The other category concerns gels consisting of low molecular weight gelators commonly abbreviated to lmwg. Rheology of selfhealing supramolecular hydrogels jing zhang1,2,3, baohao zhang1,2, qiang chen3, bao zhang1,2 and jian song1,2 abstract physical gelation behaviors of a series of dgluconic acetalbased derivatives bearing fatty alkyl amine moieties have been investigated. These hydrogels are applied for various biomedical applications, matrices are developed for the culturing of cells, and hydrogel systems are used as drug delivery vehicles. The cif file of the crystal structure of 1 and additional schemes and figures are available free of charge via the. Introduction hydrogels have recently received much attention due to their potential in medical fields, such as drug delivery, tissue cultures, medical treatments, etc. Fabrication of multistimuli responsive supramolecular. Drug delivery from a hydrogel carrier implanted under the kidney capsule is an innovative way to induce kidney tissue regeneration andor prevent kidney inflammation or fibrosis. Besides macroscopic properties, such as soft and wet, the majority of the volume of supramolecular hydrogels is micropores filled with water. Hybrid supramolecular and colloidal hydrogels that bridge multiple length scales emmarose janec. Supramolecular hydrogels crosslinked by preassembled host. Ultrastiff and tough supramolecular hydrogels with a dense and. Encoding, reading, and transforming information using. In addition, supramolecular systems offer modularity and dynamics, also found in the ecm. Tough supramolecular hydrogel based on strong hydrophobic.
Recent advances in the role of supramolecular hydrogels in. These interstices allow the hydrogels to serve as a carrier or medium of other bioactive molecules 1126. Pdf nanoparticlebased catalysis using supramolecular. Such supramolecular sm hydrogels are well suited for more complicated applications like drug. The components of the supramolecular hydrogels are biocompatible and can readily be eliminated from the body.
Nanoparticlebased catalysis using supramolecular hydrogels. These results suggest that supramolecular hydrogels derived from the. Cyclodextrinbased supramolecular hydrogels advanced. Supramolecular hydrogels are formed by trapping water within a network. Structure, morphology and mechanical properties of.
Supramolecular hydrogels are designed, synthesized and characterized with the goal to control cell and tissue. Tunable supramolecular hydrogels for selection of lineageguiding metabolites in stem cell cultures. Drugbearing supramolecular filament hydrogels as anti. View the article pdf and any associated supplements and figures for a. A sprayable dynamically crosslinked supramolecular polymernanoparticle hydrogel that robustly adheres to tissue reduces the severity of cardiac adhesions in rats and sheep. Graphene oxide hybrid supramolecular hydrogels with self. The diverse range of applications has thrust hydrogels into the spotlight of scientific research. Because secondary interactions provide intrinsic mechanisms for energy dissipation, there is a large potential for designing hightoughness supramolecular hydrogels. Generally, the selfassembly of lmwhs is triggered by a solgel process through an external stimulus able to switch their solubility.
Pectin is an anionic, watersoluble polymer predominantly consisting of covalently 1,4linked. On the other hand, the supramolecular hydrogel decomposes upon addition of bispyridyl decamethylene pyc 10 py as a competitive guest. Supramolecular grid structures for hydrogels with self. Temperature and ion dual responsive biphenyldipeptide. Supramolecular hydrogels made of the basic biological. The backbones threedimensional structures of the resulting hydrogel are the hierarchical assemblies of the lmwg undergoing the lcst phase separation. Supramolecular hydrogels for antimicrobial therapy. Supramolecular hydrogels, formed by noncovalent crosslinking of polymeric chains in water, constitute an interesting class of materials that can be developed specifically for drug delivery and biomedical applications. Selfassembly provides access to a variety of molecular materials, yet spatial control over structure formation remains difficult to achieve. Department of biological chemistry, indian association for the cultivation of science, jadavpur, kolkata 700032 india, fax. Following molecular design, we focus on various potential applications of supramolecular.
A supramolecular hydrogel for generation of a benign dna hydrogel article pdf available in rsc advances 5128 december 2015 with 291 reads how we measure reads. This naturally occurring, renewable and biodegradable polymer is underutilized in polymer science due to its insolubility in organic solvents, which renders conventional polymerization methods impractical. Visual evidence of selfhealing of a supramolecular hydrogel through noncovalent hostguest interactions between. Gmp, is a selfassembling natural nucleotide that has unique potential to form ordered supramolecular structures. Further, in vivo studies in immunocompetent mice reveal that pnp hydrogels enhance hmsc retention at the injection site and retain administered hmscs locally for upwards of 2 weeks. Polyanilinedecorated supramolecular hydrogel with tough, fatigueresistant, and selfhealable performances for allinone flexible supercapacitors.
Article pdf available in international journal of biological macromolecules 75 february 2015 with 307 reads. Stimuliresponsive supramolecular hydrogels composed of aromatic short peptide gelators have attracted intensive attention in the field of biomedicine because of their stable chemical structure, simple and convenient synthetic route and intelligent response to external stimuli. Recent advances in supramolecular hydrogels for biomedical. Pdf on jan 1, 2015, mohammad reza saboktakin and others published. These hydrogels can be engineered to display dynamic slidingring or reversible crosslinking, as well as specific binding sites. Supramolecular hydrogels formed from polyviologen cross. Supramolecular architectures of natural organic matter. After a brief introduction of methods for generating supramolecular hydrogels, we discuss supramolecular hydrogelators on the basis of their categories, such as small organic molecules, coordination complexes, peptides, nucleobases, and saccharides. Metallo supramolecular hydrogels from the copolymers of acrylic acid and 42,26. A new conceptual model for supramolecular aggregation of natural organic matter om is proposed. Selfhealable macro microscopic shape memory hydrogels based on supramolecular interaction hao meng,a,b peng xiao,a jincui gu,a xiufang wen,b jie xu,c chuanzhuang zhao,c jiawei zhanga and tao chena adivision of polymer and composite materials, ningbo institute of material technology and engineering, chineseacademy of science. A supramolecular synergy of chemistry, topology, and mechanics jiawei yang, ruobing bai, baohong chen, and zhigang suo adhering hydrogels to various materials is fundamental to a large array of established and emerging applications. Mar 16, 2017 compared with most supramolecular hydrogels, these dna crosslinked hydrogels could be relatively strong and easily adjustable via sequence variation, but it is noteworthy that these hydrogels still have excellent thixotropic properties and could be easily injected through a needle. To address the challenges of combining a wide spectrum of mechanical properties and multiple sensory capabilities in artificial skins, supramolecular hydrogels 19,20,21,22 with tunable interactions and dynamic structures may provide a versatile toolbox.
The enzymeinstructed assembly of the core of yeast prion sup35 to form supramolecular hydrogels. Selfhealing supramolecular hydrogels have emerged as a novel class of bio. Herein we report for the first time the supramolecular hydrogelation of a derivative of 3nitrotyrosine 3nt, which is an oxidized byproduct of tyrosine, produced in the presence of reactive nitrogen species in the cell. Research group supramolecular chemistry supramolecular grid structures for hydrogels with selfhealing character thesis submitted to obtain the degree of master of science in chemistry by ruben lenaerts academic year 2014 2015 promoter. Supramolecular hydrogels based on dna selfassembly. Hybrid nanocomposites were constructed based on colloidal nanofibrillar hydrogels with interpenetrating supra. Such networks are held together through physical crosslinks created by weak, noncovalent interactions such as. Download fulltext pdf supramolecular hydrogels as drug delivery systems. A hydrogel formed with phospholipids and fatty acids would be of great interest in the medical field due to the biological relevance that these molecules have in living organisms. Metallosupramolecular hydrogels from the copolymers of. The hydrogels release steroid drug in vivo with no visible residue when release is complete. As a novel class of threedimensional 3d hydrophilic crosslinked polymers, supramolecular hydrogels not only display unique physicochemical properties e. Metallosupramolecular hydrogels from the copolymers of acrylic. Apr 10, 2014 a particularly interesting group of polymeric structures that is achievable via cdbased inclusion chemistry is that of supramolecular hydrogels, which are discussed in detail.
Nano express open access hofmeister anioninduced tunable rheology of selfhealing supramolecular hydrogels jing zhang1,2,3, baohao zhang1,2, qiang chen3, bao zhang1,2 and jian song1,2 abstract physical gelation behaviors of a series of dgluconic acetalbased derivatives bearing fatty alkyl amine moieties have been investigated. So we added a reference 32 for revised manuscript as following. Gmp to form blue emitting chiral carbon dots gdots that exhibit excitation dependent downconversion and u. They could be used for surveying the usage of biological small molecules during differentiation and. Included supramolecular hydrogels with tunable viscoelastic properties. Enzymatic formation of supramolecular hydrogels based on selfassembly of dna derivatives a thesis presented to department of chemistry graduate school of arts and sciences brandeis university waltham, massachusetts by junpeng chen this thesis describes the design and synthesis of a new hydrogelator napffdcp. Pdf supramolecular hydrogels as drug delivery systems. Use of a supramolecular polymeric hydrogel as an effective. From biomedical applications in tissue engineering, drug delivery and wound healing, and consumer care products such as contact lenses to laboratory purification in chromatography and as electrophoresis gels, many researchers are looking at hydrogels for their materials solutions.
The last few years have seen transformative advances in achieving strong hydrogel adhesion. The enzymeinstructed assembly of the core of yeast prion. Ultrastrong and tough supramolecular hydrogels from multiurea linkage segmented copolymers with tractable processablity and recyclability nannan yang state. Scientific awareness of om as natural hydrogels is slowly increasing although in the literature they are primarily categorized as physical hydrogels stabilized only by weak interactions. Luminescent hydrogels are of great potential for many fields, particularly serving as biomaterials ranging from fluorescent sensors to bioimaging agents. Although the gelation process and lower critical solution temperature lcst behavior are well acknowledged in polymer systems, lowmolecularweight gelators lmwgs rarely display lcst behavior during supramolecular gelation. These materials comprise of hydrophilic threedimensional networks held together by either covalent linkages or supramolecular interactions, capable of trapping.
Freestanding supramolecular hydrogel objects by reactiondiffusion. Injectable supramolecular polymernanoparticle hydrogels. Supramolecular hydrogels formed by decorating benzene1,3,5tricarboxamide bta units with amphiphilic ethylene glycolbased side chains are presented. Users are not otherwise permitted to reproduce, republish, redistribute, or sell any supporting information from the acs website, either in whole or in part, in either machinereadable form or any other form without permission from the american chemical society. We report here on the covalent conversion of the antiinflammatory agent ketoprofen into selfassembling prodrugs that enable the effective purification of ketoprofen enantiomers, the improved selectivity and potency of ketoprofen, as well as the formation of onecomponent drugbearing supramolecular hydrogels. Supramolecular hydrogels are designed, synthesized and characterized with the goal to control cell and tissue interactions. Tunable supramolecular hydrogels for selection of lineage. Herein, we report an lmwg system with lcsttype thermoresponsiveness and an lcsttriggered supramolecular gelation process. From supramolecular polymers to hydrogel materials. Files available from the acs website may be downloaded for personal use only. Hybrid supramolecular and colloidal hydrogels that bridge.
However, the tendency of phospholipid mixtures to form vesicular or micellar aggregates at high water content hinders the formati recent open access articles. In this work, the fundamental hydrogel mechanical properties that enhance hmsc delivery processes are elucidated using basic in vitro models. Pdf a supramolecular hydrogel for generation of a benign. Supramolecular hydrogels, also known as reversible hydrogels, feature secondary interactions, such as h bonding, ionic, and hydrophobic interactions. Preparation and characterization of a supramolecular. Based on the selfassembly capability of the core segment gnnqqny of yeast prion sup35, we design and synthesise a series of structurally related precursors for the enzymatic formation of. These novel supramolecular hydrogels also possessed a favorable selfhealing ability and better biocompatibility, which endowed the smart hydrogels with potential practical and reallife applications that will be beneficial for further development of more intelligent materials with desired functionalities. Thermoresponsive hydrogel induced by dual supramolecular. Here, robust luminescent hydrogels are reported using lanthanide complexes as emitting sources via a hierarchical organicinorganic self. Polymersupramolecular polymer doublenetwork hydrogel. Supramolecular hydrogels are versatile and can be combined with biological components such as cells to print high resolution, tissuelike structures, that could be used as models of healthy and diseased tissues for biological research, drug screening, and as therapeutic implants for damaged tissues. Bioinspired supramolecular fibers drawn from a multiphase.
Multilayer bioprinting of supramolecular hydrogels three dimensional printing of supramolecular hydrogels 3d printing, supramolecular hydrogel reference media rodell, et al. We envision that supramolecular hydrogels, in combination with modern medical technology and devices, will contribute to the development of efficient and safe systems for antimicrobial therapy. Pdf supramolecular hydrogels for antimicrobial therapy. Supramolecular hydrogels based on metalligand coordination and hostguest interactions. Supramolecular hydrogel from an oxidized byproduct of. Tartaric acid, urea, and guanidine with carboxylic amide and imine moieties respectively as. Supramolecular hydrogels as drug delivery systems sciencedirect. Continuous liquid interface production of alginate. To facilitate metabolomics analysis of stem cell differentiation, alakpa et al. Although the ph and temperature sensitivity has been focused on contributing to intelligence, the system sensitive to physiological reduction condition caused by glutathione tripeptide gsh. Creating transient gradients in supramolecular hydrogels. A supramolecular protein chaperone for vaccine delivery.
Inspired by the reported supramolecular hydrogels for additive manufacturing,12 we mixed microfluidicsderived cpc supraballs structural coloration material with selfhealable hydrogel scaffold as the assembly unit, producing a new kind of injectable photonic hydrogel iph. Polyanilinedecorated supramolecular hydrogel with tough. Injectable and selfhealing hydrogels have found numerous applications in drug delivery, tissue engineering and 3d cell culture. The supramolecular selfassembly of cyclodextrins cds and polymers has led to the development of novel supramolecular hydro gels for drug delivery. Supramolecular hydrogels for regenerative medicine springerlink. It is also attractive to incorporate stimuliresponsive properties into the system to create smart hydrogels. Supramolecular hydrogels for in situ creating gold and silver nanoparticles jiangshan shen,a yilin chen, b jiale huang,c jindun chen,a,c cong zhao,a,b yangqing zheng,a,c tao yu, d yi yang, a hongwu zhanga a institute of urban environment, chinese academy of sciences, xiamen, 361021, china. Supramolecular hydrogels for biomedical applications.
Tough supramolecular hydrogel based on strong hydrophobic interactions in a multiblock segmented copolymer marko mihajlovic, mariapaola staropoli. Local joint engineering laboratory of novel functional polymeric materials, jiangsu key laboratory of advanced functional polymer design and application, college of chemistry, chemical engineering and materials science, soochow university. Supramolecular hydrogels based on metalligand coordination. Abstractsupramolecular materials with noncovalent bonds have attracted much attention due. Jan 18, 2011 as the first demonstration of an enzymeswitchregulated supramolecular hydrogel and the first formation of supramolecular hydrogels in vivo by an enzymatic reaction, this enzymecatalyzed reversible selfassembly and gelation of the hydrogelators could lead to a new type of medium for drug delivery because it allows the hydrogels to respond to. Supramolecular chemistryconcepts and applications ajay kumar manna ramananda college, department of chemistry, bishnupur, bankura, west bengal, 722122, india abstract. Versatile small molecule motifs for selfassembly in water. There is interest in the development of drugbased hydrogels for responsive sustained drug release. Supramolecular hydrogels based on inclusion complexation between cyclodextrins cds and polymers have attracted much interest because of their potential for biomedical applications. Despite the various designs and morphologies of supramolecular hydrogels, there are some common properties. Supramolecular hydrogels based on cyclodextrinpolymer inclusion are an emerging injectable biomaterial for drug controlledrelease and cell capsulation. To circumvent this problem, ceriuminitiated radical. Three dimensional printing of supramolecular hydrogels.
Hofmeister anioninduced tunable rheology of selfhealing. In general the manuscript is well written and the text is easy to follow but i have some comments. Enzymatic formation of supramolecular hydrogels based on self. Jan 22, 2018 here, the preparation of three fluorescent blue, green, and red hydrogels containing both tetracationic receptoranion recognition motifs and gel. Assembly pattern of supramolecular hydrogel induced by. Supramolecular hydrogels, obtained from small organic molecules, may be advantageous over polymeric ones for several applications, because these materials have some peculiar properties that differentiate them from the traditional polymeric hydrogels, such as. Supramolecular hydrogels for in situ creating gold and silver. Thixotropic supramolecular pectinpolyethylene glycol. Multicomponent supramolecular hydrogels are constructed for sensitive, nakedeye detection of smallmolecule biomarkers. These metrics are regularly updated to reflect usage leading up to the last few days. Cd dimervp forms a selfstanding gel, which does not relax g g in the frequency range 0.
The hydrogel had a unique network structure involving two types of supramolecular selfassemblies between cyclodextrins and polymers, that is, the hostguest complexation between. Inspired by the microscopic architecture of natural cartilage, here the engineering of a novel doublenetwork hydrogel with interconnected polymer supramolecular polymer doublenetwork psdn gel. Freestanding supramolecular hydrogel objects by reaction. Here, the authors report on the selfassembly of natural small molecule, rhein, into hydrogels. Hence, the gelation of the lmwg is only realized when the gelation temperature is above the critical transition temperature tcloud of the lcst behavior, which is different from many supramolecular or polymeric hydrogel systems. The supramolecular protein chaperone interacted with antigens by physical interactions, which. Shah, chenyan liu, ziyi yu, ji liu, xiaohe ren, matthew j. Supramolecular hydrogels were obtained by simple addition of metal ions solution to cmch solution at an appropriate ph value. Pdf as a novel class of threedimensional 3d hydrophilic crosslinked polymers, supramolecular hydrogels not only display unique physicochemical. Supramolecular hydrogels formed through noncovalent interactions of lowmolecularweight hydrogelators lmwhs show great potential applications in different fields, such as delivery of therapeutics, injectable biomaterials, catalysis, or materials chemistry. Directed selfassembly of herbal small molecules into. Cd units and adamantyl groups and the polypseudorotaxane formation between.
Supramolecular hydrogels are one of the hydrogels consisting of a solid threedimensional network with noncovalent bonds such as hydrogen bond, hydrophobic interaction, and cation. The uses of supramolecular hydrogels as intrarenal drug. This article is from beilstein journal of organic chemistry, volume 8. We report here on the development of supramolecular hydrogels for this. These features render the supramolecular hydrogels suitable as drug delivery systems and tissue engineering scaffolds. Tan, antti nyknen, marjo kettunen, janne laine, olli ikkala, and oren a. Versatile small molecule motifs for selfassembly in water and formation of biofunctional supramolecular hydrogels. Supramolecular hydrogels constructed by reversible bonds are expected to show stimuli responsiveness and selfhealing properties. This chapter gives an overview of translational research on different supramolecular hydrogels, showing systems that have been used in vivo in the field of regenerative medicine. Supramolecular selfassembled gels are based on noncovalent, dynamic bonds, which are often reversible and hence potentially able to reform in a gel after damage. Polymers free fulltext metallosupramolecular hydrogels.
These gels facilitate stiffnesstuned stem cell differentiation without having to rely on biochemical functionalization. The manuscript deals with the crosslinking the polymers with the use of metal cation and terpyridine unit. Therefore, supramolecular hydrogels made of basic biological building blocks, ultimately, may lead to soft materials with designed or unexpected biological functions. The strong supramolecular interactions between the functional biopolymers and the nps that give rise to the hydrogel structure yield in vivo depots capable of persisting for long timescales in the body. A supramolecular biomimetic skin combining a wide spectrum. Dec 23, 2015 the development of supramolecular hydrogels in the past two decades not only has underscored the above implication, but also has provided a fundamentally new approach for chemists to control the properties of soft materials via the molecular engineering of a diverse set of substrates for a wide range of applications. Chemically reactive supramolecular hydrogel coupled with a. Such networks are held together through physical crosslinks created by weak, noncovalent interactions such as hydrogen bonds. Although many attempts are made to develop new hydrogels with good self. Ultrastrong and tough supramolecular hydrogels from. Bioinspired supramolecular fibers drawn from a multiphase selfassembled hydrogel yuchao wu, darshil u. Lightresponsive and selfhealing behavior of azobenzene. Request pdf supramolecular hydrogels for biomedical applications front cover. The 9fluorenylmethyloxycarbonyl fmoc derivative of 3nt, fnt, can form selfsupported hydrogels at a wide range of ph values 4.
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