研究领域： 高分子间的相互作用和分子组装 水溶性高分子的疏水缔合、离聚物 聚合物改性及嵌段和接枝共聚物 研究课题： 国家自然科学基金重大课题：有序高级结构分子聚结体的结构,构筑与性能 攀登计划项目：高分子凝聚态物理中的基本问题的研究 国际合作项目：Studies of selective distribution of inorganic fillers in the selected polymer domain of binarypolymer alloys 国家自然科学基金重大项目：聚合物胶束的制备及其功能化材料的基础研究 国家自然科学基金重点项目：基于主客体分子识别的超分子聚合与大分子自组装 自然科学基金面上项目：基于包结络合作用的金纳米粒子的可逆聚集与高分子的自组装 请参阅本课题组的代表作和及本课题组最新发表的文章以作深入了解
Protein Crystalline Frameworks with Controllable Interpenetration Directed by Dual Supramolecular Interactions
Fuji Sakaia, Guang Yanga, Manfred S. Weissb, Yijiang Liua, Guosong Chena*, Ming Jianga*
Protein crystalline framework is very special and attractive for biomimetic and nano-technological studies because it could augment the useful functionalities of numerous proteins through dense packing and uniform orientation. However its formation and precise control is very challenging. Here we present novel protein crystalline frameworks with controllable interpenetration The homotetrameric lectin concanavalin A is crosslinked by predetermined inducing ligands containing monosaccharide and rhodamine groups connected by an oligo(ethylene oxide) spacer. Two non-covalent interactions, i.e., sugar-lectin binding and the dimerization of RhB, are responsible for the framework formation. The three-dimensional structure of the framework is fully characterized by X-ray crystallographic methods. For the first time, either interpenetrating or non-interpenetrating frameworks are obtained, and they are controlled by the spacer length of the inducing ligand. Further kinetics and mechanistic investigations reveal that, in the self-assembly process, the carbohydrate-protein binding occurs first, followed by RhB dimerization. This sequence favors rapid crystallization with a high yield when an excess amount of inducing ligand is used. In short, by using well-controlled dual non-covalent interactions, fast and versatile preparation of protein crystalline framework was achieved with high crystallization ratio of the proteins, which may shed light on protein crystallization in near future.
Glyco-regioisomerism E?ect on Lectin-Binding and Cell-Uptake
Pathway of Glycopolymer-Containing Nanoparticles
Pengfei Sun, Yu He, Mingchang Lin, Yu Zhao, Yu Ding,*, Guosong Chen*, and Ming Jiang
Sugar regioisomerism (glycosidic linkage on di?erent hydroxyl groups of the same sugar) widely exists in various polysaccharides and glycans with a signi?cant contribution to their biological functions. However, the e?ects of this regioisomersim in glycopolymers and their self-assembled nanoparticles on such functions were almost not investigated previously. In this paper, this regioisomersim e?ect is studied for self-assembled nanoparticles NP-1-Gal and NP-6-Gal from triblock copolymers carrying di?erent constitutional isomers of the pendent sugar species (1 and 6 denote the glycosidic linkage from the anomeric position and 6 position of the galactose unit, respectively). NP-1-Gal shows strong binding to lectins of Peanut (Arachis hypogea) agglutinin (PNA) and Erythrina cristagalliagglutinin (ECA), while NP-6-Gal does not. More importantly, they show binding behavior similar to the asialoglycoprotein receptor (ASGPR) but di?erent internalization pathways in the Hep G2 cell after ASGPR-mediated endocytosis; i.e., NP-1-Galcan reach the early endosome, late endosome, as well as lysosome, while NP-6-Gal enters the early endosome only but not the others
On PublishPengfei Sun, Yu He, Mingchang Lin, Yu Zhao, Yu Ding,*, Guosong Chen*, and Ming Jiang, ACS Macro Lett. 2014, 3, 96−101
Polymeric vesicles mimicking glycocalyx (PV-Gx) for studying carbohydrate-protein interactions in solution Lu Su, Yu Zhao, Guosong Chen*, Ming Jiang
Sugar regioisomerism (glycosidic linkage on di?erent hydroxyl groups of the same sugar) widely exists in various polysaccharidesGlycocalyx, the carbohydrate coat on cell surface, has been proved particularly important in a variety of biological events. In this work, polymeric vesicle mimicking glycocalyx (PV-Gx), as a simplified model system, is achieved via our NCCM strategy, using dynamic covalent bond between phenylboronic acid and sugar as the non-covalent linkage. Dynamic light scattering (DLS) has been employed to monitor the binding process between the sugars on PV-Gx and three different lectins. The results clearly proved that the PV-Gx constructed from the polymers with well-defined sugar units is a promising platform for the study of carbohydrate-protein interactions in solution without fluorescent labeling of proteins. and glycans with a signi?cant contribution to their biological functions. However, the e?ects of this regioisomersim in glycopolymers and their self-assembled nanoparticles on such functions were almost not investigated previously. In this paper, this regioisomersim e?ect is studied for self-assembled nanoparticles NP-1-Gal and NP-6-Gal from triblock copolymers carrying di?erent constitutional isomers of the pendent sugar species (1 and 6 denote the glycosidic linkage from the anomeric position and 6 position of the galactose unit, respectively). NP-1-Gal shows strong binding to lectins of Peanut (Arachis hypogea) agglutinin (PNA) and Erythrina cristagalliagglutinin (ECA), while NP-6-Gal does not. More importantly, they show binding behavior similar to the asialoglycoprotein receptor (ASGPR) but di?erent internalization pathways in the Hep G2 cell after ASGPR-mediated endocytosis; i.e., NP-1-Galcan reach the early endosome, late endosome, as well as lysosome, while NP-6-Gal enters the early endosome only but not the others
Su L, Zhao Y, Chen GS, Jiang M. Polym. Chem., 2012, DOI:10.1039/C2PY20110K.
Self-assembly of particles—The regulatory role of particle flexibility Kaka Zhang, Ming Jiang, Daoyong Chen*
Aspects of the self-assembly of particles, which uses nanometer or micrometer sized building blocks to bridge the gap between microscopic and macroscopic scales, are reviewed. Particle self-assembly has been the focus of considerable research in recent years because it can lead to superstructures with a complexity inaccessible by molecular self-assembly, and functionalities entirely different from or superior to those of the primary particles. Examples in molecular self-assembly suggests that anisotropic interactions could be useful in promoting particle self-assembly, with the exception of colloidal crystallization, which requires particles of uniform size and shape. Anisotropic particles prepared by surface modification of precursor particles are often rigid and submicron or micron sized, and thus relatively strong isotropic van der Waals interactions tend to resist self-assembly into regular superstructures. In addition, the relatively large contact area between particles needed for a sufficient binding enthalpy to stabilize a superstructure is difficult for rigid spherical particles. In contrast, flexible anisotropic polymeric particles dispersed in solvents have been shown to self-assemble into various superstructures. The flexibility of primary anisotropic particles enables them to fuse and stabilize into a superstructure. Some flexible and multicomponent particles that are isotropic in common solvents can undergo deformation and sufficient material redistribution to anisotropically self-assemble into regular superstructures in selective solvents. The self-assembly is also driven by anisotropic interactions, which is induced during self-assembly rather than in the particles as synthesized. This review focuses on recent achievements in soft particle self-assembly and describes briefly the advancements in rigid particle self-assembly. The presentation is divided into discussion of self-assembly by the colloidal crystallization of isotropic rigid particles, anisotropic rigid particles, anisotropic soft particles and isotropic soft particles, in that order.
Does PNIPAM block really retard the micelle-to-vesicle transition of its copolymer?
Kongchang Wei, Lu Su, Guosong Chen*, Ming Jiang*
Asymmetrically modified PNIPAM (Mw 10K), i.e. C12-PNIPAM-CA with a hydrophobic hydrocarbon chain -C12H25 (C12) at one end and a hydrophilic carboxyl group -COOH (CA) as the other, was prepared and found to form micelles with a core of the lightly associated hydrocarbon chains. When temperature is increased to the LCST of PNIPAM, the transformation from micelles to vesicles can be realized within 30 min, while the reverse process only takes a few minutes. Based on full monitoring of the transition process, it is proposed that the micelles serve as building blocks in constructing the vesicles via processes of combination, fusion, and etc., in which only local conformation adjustment of PNIPAM is involved.
Cyclodextrin-based Inclusion Complexation Bridging Supramolecular Chemistry and Macromolecular Self-Assembly Guosong Chen, Ming Jiang*
In this invited review, we address how inclusion complexation has been employed and used to promote the recent developments in macromolecular self-assembly, especially with responsive functionalities. These include the amphiphilicity adjustment of macromolecules, non-covalent linkages for forming pseudo block copolymers and micelles, surface modification and functionalization of polymeric micelles and vesicles, and the combination of synthetic polymeric assemblies with biological moieties.
Photoresponsive Pseudopolyrotaxane Hydrogels Based on Competition of Host–Guest Interactions Xiaojuan Liao, Guosong Chen, Xiaoxia Liu, and Ming Jiang*
A photo reversible hydrogel has been achieved via supramolecular competition. Briefly, a pseudopolyrotaxane Hydrogel formed by the inclusion complexation between α-cyclodextrin and poly(ethylene glycol) (PEG). After trans-azobenzene (trans-Azo) was added, the hydrogel transformed to solution because of the stronger binding ability of trans-Azo with α-CD than PEG. After UV light irradiation, trans-Azo isomerized to its cis form, which can not hold a-CD any more, which induced the formation of hydrogel again.
Dual Stimuli-Responsive Supramolecular Hydrogel Constructed by Hybrid Inclusion Complex (HIC) formation Jianghua Liu, Guosong Chen, Mingyu Guo, Ming Jiang
A novel dual-responsive supramolecular hydrogel composed of an azobenzene (AZO) end- functionalized block copolymer PDMA-b-PNIPAM (AZO-(PDMA-b-PNIPAM)) and β-cyclodextrin-modified CdS quantum dot (β-CD@QD) has been demonstrated. Based on the host-guest inclusion complexation of AZO of the block copolymers and CD cavities on β-CD@QD, they form a hybrid inclusion complex (HIC). The inclusion complex and the domains of the collapsed PNIPAM chains serve as two distinct crosslinks and render the hydrogel excellent dual sensitivity to competitive hosts/guests substitution and to temperature variation.
Non-covalently connected micelles (NCCMs): the origins and development ofa new concept Mingyu Guo and Ming Jiang
Nearly ten years ago, we suggested a new concept of non-covalently connected micelles (NCCMs) to describe and name a novel family of polymeric micelles. In NCCMs the components that form the core and shell are connected by hydrogen bonding instead of the normal covalent bonding that exists in all micelles formed from block copolymers. Investigations by us, as well as by others, in recent years have shown that the concept of NCCMs, and the methodology to attain them, are in fact much broader than our original suggestion.
Guo MY and Jiang M.Soft Matter 2009, 5, 495-500
Functional nanohybrids self-assembly from amphiphilic calixbiscrowns and noble metals Bing Guan, Qing Liang, Yuan Zhu, Minghua Qiao, Jiong Zou and Ming Jiang
One-dimensional nanohybrids made of organic templates of calixcrowns and in-situ formed metal nanoparticles were fabricated. The structure and catalytic properties of the hybrids were investigated.
Guan B, Liang Q, Jiang M, et al.JOURNAL OF MATERIALS CHEMISTRY 2009,19, 7610-7613
Dual Reversible Self-Assembly of PNIPAM-Based Amphiphilies Formed by Inclusion Complexation
Jiong Zou, Bing Guan, Xiaojuan Liao, Ming Jiang, and Fenggang Tao
β-Cyclodextrin (β-CD)-ended linear poly(N-isopropylacrylamide) (β-CD-PNIPAM) and Frechet-type benzyl ether dendron with an azobenzene group (Gx-Azo) at the apex site form noncovalently connected amphiphiles (NCCAs) by inclusion complexation between the azo group and β-CD. The NCCAs self-assemble into vesicles in water. Optical switching of the assembly and disassembly is realized by alternating visible andUVirradiation, which causes the isomerization of the azo groups and their consequent complexation and decomplexation with β-CD. The structure and morphology of the vesicles were characterized by dynamic light scattering (DLS), static light scattering (SLS), SEM, TEM, and AFM. These photoresponsive vesicles can further respond to heat stimuli resulting in reversible aggregation and disaggregation of the vesicles.
Zou J, Guan B, Jiang M, et al. Macromolecules 2009, 42, 7465-7473
Self-assembly of amphiphilic calix crowns: from vesicles to nanotubes
Guan, B(官冰); Jiang, M（江明）; Yang, XG（杨晓刚）, et al.
In conclusion, to our knowledge, this communication presents the first e点击放大图片xample of a morphological transition from vesicles to nanotubes in self-assemblies of calixarenes. Unlike the remarkably broad and deep studies on self-assembly of block copolymers which started in the 1970’s, the investigation on self-assembly of the calixarenes is still at the very beginning. Great efforts are needed to exploit the relationship between the resultant morphologies and the structural parameters of the calixarenes, including the conformation of the framework, the structure and length of the attached hydrophilic chains etc, some of which is currently underway in our laboratory.
Surface Modification of Polymeric Vesicles via Host-Guest Inclusion Complexation Mingyu, Guo（郭明雨）; Ming, Jiang（江明）; Guangzhao, Zhang（张广照）
As schematically summarized in Scheme 2, a novel kind of vesicle, which is reactive in supramolecular chemistry, was prepared through β-CD-ended polyether imide in water. On both the outer and inner surfaces of the vesicles, β-CD cavities are available for further surface modification via inclusion complexation between β-CD and adamantane-monoended PEG. For Ada-PEG2K and Ada-PEG1.1K, both the inner andou点击放大图片ter surfaces can be fully modified whereas for Ada-PEG5K the inner surfaces can be only partially modified. We emphasis that our surface modification of the vesicles is completely based on supramolecular chemistry and thus the guest polymers are no covalently connected to the surfaces. This study opens a new, simple, mild avenue to the surface modification and functionalization of the vesicles, which of course would promote their applications in various areas.
In summary, reversible thermochromism was achieved in hierarchically self-assembled PVP/PDA nanoaggregates using a hydrogen-bonding-assisted NCCM approach. Intr点击放大图片iguingly, a “bricks and mortar” structure in PVP/DA nanoaggregates was obtained by annealing the sample at a temperature (65°C) slightly higher than the melting point of pure DA crystals (63°C). After topochemical polymerization, the resultant PVP/PDA “bricks and mortar” structurewas further stabilized at high temperatures (up to 120°C). Contrary to pure irreversible PDA crystals, PVP-intercalated PDA nanoaggregates showed reversible thermochromic transitions in both aqueous suspension and dry films. The cooperative interaction between PVP and PDA through tethering carboxylic acid head groups in the side chains of PDA to PVP layers via hydrogen bonding is believed to be responsible for reversible conformational transitions between the “red” and “blue” states. This study not only opens a new avenue for further understanding of reversible thermochromism in polydiacetylenes but also leads to more effective ways of preparing thermally reversible polydiacetylene-based materials utilizing commercially available polymers and diacetylene monomers.
Hydrogen-Bonded Dendronized Polymers and Their Self-Assembly in Solution
Xie D (谢荡), Jiang M (江明), Zhang GZ (张广照), Chen DY (陈道勇)
Frechet-type benzyl ether dendrons of second and third generations with a carboxyl group (G2, G3) at the apex site could attach to poly(4-vinylpyridine) (PVP), forming hydrogen-bonded dendronized polymers (HB denpols) in their common solvent, chloroform. 点击放大图片The HB denpols show unique self-assembly behavior, forming vesicles in the common solvent under ultrasonic treatment.The structure and morphologyof the vesicles were characterized by dynamic light scattering (DLS), static light scattering(SLS), SEM, TEM,and AFM. The size of the vesicles decreases and thethickness of the vascular membrane increases as the molar ratio of Gx/PVP increases. The hydrogen bonding, pi-pi aromatic stacking of the dendrons, and the considerable difference in architecture between the dendron Gx and PVP are themain factors facilitating the assembly of the HB denpols in the common solvent.
Abstract The self-assembly of β-casein and lysozyme, a linear and a globular protein with isoelectric point of pH 5.0 and 10.7, respectively, was studied. Polydisperse electrostatic complex micelles formed when mixing β-casein and lysozyme aqueous solutions. After the micelle solution was heated, lysozyme ge点击放大图片lated and β-casein was trapped in the gel, producing narrowly dispersed nanoparticles. The nanoparticles were characterized with laser light scattering, ζ-potential, steady state fluorescence, atomic force microscopy, and transmission electron microscopy. The nanoparticles have spherical shape and their sizes depend on the pH of the heat treatment and the molar ratio of β-casein to lysozyme. The nanoparticles display amphoteric property and are relatively hydrophobic at pH around 5 and around 10. The net charges on the surface stabilize the nanoparticles in the solution
Micellization induced by the inclusion complexation between β-CD and adamantly group (ADA)
Jing Wang (王竞), Ming Jiang* (江明)
We developed a new route to fabricate non-covalently connected micelles (NCCM) of PGMA-CD/PtBA-ADA in aqueous media based on host-guest intera点击放大图片ction of β-CD and ADA. The presence of the β-CD cavities in the micellar shell provides broad opportunities to modify the micellar surface to meet different requirements in applications. Via shell-crosslinking and core-removal of the micelles, hollow spheres composed of β-CD-containing polymers were also obtained. These follow spheres possess multi-scale holes i.e. the large central one in size of 102 nm and many small β-CD cavities in 0.7 nm.
pH-Dependent Self-Assembly: Micellization and Micelle–Hollow-Sphere Transition of Cellulose-Based Copolymers
Hongjing Dou (窦红静), Ming Jiang* (江明)
The micellization of HEC-graft-poly(acrylic acid) (HEC-g-PAA),driven by the complexation between PAA grafts and HEC chains, and the transition between micelles and hollow spheres of in water were found to be pH-dependent and reversible. 点击放大图片
A Novel Route to Thermo-Sensitive Polymeric Core-shell Aggregates and Hollow Spheres in Aqueous Media
Youwei Zhang (张幼维), Ming Jiang* (江明)
The Poly(ε-carprolactone)(PCL)/Poly(N-isopropylacrylamide)(PNIPAM) core-shell particles was obtained by localizing the polymerization of NIPAM and crosslinker 点击放大图片methylene bisacrylamide around the surface of the PCL nanoparticles. The resultant particles were converted to hollow spheres by simply degradating the PCL core with enzyme. The attained hollow spheres is thermo-sensitive and displays reversible swelling and de-swelling around 32℃. Youwei Zhang, Jiang Ming et.al. Adv.Funct.Mater. 2005,15,695
Optical Switching of Self-Assembly: Micellization and Micelle–Hollow Sphere Transition of Hydrogen-Bonded Polymers
Xikui Liu (刘习奎), Ming Jiang*(江明)
The work reports reversible optical switching of micellization and micelle-hollow sphere transition in a blend solution of poly(4-phenylazomaleinanil- co-4-vinyl pyridine) (AzoMI-VPy) and carboxyl-ended polybutadiene CPB. Under UV irradiation, the trans-azobenzene units transformed into polar cis conformation and made AzoMI-VPy insoluble. Thus micelles formed with (AzoMI-VPy) core stabilized CPB shell through interpolymer hydrogen bonding. Upon visible light irradiation, the micelles quickly disassociated due to the cis form returning to 点击放大图片trans form. After core crosslinking, the micelles showed a reversible morphology change responding to light irradiation: visible light caused the formation of hollow spheres due to the core dissociation as a result of cis azobenzene turning to trans while UV light made the hollow spheres return to micelles due to the isomerization in the opposite direction. Xikui Liu, Ming Jiang Angew.Chem.Int.Ed 2006, 45, 3846
Preparation of Core-Stabilized Polymeric Micelles with a Mixed Shell Formed by Two Incompatible Polymers
Taoran Hui (惠陶然), Daoyong Chen* (陈道勇), Ming Jiang
The preparation of core-stabilized micelles with PEO/PS as th点击放大图片e shell by directly cross-linking P2VP in PS-b-P2VP and PEO-b-P2VP mixture in DMF, which is the common solvent of the block copolymers, using 1,4-dibromobutane as the cross-linker. Although the PEO chains and the PS chains are strongly incompatible, the cross-linking of P2VP blocks connects both the PEO and the PS chains to a common core and enables the sufficient mixing of the unlike blocks in the shell.
Short-life core-shell structured nano-aggregates formed by the self-assembly of PEO-b-PAA/ETC (1-(3-dimethylaminopropyl) -3-ethylcarbodiimide methiodide) and their stabilization
Chunfeng Gu (顾春锋), Daoyong Chen* (陈道勇), Ming Jiang
点击放大图片The self-association takes place in the aqueous solution of PEO-b-PAA/ETC at the early stage of the reaction between PAA and ETC. Due to the reaction cycle of ETC with PAA (as indicated in the scheme), the aggregates have a limited life in water. After staying unchanged for several days in the aqueous solutions, the aggregates dissociate and finally disappear 1 to 3 weeks after their formation.
Shaoyong Yu (喻绍勇), Xiaoyun Pan (潘晓赟), Ping Yao*, Ming Jiang
A new method was developed to produce nanogels with oppositely charged protein pairs or protein-polysaccharide pairs, such as chitosan-ovalbumin and ovalbumin-lysozyme pairs. The na点击放大图片nogels have core-shell structure. The dispersibility, the size and the hydrophobicity / hydrophilicity of the nanogels are pH responsible. Left figure is an illustration of the charge change of ovalbumin-lysozyme nanogels at different pH.Casein-g-dextran copolymer was prepared through the Maillard reaction. The copolymers form micelles at the pI of casein and the micelles dissociate when pH is away from t点击放大图片he pI. β-carotene can induce the copolymer micellization through hydrophobic interactions during the β-carotene encapsulation procedure.
Interactions of Apo Cytochrome c with Alternating Copolymers of Maleic Acid and Alkene
Li Liang(梁丽), Ping Yao*, Ming Jiang
The interactions of apo cytochrome c (apo cyt c) with poly(isobutylene-alt-maleic acid) (PIMA) and poly(1-tetradecene-alt-maleic acid) (PTMA) lead to点击放大图片 apo cyt c a conformational change from random coil to -helical structure. The -helix content is influenced by the copolymer concentration, the length of alkyl chain of the copolymers, and media pH. The interactions of PIMA or PTMA with apo cyt c at neutral and alkali pH destroy the hydrophobic aggregation of PTMA or apo cyt c and form new complex particles.
这里我们选择10篇代表性论文作简单交流，由此可以对我组研究工作的过去和现状有一个初步的了解。请点击文章名下载，下载之前请先安装Adobe AcrobatReader。 1． Ming Jiang, Hankun Xie Miscibility and Morphology in Copolymer/homopolymer Blends,Prog.Polym.Sci.1991,16,977 本组建立伊始，研究由均聚物／嵌段共聚物的相容性问题起步，积5－6年研究成果，提出此类共混物相容性的“共聚物链构造效应”（chain-architectural effect），本组成果及国际学术界在此领域于八十年代的进展均总结于此文中。