thickness of 40 nm. An unusual non-emulsion soft template mechanism has been disclosed to explain the formation of capsules. The results indicate that the capsule structure is highly dependent on the volume fraction of tetrahydrofuran as well as the solvent, and the shell thickness of capsules can be controlled by adjusting the reaction time and dopamine concentration.
Co-reporter:Dapeng Zhang, Yujiao Fan, Huimei Li, Ke Li, Yuan Yao, Yongfeng Zhou and Deyue Yan
RSC Advances 2015 vol. 5(Issue 59) pp:47762-47765
Publication Date(Web):22 May 2015
DOI:10.1039/C5RA08661B
This work reports the synthesis, self-assembly and light-responsive disassembly of a novel dumbbell-like supramolecular triblock copolymer (DSTC). The DSTC has an amphiphilic hyperbranched-linear-hyperbranched structure and can self-assemble into monolayer vesicles in water. In addition, the vesicles could disassemble into unimers under UV light due to the trans-to-cis isomerization of the AZO groups.
Co-reporter:Haibao Jin, Yongfeng Zhou, Wei Huang, Yongli Zheng, Xinyuan Zhu and Deyue Yan
Chemical Communications 2014 vol. 50(Issue 46) pp:6157-6160
Publication Date(Web):11 Mar 2014
DOI:10.1039/C4CC00609G
Large-scale and robust vesicle aggregates were obtained through molecular recognition among cell-sized polymer vesicles, carbon nanotubes and AuNPs, driven by adhesion interactions between Au and polydopamine. Vesicle fusion was effectively avoided in this three-component vesicle aggregation process.
Co-reporter:Tong Huang, Xiaohua Huang, Xiaoyi Sun, Yongfeng Zhou, Yongping Bai and Deyue Yan
Chemical Communications 2014 vol. 50(Issue 55) pp:7363-7366
Publication Date(Web):21 May 2014
DOI:10.1039/C4CC02520B
This study describes a new method to prepare monodisperse polystyrene (PS) colloidal nanoparticles with controlled size ranging from 60 nm to 140 nm by the direct polymerization of styrene and divinylbenzene inside the bilayers of the polydisperse hyperbranched polymer vesicles.
Co-reporter:Dr. Yuling Wang;Dr. Bin Li;Haibao Jin; Yongfeng Zhou; Zhongyuan Lu;Deyue Yan
Chemistry – An Asian Journal 2014 Volume 9( Issue 8) pp:2281-2288
Publication Date(Web):
DOI:10.1002/asia.201402146
Abstract
Hyperbranched multiarm copolymers (HMCs) have been shown to hold great potential as precursors in self-assembly, and many impressive supramolecular structures have been prepared through the self-assembly of HMCs in solution. However, theoretical studies on the corresponding self-assembly mechanism have been greatly lagging behind. Herein, we report the self-assembly of normal or reverse vesicles from amphiphilic HMCs by dissipative particle dynamics (DPD) simulation. The simulation disclosed both the self-assembly mechanisms and dynamics of vesicles. It indicates that the self-assembly of HMCs involves several steps, from randomly distributed unimolecular micelles to small spherical micelles, to membrane-like micelles, to finally small vesicles. The membranes are formed through the direct aggregation and lateral fusion of small micelles, and the bending and closing of the membranes give rise to small vesicles. Finally, large and steady vesicles are formed through the fusion of small vesicles. In addition, the bilayer or monolayer molecular packing modes as well as the mircrophase separation behaviors of HMCs in normal or reverse vesicles have also been studied. These simulation results explore details that cannot be observed in the experiments to a certain degree, and have extended the understanding of the vesicular self-assembly process of HMCs.
Co-reporter:Songrui Yu, Ruijiao Dong, Jianxin Chen, Feng Chen, Wenfeng Jiang, Yongfeng Zhou, Xinyuan Zhu, and Deyue Yan
Biomacromolecules 2014 Volume 15(Issue 5) pp:
Publication Date(Web):April 21, 2014
DOI:10.1021/bm5002203
A novel targeting cancer imaging platform based on aptamer-functionalized amphiphilic hyperbranched copolymer conjugates, which can self-assemble into nanoscopic micelles with a core–shell structure and a narrow size distribution, has been designed and synthesized. The size, morphology, fluorescence performance, and cytotoxicity of micelles were studied by dynamic light scattering, transmission electron microscopy, fluorescence spectroscopy, and a 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide colorimetric assay. The results indicate that these micelles have low cytotoxicity against MCF-7 cells and can be easily internalized by MCF-7 cells. In addition, they also exhibit enhanced cell uptake, excellent fluorescence properties, and smart targeting capability in vitro, indicating great potential to be promising carriers for bioimaging and cancer specific delivery.
Co-reporter:Yong Liu ; Chunyang Yu ; Haibao Jin ; Binbin Jiang ; Xinyuan Zhu ; Yongfeng Zhou ; Zhongyuan Lu ;Deyue Yan
Journal of the American Chemical Society 2013 Volume 135(Issue 12) pp:4765-4770
Publication Date(Web):March 6, 2013
DOI:10.1021/ja3122608
Herein, we report a novel Janus particle and supramolecular block copolymer consisting of two chemically distinct hyperbranched polymers, which is coined as Janus hyperbranched polymer. It is constructed by the noncovalent coupling between a hydrophobic hyperbranched poly(3-ethyl-3-oxetanemethanol) with an apex of an azobenzene (AZO) group and a hydrophilic hyperbranched polyglycerol with an apex of a β-cyclodextrin (CD) group through the specific AZO/CD host–guest interactions. Such an amphiphilic supramolecular polymer resembles a tree together with its root very well in the architecture and can further self-assemble into unilamellar bilayer vesicles with narrow size distribution, which disassembles reversibly under the irradiation of UV light due to the trans-to-cis isomerization of the AZO groups. In addition, the obtained vesicles could further aggregate into colloidal crystal-like close-packed arrays under freeze-drying conditions. The dynamics and mechanism for the self-assembly of vesicles as well as the bilayer structure have been disclosed by a dissipative particle dynamics simulation.
Co-reporter:Ruijiao Dong, Bangshang Zhu, Yongfeng Zhou, Deyue Yan and Xinyuan Zhu
Polymer Chemistry 2013 vol. 4(Issue 4) pp:912-915
Publication Date(Web):07 Jan 2013
DOI:10.1039/C2PY21060F
A novel class of azobenzene-containing polymeric systems with reversible trans–cis photoisomerization behavior driven by visible light (ca. 450 nm) has been successfully prepared and this opens up a pathway for azobenzene-based systems in biomedical applications.
Co-reporter:Yuling Wang, Bin Li, Yongfeng Zhou, Zhongyuan Lu and Deyue Yan
Soft Matter 2013 vol. 9(Issue 12) pp:3293-3304
Publication Date(Web):08 Feb 2013
DOI:10.1039/C3SM27396B
Dendritic multiarm copolymers, including dendrimer multiarm copolymers and hyperbranched multiarm copolymers, have shown great potential to be excellent precursors in self-assembly, and many impressive supramolecular structures have been prepared through the solution self-assembly of them. However, the corresponding theoretical studies on the self-assembly mechanism have been greatly lagging behind. Herein, we report the micellization behaviors of amphiphilic dendritic multiarm copolymers with a hydrophobic dendritic core and many hydrophilic arms by dissipative particle dynamics simulations. Both the self-assembly mechanisms and the dynamic self-assembly processes for the formation of unimolecular micelles, microphase-separated small micelles, and large multimolecular micelles have been disclosed through the simulations. Most importantly, the work has proved the large multimolecular micelles are a kind of multimicelle aggregate (MMA) with two formation mechanisms. One is called the unimolecular micelle aggregate (UMA) mechanism, which describes the formation of large multimolecular micelles from direct aggregation of unimolecular micelles; the other is called the small micelle aggregate (SMA) mechanism, which shows that the dendritic multiarm copolymers first self-assemble into small micelles and then the small micelles further aggregate into large multimolecular micelles. In addition, the microphase separation model of the dendritic multiarm copolymers as well as the effects on the formations of UMAs and SMAs are also discussed. These simulation results agree well with experimental observations, and have extended the understanding of the micellization process of dendritic multiarm copolymers.
Co-reporter:Yongping Bai, Lei Huang, Tong Huang, Jun Long, Yongfeng Zhou
Polymer 2013 Volume 54(Issue 16) pp:4171-4176
Publication Date(Web):19 July 2013
DOI:10.1016/j.polymer.2013.05.070
A novel water-soluble copolyamide based on Nylon 66 was synthesized via solution-melt polycondensation of hexanedioic acid and sodium 5-sulfoisophthalate with 1,6-diaminohexane. The chemical structures of the products were ascertained by various spectroscopic techniques (FT-IR, Raman, and 1H NMR). The thermal properties of the polyamides under consideration were measured by TGA and DSC. According to the temperature dependence of FTIR spectra, it was found that the average strength of the intermolecular hydrogen bond of the water-soluble copolyamides becomes weak with increasing the temperature. It was found that the obtained random copolyamides could self-assemble into spherical micelles in aqueous solution with the size dependent on the hydrophilic fraction according to the DLS and TEM measurements.
Co-reporter:Haibao Jin, Wei Huang, Xinyuan Zhu, Yongfeng Zhou and Deyue Yan
Chemical Society Reviews 2012 vol. 41(Issue 18) pp:5986-5997
Publication Date(Web):13 Jul 2012
DOI:10.1039/C2CS35130G
Self-assembly of amphiphilic hyperbranched polymers (HBPs) is a newly emerging research area and has attracted increasing attention due to the great advantages in biomedical applications. This tutorial review focuses on the self-assembly of biocompatible or biodegradable amphiphilic HBPs and their cytomimetic applications, and specialities or advantages therein owing to the hyperbranched structure have also been summarized. As shown here, various supramolecular structures including micelles, vesicles, tubes, fibers and films have been prepared through the primary self-assembly processes. The primary self-assemblies can be further assembled into more complex structures through hierachical self-assembly processes. Besides, the hyperbranched polymer vesicles have demonstrated great potential to be used as model membranes to mimic cellular behaviors, such as fusion, fission and cell aggregation. Other biomedical applications of HBPs as well as their self-assemblies are also briefly summarized.
Co-reporter:Yong Liu, Yuan Gao, Qinghua Lu, Yongfeng Zhou and Deyue Yan
Nanoscale 2012 vol. 4(Issue 1) pp:224-230
Publication Date(Web):10 Nov 2011
DOI:10.1039/C1NR11151E
As inspired from nature's strategy to prepare collagen, herein we report a hierarchical solution self-assembly method to prepare multi-dimensional and multi-scale supra-structures from the building blocks of pristine titanate nanotubes (TNTs) around 10 nm. With the help of amylose, the nanotubes was continuously self-assembled into helically wrapped TNTs, highly aligned fibres, large bundles, 2D crystal facets and 3D core–shell hybrid crystals. The amyloses work as the glue molecules to drive and direct the hierarchical self-assembly process extending from microscopic to macroscopic scale. The whole self-assembly process as well as the self-assembly structures were carefully characterized by the combination methods of 1H NMR, CD, Hr-SEM, AFM, Hr-TEM, SAED pattern and EDX measurements. A hierarchical self-assembly mechanism was also proposed.
Co-reporter:Songrui Yu, Jianxin Chen, Ruijiao Dong, Yue Su, Bing Ji, Yongfeng Zhou, Xinyuan Zhu and Deyue Yan
Polymer Chemistry 2012 vol. 3(Issue 12) pp:3324-3329
Publication Date(Web):29 Aug 2012
DOI:10.1039/C2PY20487H
Poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) is a well-known cationic polymer candidate for non-viral vectors for gene transfection. However, such an application has been greatly limited due to the cytotoxicity of the polymers. Herein, PDMAEMAs are grafted from hydrophobic hyperbranched PEHO cores (PEHO means poly(3-ethyl-3-(hydroxymethyl)-oxetane)), and the obtained hyperbranched multiarm copolymers of PEHO-g-PDMAEMAs show higher transfection efficiency than that of branched polyethylenimine (PEI) and PDMAEMA homopolymers, due to the improved cytotoxicity, DNA compaction, buffering ability and cellular uptake. In addition, to disclose the structure–property relationship, a series of PEHO-g-PDMAEMAs with different topological architectures are synthesized by changing the degrees of branching (DBs) of the PEHO cores and the lengths of the PDMAEMA arms. The ability of these vectors in DNA compaction, buffering ability, cytotoxicity and gene transfection efficiency is also investigated. It has been found the gene transfection efficiency of the vectors is dependent on the DB of the PEHO cores, but almost independent of the PDMAEMA arms in the experimental range.
Co-reporter:Binbin Jiang;Wei Tao;Xin Lu;Yong Liu;Haibao Jin;Yan Pang;Xiaoyi Sun;Deyue Yan
Macromolecular Rapid Communications 2012 Volume 33( Issue 9) pp:767-772
Publication Date(Web):
DOI:10.1002/marc.201100877
Abstract
A polyhedral oligomeric silsesquioxane (POSS)-based supramolecular amphiphile is prepared from the host–guest inclusion complexation between a mono adamantane-functionalized POSS (AD-POSS) and a β-cyclodextrin oligomer (P(β-CD)). Assisted by the interface of H2O/toluene, the obtained supramolecular hybrids self-assemble into stable hollow nanospheres with thick walls. These hollow nanospheres aggregate together into a sphere layer through a spin coating technique, which then further transforms into a thin porous film containing nanometer-scale holes. The hollow nanospheres have a low cytotoxicity. The in vitro cell culture indicates the nanoporous films promote adhesion and proliferation of cells. The self-assembly morphologies and structures have been carefully characterized by SEM, TEM, AFM, DLS, XPS and water-contact angle measurements, and the self-assembly mechanism has also been discussed.
Co-reporter:Haibao Jin, Yong Liu, Yongli Zheng, Wei Huang, Yongfeng Zhou, and Deyue Yan
Langmuir 2012 Volume 28(Issue 4) pp:2066-2072
Publication Date(Web):November 30, 2011
DOI:10.1021/la203857s
Herein, we have shown a large-scale cell-mimetic (cytomimetic) aggregation process by using cell-sized polymer vesicles as the building blocks and intervesicular host–guest molecular recognition interactions as the driving force. We first prepared the hyperbranched polymer vesicles named branched polymersomes (BPs) around 5–10 μm through the aqueous self-assembly of a hyperbranched multiarm copolymer of HBPO-star-PEO [HBPO = hyperbranched poly(3-ethyl-3-oxetanemethanol); PEO = poly(ethylene oxide)]. Subsequently, adamantane-functionalized BPs (Ada-BPs) or β-cyclodextrin-functionalized BPs (CD-BPs) were prepared through the coassembly of HBPO-star-PEO and Ada-modified HBPO-star-PEO (HBPO-star-PEO-Ada), or of HBPO-star-PEO and CD-modified HBPO-star-PEO (HBPO-star-PEO-CD), respectively. Macroscopic vesicle aggregates were obtained by mixing CD-BPs and Ada-BPs. The intervesicular host–guest recognition interactions between β-CD units in CD-BPs and Ada units in Ada-BPs, which were proved by 1H nuclear Overhauser effect spectroscopy (NOESY) spectrum and the fluorescence probe method, are responsible for the vesicle aggregation. Additionally, the vesicle fusion events happened frequently in the process of vesicle aggregation, which were certified by double-labeling fluorescent assay, real-time observation, content mixing assay, and component mixing assay.
Co-reporter:Dr. Ruijiao Dong; Bangshang Zhu; Yongfeng Zhou;Deyue Yan;Xinyuan Zhu
Angewandte Chemie 2012 Volume 124( Issue 46) pp:11801-11805
Publication Date(Web):
DOI:10.1002/ange.201206362
Co-reporter:Dr. Ruijiao Dong; Bangshang Zhu; Yongfeng Zhou;Deyue Yan;Xinyuan Zhu
Angewandte Chemie International Edition 2012 Volume 51( Issue 46) pp:11633-11637
Publication Date(Web):
DOI:10.1002/anie.201206362
Co-reporter:Haibao Jin; Wei Huang;Yongli Zheng;Deyue Yan
Chemistry - A European Journal 2012 Volume 18( Issue 28) pp:8641-8646
Publication Date(Web):
DOI:10.1002/chem.201201401
Abstract
Vesicle–vesicle aggregation to mimic cell–cell aggregation has attracted much attention. Here, hyperbranched polymer vesicles (branched-polymersomes, BPs) with a cell-like size were selected as model membranes, and the vesicle aggregation process, triggered by click chemistry of the copper-catalysed azide-alkyne cycloaddition reaction, was systematically studied. For this purpose, azide and alkynyl groups were loaded on the membranes of BPs through the co-assembly method to obtain N3-BPs and Alk-BPs, respectively. Subsequently, macroscopic vesicle aggregates were obtained when these two kinds of functional BPs were mixed together with the ratio of azide to alkynyl groups of about 1:1. Both the vesicle fusion events and lateral phase separation on the vesicle membrane occurred during such a vesicle aggregation process, and the fusion rate and phase-separation degree could be controlled by adjusting the clickable group content. The vesicle aggregation process with N3-micelles as desmosome mimics to connect with Alk-BPs through click-chemistry reaction was also studied, and large-scale vesicle aggregates without vesicle fusion were obtained in this process. The present work has extended the controllable cytomimetic vesicle aggregation process with the use of covalent bonds, instead of noncovalent bonds, as the driving force.
Co-reporter:Wei Tao ; Yong Liu ; Binbin Jiang ; Songrui Yu ; Wei Huang ; Yongfeng Zhou ;Deyue Yan
Journal of the American Chemical Society 2011 Volume 134(Issue 2) pp:762-764
Publication Date(Web):December 23, 2011
DOI:10.1021/ja207924w
A linear-hyperbranched supramolecular amphiphile was synthesized through the noncovalent coupling of adamantane-functionalized long alkyl chain (AD-Cn, n = 12, 18, 30) and hyperbranched polyglycerol grafted from β-cyclodextrin (CD-g-HPG) by the specific AD/CD host–guest interactions. The obtained supramolecular Cn-b-HPGs self-assembled into unilamellar vesicles with great ductility that could be disassembled readily under a competitive host of β-CD.
Co-reporter:Ruijiao Dong, Yong Liu, Yongfeng Zhou, Deyue Yan and Xinyuan Zhu
Polymer Chemistry 2011 vol. 2(Issue 12) pp:2771-2774
Publication Date(Web):17 Oct 2011
DOI:10.1039/C1PY00426C
A novel class of photo-responsive A2–B3 type supramolecular hyperbranched polymer with excellent optical properties can be polymerized and depolymerized reversibly by alternating UV/Vis light irradiation.
Co-reporter:Dr. Haibao Jin;Yongli Zheng;Yong Liu;Haixing Cheng; Yongfeng Zhou;Deyue Yan
Angewandte Chemie International Edition 2011 Volume 50( Issue 44) pp:10352-10356
Publication Date(Web):
DOI:10.1002/anie.201103164
Co-reporter:Dr. Haibao Jin;Yongli Zheng;Yong Liu;Haixing Cheng; Yongfeng Zhou;Deyue Yan
Angewandte Chemie 2011 Volume 123( Issue 44) pp:10536-10540
Publication Date(Web):
DOI:10.1002/ange.201103164
Co-reporter:Xiaoyi Sun, Wei Huang, Yongfeng Zhou and Deyue Yan
Physical Chemistry Chemical Physics 2010 vol. 12(Issue 38) pp:11948-11953
Publication Date(Web):16 Aug 2010
DOI:10.1039/C002463E
A novel narrowly-distributed (ND) polymeric micelle obtained in combination with host–guest recognition and self-assembly is reported. First, the adamantyl-terminated hyperbranched poly[3-ethyl-3-(hydroxymethyl)oxetane] (HBPO-AD) was synthesized by esterification of hyperbranched poly[3-ethyl-3-(hydroxymethyl)oxetane] (HBPO) with 1-adamantanecarbonyl chloride. Then the ND polymeric core-shell micelles, with the hydrophobic HBPO-AD cores and hydrophilic beta-cyclodextrin (β-CD) shells, were prepared via host–guest inclusion complexation of HBPO-AD and β-CD. The resultant polymer micelles were well characterized by dynamic light scattering (DLS), transmission electron microscopy (TEM) and scanning electron microscopy (SEM). Interestingly, after annealing at a temperature above the glass transition temperature (Tg) for a certain time, the polymeric micelles can further self-assemble and fuse into two-dimensional (2D) sheets. The TEM, SEM and atomic force microscopy (AFM) characterization validate that the sheets are formed through stacking and fusion of tightly packed nanoparticles. In addition, the formation mechanism of polymeric complex micelles and 2D sheets has also been discussed.
Co-reporter:Xiaoyi Sun;Deyue Yan
Macromolecular Chemistry and Physics 2010 Volume 211( Issue 17) pp:1940-1946
Publication Date(Web):
DOI:10.1002/macp.201000250
Co-reporter:Bo Guo;XiaoYi Sun;DeYue Yan
Science China Chemistry 2010 Volume 53( Issue 3) pp:487-494
Publication Date(Web):2010 March
DOI:10.1007/s11426-010-0083-2
A novel temperature-responsive hyperbranched multiarm copolymer with a hydrophobic hyperbranched poly(3-ethyl-3-(hydroxymethyl) oxetane) (HBPO) core and thermosensitive poly(N-isopropylacrylamide) (PNIPAM) arms was synthesized via the atom transfer radical polymerization (ATRP) of NIPAM monomers from a hyperbranched HBPO macroinitiator. It was found that HBPO-star-PNIPAM self-assembled into multimolecular micelles (around 60 nm) in water at room temperature according to pyrene probe fluorescence spectrometry, 1H NMR, TEM, and DLS measurements. The micelle solution showed a reversible thermosensitive phase transition at a lower critical solution temperature (LCST) (around 32°C) observed by variable temperature optical absorbance measurements. Variable temperature NMR and DLS analyses demonstrated that the LCST transition originated from the secondary aggregation of the micelles driven by increasing hydrophobic interaction due to the dehydration of PNIPAM shells upon heating. The drug loading and release properties of HBPO-star-PNIPAM micelles were also investigated using prednisone acetate as a model drug. The micelles showed a much improved drug encapsulation efficiency and temperature-dependent sustainable release behavior due to the special micellar structure. The micelles exhibited no apparent cytotoxicity against human HeLa cells.
Co-reporter:Haixing Cheng, Shaoai Xie, Yongfeng Zhou, Wei Huang, Deyue Yan, Jintian Yang and Bing Ji
The Journal of Physical Chemistry B 2010 Volume 114(Issue 19) pp:6291-6299
Publication Date(Web):April 22, 2010
DOI:10.1021/jp100714j
This work reports for the first time the influence of degree of branching (DB) on the thermoresponsive phase transition behaviors of hyperbranched multiarm copolymers. Two series of PEHO-star-PEOs (series A) and PEHO-star-PDMAEMAs (series B) with the hydrophobic DB-variable PEHO core and different kinds of linear arms (PEO arms or PDMAEMA arms) were synthesized. It was found these two series demonstrate thermoresponsive phase transitions with the lower critical solution temperature (LCST). The studies on the LCST transition mechanism indicate that series A belongs to the thermoresponsive polymer system with LCST transition based on hydrophilic−hydrophobic balance, while series B belongs to the thermoresponsive polymer system with LCST transition based on coil-to-globule transition. Correspondingly, there is a big difference in the DB dependence of LCST transition between series A and series B. For series A, the LCST phase transition is highly dependent on the DB of the PEHO core in copolymers. For series B, the LCST phase transition is independent of the DB but dependent on solution pH. Such results may extend the knowledge on the structure−activity relationship of thermoresponsive highly branched polymers.
Co-reporter:Haibao Jin, Yongfeng Zhou, Wei Huang, and Deyue Yan
Langmuir 2010 Volume 26(Issue 18) pp:14512-14519
Publication Date(Web):August 20, 2010
DOI:10.1021/la102963w
We demonstrate a high-leveled hierarchical self-assembly process into fractal structures. Two hyperbranched multiarm copolymers are first coassembled into binary isotropic vesicles in the primary self-assembly. Then, these primary vesicles are in situ endowed with anisotropic hydrophobic “binding sites” through a pH-induced lateral microphase separation, undergoing an isotropic−anisotropic transition. Subsequently, the anisotropic vesicles further assemble together through the specific self-recognition between the binding sites into linear, branched, cyclization, and network-like vesicle chains. Furthermore, the obtained vesicle chains can transform into linear, branched, ring-like, and network tubes through successive vesicle fusion. Such a hierarchical process is pH-triggered and well-controlled by adjusting the vesicle compositions and is coined as “polymerization-like” self-assembly due to the striking analogy between the vesicle association model and polymerization process.
Co-reporter:Yongli Zheng;Ling Zhong;Wei Huang;Deyue Yan
Journal of Polymer Science Part A: Polymer Chemistry 2010 Volume 48( Issue 20) pp:4428-4438
Publication Date(Web):
DOI:10.1002/pola.24230
Abstract
In this article, we report the self-assembly of flocculation-resistant multimolecular micelles with thermoresponsive corona from novel dendritic heteroarm star copolymers. The micelles have a core-shell-corona structure at room temperature according to pyrene probe fluorescence spectrometry, proton nuclear magnetic resonance (1H NMR), transmission electron microscopy, and dynamic light scattering measurements. Increasing the temperature above the lower critical solution temperature (LCST), the micelles show high flocculation-resistant ability resulting from a structure transition from core-shell-corona to core-shell confirmed by a quantitative variable temperature 1H NMR analysis method using potassium hydrogen phthalate as an external standard. A big volume change of the micelles is observed during the LCST transition. The drug loading and temperature-dependent release properties of the micelles are also investigated by using coumarin 102 as a model drug, which displays a rapid drug release at a temperature above the LCST. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010
Co-reporter:Haixing Cheng, Xijing Yuan, Xiaoyi Sun, Kunpeng Li, Yongfeng Zhou and Deyue Yan
Macromolecules 2010 Volume 43(Issue 2) pp:1143-1147
Publication Date(Web):November 23, 2009
DOI:10.1021/ma902452p
Co-reporter:Yongfeng Zhou and Deyue Yan
Chemical Communications 2009 (Issue 10) pp:1172-1188
Publication Date(Web):13 Jan 2009
DOI:10.1039/B814560C
This feature article describes the supramolecular self-assembly of hyperbranched polymers (HBPs), including the progress, unique characteristics and future perspectives. HBPs are irregular in molecular structure compared with that of linear block copolymers and dendrimers. However, similar to these well-defined polymer tectons, HBPs have displayed great potential to be excellent precursors in solution self-assembly, interfacial self-assembly and hybrid self-assembly. Many impressive supramolecular aggregates and hybrids at all scales and dimensions, such as macroscopic tubes, micro- or nano-vesicles, fibers, spherical micelles and honeycomb films, have been generated. In addition, HBPs also demonstrate unique characteristics or advantages in supramolecular self-assembly behaviours, including controllable morphologies and structures, special properties, characteristic self-assembly mechanism and facile functionalization process. Although still being at the early stage, self-assembly of HBPs has provided a new avenue for the development of supramolecular chemistry.
Co-reporter:Haixing Cheng, Siguang Wang, Jintian Yang, Yongfeng Zhou, Deyue Yan
Journal of Colloid and Interface Science 2009 Volume 337(Issue 1) pp:278-284
Publication Date(Web):1 September 2009
DOI:10.1016/j.jcis.2009.05.026
A series of palmitoyl chloride-grafted hyperbranched polyglycerols were synthesized through cationic ring-opening polymerization and end-group modification. The obtained grafted copolymer of HPG-C16 possesses a hydrophilic hyperbranched polyether core and many hydrophobic alkyl arms, which shows interesting self-assembly behavior in THF and water. The results indicate that the copolymers with a relatively high alkyl grafting ratio can form unimolecular micelles in THF and will further assemble into giant vesicles around 1–10 μm in THF/water mixed solvents. However, the HPG-C16 with a low alkyl grafting ratio of 15.6% can directly assemble into vesicles in THF and form micelles in water.An amphiphilic multiarm copolymer with a hydrophilic hyperbranched polyglycerol core and many hydrophobic alkyl chains can self-assemble into either vesicles or large multimolecular micelles depending on selective solvents or graft ratios.
Co-reporter:Yuan Gao;DeYue Yan
Science China Chemistry 2009 Volume 52( Issue 3) pp:344-350
Publication Date(Web):2009 March
DOI:10.1007/s11426-009-0001-7
This work successfully prepared nanohybrids by in situ atom transfer radical polymerization (ATRP) of styrene from titanate nanotubes (TNTs). Fourier-transform infrared (FT-IR), pronton nuclear magnetic resonance spectroscopy (1H NMR), and thermal gravimetric analysis (TGA) were used to verify the successful graft of polystyrene (PS) chains from TNTs. Transmission electron microscopy (TEM) displayed that the obtained PS-g-TNTs nanohybrids had a core-shell structure of TNT core and PS shell. The grafted PS content was well controlled and increased with increasing of the monomer/initiator ratio. Further copolymerization of tert-butyl acrylate (tBA) from the surface of PS-g-TNTs was studied, illustrating the “living” characteristics of the surface-induced ATRP method used in this work.
Co-reporter:Bo Guo, Zengqian Shi, Yuan Yao, Yongfeng Zhou and Deyue Yan
Langmuir 2009 Volume 25(Issue 12) pp:6622-6626
Publication Date(Web):May 19, 2009
DOI:10.1021/la901366g
This work reported for the first time a facile template-free method to prepare polypeptide-based vesicles (peptosomes) through one-step complex self-assembly of carboxyl-terminated hyperbranched polyester and cationic poly-l-lysine (PLL). The preparation of such peptosomes, named complex peptosomes (CPs) here, is very simple just by mixing two kinds of polymer aqueous solutions together. The CP size can be readily controlled from nanosize to microsize through the adjustment of polymer concentration. The resulting nanosized CPs show unexpected size stability independent of a broad solution pH range, long-term storage stability, and almost no cytotoxicity and have demonstrated great potential to be used as the carriers in drug delivery.
Co-reporter:Yuan Gao, Yongfeng Zhou, Deyue Yan
Polymer 2009 50(12) pp: 2572-2577
Publication Date(Web):
DOI:10.1016/j.polymer.2009.04.018
Co-reporter:Zengqian Shi;Deyue Yan
Macromolecular Rapid Communications 2008 Volume 29( Issue 5) pp:412-418
Publication Date(Web):
DOI:10.1002/marc.200700673
Co-reporter:Ling Zhong;Deyue Yan;Caiyuan Pan
Macromolecular Rapid Communications 2008 Volume 29( Issue 16) pp:1385-1391
Publication Date(Web):
DOI:10.1002/marc.200800223
Co-reporter:Haiyan Hong;Yiyong Mai;Deyue Yan;Yan Chen
Journal of Polymer Science Part A: Polymer Chemistry 2008 Volume 46( Issue 2) pp:668-681
Publication Date(Web):
DOI:10.1002/pola.22415
Abstract
A novel amphiphilic thermosensitive star copolymer with a hydrophobic hyperbranched poly (3-ethyl-3-(hydroxymethyl)oxetane) (HBPO) core and many hydrophilic poly(2-(dimethylamino) ethyl methacrylate) (PDMAEMA) arms was synthesized and used as the precursor for the aqueous solution self-assembly. All the copolymers directly aggregated into core–shell unimolecular micelles (around 10 nm) and size-controllable large multimolecular micelles (around 100 nm) in water at room temperature, according to pyrene probe fluorescence spectrometry and 1H NMR, TEM, and DLS measurements. The star copolymers also underwent sharp, thermosensitive phase transitions at a lower critical solution temperature (LCST), which were proved to be originated from the secondary aggregation of the large micelles driven by increasing hydrophobic interaction due to the dehydration of PDMAEMA shells on heating. A quantitative variable temperature NMR analysis method was designed by using potassium hydrogen phthalate as an external standard and displayed great potential to evaluate the LCST transition at the molecular level. The drug loading and temperature-dependent release properties of HBPO-star-PDMAEMA micelles were also investigated by using indomethacin as a model drug. The indomethacin-loaded micelles displayed a rapid drug release at a temperature around LCST. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 668–681, 2008
Co-reporter:Haiyan Hong;Yiyong Mai;Deyue Yan;Jun Cui
Macromolecular Rapid Communications 2007 Volume 28(Issue 5) pp:591-596
Publication Date(Web):12 MAR 2007
DOI:10.1002/marc.200600752
This work focused on the synthesis and aqueous self-assembly of a series of novel hyperbranched star copolymers with a hyperbranched poly[3-ethyl-3-(hydroxymethyl)oxetane] (HBPO) core and many linear poly[2-(dimethylamino)ethyl methacrylate] (PDMAEMA) arms. The copolymers can synchronously form unimolecular micelles (around 10 nm) and large multimolecular micelles (around 100 nm) in water at room temperature. TEM measurements have provided direct evidence that the large micelles are a kind of multimicelle aggregates (MMAs) with the basic building units of unimolecular micelles. It is the first demonstration of the self-assembly mechanism for the large multimolecular micelles generated from the solution self-assembly of hyperbranched copolymers.
Co-reporter:Wenyong Dong, Yongfeng Zhou, Deyue Yan, Huiqin Li and Yu Liu
Physical Chemistry Chemical Physics 2007 vol. 9(Issue 10) pp:1255-1262
Publication Date(Web):23 Jan 2007
DOI:10.1039/B615525C
This work has presented a typical example to reveal the great influence of the terminal groups on the self-assembly of hyperbranched polymers. The hyperbranched polymers with hydroxyl terminal groups (HBPO-OH) were hydrophobic and precipitated in water, however, they displayed a pH-responsive self-assembly behavior when the terminal groups were replaced by carboxyl groups. The obtained carboxyl-terminated hyperbranched polymers (HBPO-COOH) existed as unimolecular micelles at high pH (12.21) due to the ionization of carboxyl groups, while the polymers aggregated into multimolecular micelles from 10 to 500 nm with the decrease of pH as a result of the partial protonation of the carboxyl groups. The size of the obtained micelles depended strongly on the solution pH—the lower the pH, the bigger the micelles. TEM, DLS, ATR-FT-IR, 1H NMR and AFM measurements substantiated that the multimolecular micelles were formed by the secondary aggregation of unimolecular micelles driven by the hydrogen bonding interaction depending on the solution pH.
Co-reporter:Feng Chen, Yunzhou Ni, Bing Liu, Tongtong Zhou, Chunyang Yu, Yue Su, Xinyuan Zhu, Xiaowei Yu, Yongfeng Zhou
Carbohydrate Polymers (15 June 2017) Volume 166() pp:
Publication Date(Web):15 June 2017
DOI:10.1016/j.carbpol.2017.02.059
•Developing an injectable hyaluronic acid/RGD-functionalized pectin hydrogel.•Adopting an efficient and non-cytotoxic hydrazone crosslinking strategy.•The hydrogel displays the suitable gelation time and tunable mechanical properties.•The hydrogel can provide an ECM-mimetic microenvironment for enhancing chondrogenesis.•The biomimetic hydrogel has good biodegradability and tissue compatibility.In the present study, we developed a biomimetic injectable hydrogel system based on hyaluronic acid-adipic dihydrazide and the oligopeptide G4RGDS-grafted oxidized pectin, in which their hydrazide and aldehyde-derivatives enable covalent hydrazone crosslinking of polysaccharides. The hydrazone crosslinking strategy is simple, while circumventing toxicity, making this injectable system feasible, minimally invasive and easily translatable for regenerative purposes. By varying their weight ratios, the physicochemical properties of the mechanically stable hydrogel system were easily adjustable. Additionally, the preliminary studies demonstrated that chondrocyte behavior was dependent on HA/pectin composition and the presence of integrin binding moieties. Specifically, the incorporation of a certain amount of G4RGDS oligopeptide into HA/pectin-based hydrogels could serve as a biologically active microenvironment that supported chondrocyte phenotype and facilitated chondrogenesis. Furthermore, the hydrogel system exhibited acceptable tissue compatibility by using a mouse subcutaneous implantation model. Overall, the novel injectable multicomponent hydrogel presented here is expected to be useful biomaterial scaffold for cartilage tissue regeneration.
Co-reporter:Yongfeng Zhou and Deyue Yan
Chemical Communications 2009(Issue 10) pp:NaN1188-1188
Publication Date(Web):2009/01/13
DOI:10.1039/B814560C
This feature article describes the supramolecular self-assembly of hyperbranched polymers (HBPs), including the progress, unique characteristics and future perspectives. HBPs are irregular in molecular structure compared with that of linear block copolymers and dendrimers. However, similar to these well-defined polymer tectons, HBPs have displayed great potential to be excellent precursors in solution self-assembly, interfacial self-assembly and hybrid self-assembly. Many impressive supramolecular aggregates and hybrids at all scales and dimensions, such as macroscopic tubes, micro- or nano-vesicles, fibers, spherical micelles and honeycomb films, have been generated. In addition, HBPs also demonstrate unique characteristics or advantages in supramolecular self-assembly behaviours, including controllable morphologies and structures, special properties, characteristic self-assembly mechanism and facile functionalization process. Although still being at the early stage, self-assembly of HBPs has provided a new avenue for the development of supramolecular chemistry.
Co-reporter:Yannan Liu, Shanlong Li, Ke Li, Yongli Zheng, Meng Zhang, Caiyun Cai, Chunyang Yu, Yongfeng Zhou and Deyue Yan
Chemical Communications 2016 - vol. 52(Issue 60) pp:NaN9397-9397
Publication Date(Web):2016/06/13
DOI:10.1039/C6CC03595G
A novel hybrid light-harvesting antenna with a srikaya-like structure of multi-graphene quantum dots (GQDs) as donors and one porphyrin unimolecular micelle as the acceptor was constructed through electrostatic self-assembly. The constructed antenna showed a high energy transfer efficiency of up to 93.6% and an antenna effect of 7.3 in an aqueous solution.
Co-reporter:Tong Huang, Xiaohua Huang, Xiaoyi Sun, Yongfeng Zhou, Yongping Bai and Deyue Yan
Chemical Communications 2014 - vol. 50(Issue 55) pp:NaN7366-7366
Publication Date(Web):2014/05/21
DOI:10.1039/C4CC02520B
This study describes a new method to prepare monodisperse polystyrene (PS) colloidal nanoparticles with controlled size ranging from 60 nm to 140 nm by the direct polymerization of styrene and divinylbenzene inside the bilayers of the polydisperse hyperbranched polymer vesicles.
Co-reporter:Haibao Jin, Yongfeng Zhou, Wei Huang, Yongli Zheng, Xinyuan Zhu and Deyue Yan
Chemical Communications 2014 - vol. 50(Issue 46) pp:NaN6160-6160
Publication Date(Web):2014/03/11
DOI:10.1039/C4CC00609G
Large-scale and robust vesicle aggregates were obtained through molecular recognition among cell-sized polymer vesicles, carbon nanotubes and AuNPs, driven by adhesion interactions between Au and polydopamine. Vesicle fusion was effectively avoided in this three-component vesicle aggregation process.
Co-reporter:Wenyong Dong, Yongfeng Zhou, Deyue Yan, Huiqin Li and Yu Liu
Physical Chemistry Chemical Physics 2007 - vol. 9(Issue 10) pp:NaN1262-1262
Publication Date(Web):2007/01/23
DOI:10.1039/B615525C
This work has presented a typical example to reveal the great influence of the terminal groups on the self-assembly of hyperbranched polymers. The hyperbranched polymers with hydroxyl terminal groups (HBPO-OH) were hydrophobic and precipitated in water, however, they displayed a pH-responsive self-assembly behavior when the terminal groups were replaced by carboxyl groups. The obtained carboxyl-terminated hyperbranched polymers (HBPO-COOH) existed as unimolecular micelles at high pH (12.21) due to the ionization of carboxyl groups, while the polymers aggregated into multimolecular micelles from 10 to 500 nm with the decrease of pH as a result of the partial protonation of the carboxyl groups. The size of the obtained micelles depended strongly on the solution pH—the lower the pH, the bigger the micelles. TEM, DLS, ATR-FT-IR, 1H NMR and AFM measurements substantiated that the multimolecular micelles were formed by the secondary aggregation of unimolecular micelles driven by the hydrogen bonding interaction depending on the solution pH.
Co-reporter:Xiaoyi Sun, Wei Huang, Yongfeng Zhou and Deyue Yan
Physical Chemistry Chemical Physics 2010 - vol. 12(Issue 38) pp:NaN11953-11953
Publication Date(Web):2010/08/16
DOI:10.1039/C002463E
A novel narrowly-distributed (ND) polymeric micelle obtained in combination with host–guest recognition and self-assembly is reported. First, the adamantyl-terminated hyperbranched poly[3-ethyl-3-(hydroxymethyl)oxetane] (HBPO-AD) was synthesized by esterification of hyperbranched poly[3-ethyl-3-(hydroxymethyl)oxetane] (HBPO) with 1-adamantanecarbonyl chloride. Then the ND polymeric core-shell micelles, with the hydrophobic HBPO-AD cores and hydrophilic beta-cyclodextrin (β-CD) shells, were prepared via host–guest inclusion complexation of HBPO-AD and β-CD. The resultant polymer micelles were well characterized by dynamic light scattering (DLS), transmission electron microscopy (TEM) and scanning electron microscopy (SEM). Interestingly, after annealing at a temperature above the glass transition temperature (Tg) for a certain time, the polymeric micelles can further self-assemble and fuse into two-dimensional (2D) sheets. The TEM, SEM and atomic force microscopy (AFM) characterization validate that the sheets are formed through stacking and fusion of tightly packed nanoparticles. In addition, the formation mechanism of polymeric complex micelles and 2D sheets has also been discussed.
Co-reporter:Yun-Zhou Ni, Wen-Feng Jiang, Gang-Sheng Tong, Jian-Xin Chen, Jie Wang, Hui-Mei Li, Chun-Yang Yu, Xiao-hua Huang and Yong-Feng Zhou
Organic & Biomolecular Chemistry 2015 - vol. 13(Issue 3) pp:NaN690-690
Publication Date(Web):2014/11/14
DOI:10.1039/C4OB02080D
A miscible tetrahydrofuran–tris buffer mixture has been used to fabricate polydopamine hollow capsules with a size of 200 nm and with a shell thickness of 40 nm. An unusual non-emulsion soft template mechanism has been disclosed to explain the formation of capsules. The results indicate that the capsule structure is highly dependent on the volume fraction of tetrahydrofuran as well as the solvent, and the shell thickness of capsules can be controlled by adjusting the reaction time and dopamine concentration.
Co-reporter:Haibao Jin, Wei Huang, Xinyuan Zhu, Yongfeng Zhou and Deyue Yan
Chemical Society Reviews 2012 - vol. 41(Issue 18) pp:NaN5997-5997
Publication Date(Web):2012/07/13
DOI:10.1039/C2CS35130G
Self-assembly of amphiphilic hyperbranched polymers (HBPs) is a newly emerging research area and has attracted increasing attention due to the great advantages in biomedical applications. This tutorial review focuses on the self-assembly of biocompatible or biodegradable amphiphilic HBPs and their cytomimetic applications, and specialities or advantages therein owing to the hyperbranched structure have also been summarized. As shown here, various supramolecular structures including micelles, vesicles, tubes, fibers and films have been prepared through the primary self-assembly processes. The primary self-assemblies can be further assembled into more complex structures through hierachical self-assembly processes. Besides, the hyperbranched polymer vesicles have demonstrated great potential to be used as model membranes to mimic cellular behaviors, such as fusion, fission and cell aggregation. Other biomedical applications of HBPs as well as their self-assemblies are also briefly summarized.
Co-reporter:Chunyang Yu, Li Ma, Ke Li, Shanlong Li, Yannan Liu, Yongfeng Zhou and Deyue Yan
Physical Chemistry Chemical Physics 2016 - vol. 18(Issue 32) pp:NaN22457-22457
Publication Date(Web):2016/07/19
DOI:10.1039/C6CP03726G
Hyperbranched polyglycerol (HPG) is one of the most important hyperbranched polymers (HBPs) due to its interesting properties and applications. Herein, the conformation of HPGs depending on the degree of polymerization (DP) and the degree of branching (DB) is investigated explicitly by molecular dynamics simulations. This study shows that the radius of gyration (Rg) scales as Rg ∼ DP1/3, which is in close agreement with the result of the SANS experiment. For HPGs with the same DP, the radius of gyration, asphericities and solvent accessible surface area all monotonically decrease with the increase of DB; while for HPGs with the same DB, the molecular anisotropy decreases with the increase of DP. The radial density investigation discloses that the cavities are randomly distributed in the interior of the HPG core to support the “dendritic box effect”, which can be used to encapsulate the guest molecules. Interestingly, the terminal groups of HPGs with a high Wiener index (WI) are more favorable to fold back into the interiors than those with the low WI when in water. For the hyperbranched multi-arm copolymer with a HPG core and many polyethylene glycol (PEG) arms, drug encapsulation studies show that the PEG caps can not only effectively prevent tamoxifen from leaving the HPG core, but also encapsulate tamoxifen inside the PEG chains. These simulation results have provided more details for understanding the structure–property relationships of HPGs in water.
Co-reporter:Wenfeng Jiang, Yong Liu, Chunyang Yu, Shanlong Li, Yongjin Li and Yongfeng Zhou
Chemical Communications 2016 - vol. 52(Issue 53) pp:NaN8226-8226
Publication Date(Web):2016/05/13
DOI:10.1039/C6CC03445D
This study reports a new category of stimuli-responsive morphological transitions, i.e., from one morphology (e.g., vesicles) to another two different ones (e.g., nanosheets and nanofibers), by investigating the light-responsive self-assembly behaviour of a “latent double-amphiphilic” linear-hyperbranched supramolecular block copolymer.
Co-reporter:Wenfeng Jiang, Yongfeng Zhou and Deyue Yan
Chemical Society Reviews 2015 - vol. 44(Issue 12) pp:NaN3889-3889
Publication Date(Web):2014/10/22
DOI:10.1039/C4CS00274A
Vesicles, including lipid vesicles, surfactant vesicles, as well as polymer vesicles, have been extensively investigated over the past fifty years. Among them, polymer vesicles have attracted more and more attention because of their low permeability, superior stability and toughness, in addition to the numerous possibilities for tailoring physical, chemical and biological properties. Polymer vesicles are generally fabricated through the self-assembly of amphiphilic polymers with a linear architecture. Recently, as representative polymers with a highly branched three-dimensional architecture, hyperbranched polymers have also exhibited great potential for preparing vesicles. The resultant hyperbranched polymer vesicles, defined as branched-polymersomes (BPs), have shown unique properties, such as giant and easily tuned vesicle sizes, facile functionalization, a special formation mechanism, and appealing solution behaviours. In this tutorial review, ten years of advances in BPs have been summarized since their first discovery in the year 2004, including the syntheses of vesicle-forming hyperbranched polymers, self-assembly methods, self-assembly mechanisms, as well as the special properties. In addition, the cytomimetic, biomedical and other initiatory applications of BPs are also included.
Co-reporter:Yujiao Fan, Dapeng Zhang, Jie Wang, Haibao Jin, Yongfeng Zhou and Deyue Yan
Chemical Communications 2015 - vol. 51(Issue 33) pp:NaN7237-7237
Publication Date(Web):2015/03/19
DOI:10.1039/C5CC01802A
This work reports the self-assembly of anion-exchangeable vesicles from an amphiphilic hyperbranched polymeric ionic liquid (HBPIL). By a simple one-step anion exchange with methyl orange, the obtained HBPILs could self-assemble into pH-indicative and colorful vesicles in water with color changes directly visible to the naked eye in response to solution pH. In addition, by another step of anion exchange with bovine serum albumin (BSA), the BSA-coated vesicles could also be readily prepared.
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