Gel

For other uses, see Gel (disambiguation).

A gel is a solid jelly-like material that can have properties ranging from soft and weak to hard and tough. Gels are defined as a substantially dilute cross-linked system, which exhibits no flow when in the steady-state.[1] By weight, gels are mostly liquid, yet they behave like solids due to a three-dimensional cross-linked network within the liquid. It is the crosslinking within the fluid that gives a gel its structure (hardness) and contributes to the adhesive stick (tack). In this way gels are a dispersion of molecules of a liquid within a solid in which the solid is the continuous phase and the liquid is the discontinuous phase. The word gel was coined by 19th-century Scottish chemist Thomas Graham by clipping from gelatine.[2]

IUPAC definition

Gel: Nonfluid colloidal network or polymer network that is expanded throughout its whole volume by a fluid.[3]

Note 1: A gel has a finite, usually rather small, yield stress.

Note 2: A gel can contain:

(i) a covalent polymer network, e.g., a network formed by crosslinking polymer chains or by nonlinear polymerization;
(ii) a polymer network formed through the physical aggregation of polymer chains, caused by hydrogen bonds, crystallization, helix formation, complexation, etc., that results in regions of local order acting as the network junction points. The resulting swollen network may be termed a “thermoreversible gel” if the regions of local order are thermally reversible;
(iii) a polymer network formed through glassy junction points, e.g., one based on block copolymers. If the junction points are thermally reversible glassy domains, the resulting swollen network may also be termed a thermoreversible gel;
(iv) lamellar structures including mesophases {Ref.[4] defines lamellar crystal and mesophase}, e.g., soap gels, phospholipids, and clays;
(v) particulate disordered structures, e.g., a flocculent precipitate usually consisting of particles with large geometrical anisotropy, such as in V2O5 gels and globular or fibrillar protein gels.

Note 3: Corrected from ref.,[5] where the definition is via the property identified in Note 1 (above) rather than of the structural characteristics that describe a gel.[6]

Hydrogel: Gel in which the swelling agent is water.

Note 1: The network component of a hydrogel is usually a polymer network.

Note 2: A hydrogel in which the network component is a colloidal network may be referred to as an aquagel.

Note 3: Definition quoted from refs.[6][7][8]

An upturned vial of hair gel

Composition

Gels consist of a solid three-dimensional network that spans the volume of a liquid medium and ensnares it through surface tension effects. This internal network structure may result from physical bonds (physical gels) or chemical bonds (chemical gels), as well as crystallites or other junctions that remain intact within the extending fluid. Virtually any fluid can be used as an extender including water (hydrogels), oil, and air (aerogel). Both by weight and volume, gels are mostly fluid in composition and thus exhibit densities similar to those of their constituent liquids. Edible jelly is a common example of a hydrogel and has approximately the density of water.

Polyionic polymers

Polyionic polymers are polymers with an ionic functional group. The ionic charges prevent the formation of tightly coiled polymer chains. This allows them to contribute more to viscosity in their stretched state, because the stretched-out polymer takes up more space. See polyelectrolyte for more information.

Types

Hydrogels

A micropump based on a hydrogel bar (4×0.3×0.05 mm size) actuated by applied voltage. This pump can be continuously operated with a 1.5 V battery for at least 6 months.[9]

A hydrogel is a network of polymer chains that are hydrophilic, sometimes found as a colloidal gel in which water is the dispersion medium. Hydrogels are highly absorbent (they can contain over 90% water) natural or synthetic polymeric networks. Hydrogels also possess a degree of flexibility very similar to natural tissue, due to their significant water content. The first appearance of the term 'hydrogel' in the literature was in 1894.[10] Common uses for hydrogels include:

Other, less common uses include

Common ingredients include polyvinyl alcohol, sodium polyacrylate, acrylate polymers and copolymers with an abundance of hydrophilic groups.

Natural hydrogel materials are being investigated for tissue engineering; these materials include agarose, methylcellulose, hyaluronan, and other naturally derived polymers.

Organogels

See also: Organogels

An organogel is a non-crystalline, non-glassy thermoreversible (thermoplastic) solid material composed of a liquid organic phase entrapped in a three-dimensionally cross-linked network. The liquid can be, for example, an organic solvent, mineral oil, or vegetable oil. The solubility and particle dimensions of the structurant are important characteristics for the elastic properties and firmness of the organogel. Often, these systems are based on self-assembly of the structurant molecules.[14][15] (An example of formation of an undesired thermoreversible network is the occurrence of wax crystallization in petroleum.[16])

Organogels have potential for use in a number of applications, such as in pharmaceuticals,[17] cosmetics, art conservation,[18] and food.[19]

Xerogels

A xerogel /ˈzɪəroʊˌdʒɛl/ is a solid formed from a gel by drying with unhindered shrinkage. Xerogels usually retain high porosity (15–50%) and enormous surface area (150–900 m2/g), along with very small pore size (1–10 nm). When solvent removal occurs under supercritical conditions, the network does not shrink and a highly porous, low-density material known as an aerogel is produced. Heat treatment of a xerogel at elevated temperature produces viscous sintering (shrinkage of the xerogel due to a small amount of viscous flow) and effectively transforms the porous gel into a dense glass.

Nanocomposite hydrogels

Nanocomposite hydrogels[20][21] are also known as hybrid hydrogels, can be defined as highly hydrated polymeric networks, either physically or covalently crosslinked with each other and/or with nanoparticles or nanostructures. Nanocomposite hydrogels can mimic native tissue properties, structure and microenvironment due to their hydrated and interconnected porous structure. A wide range of nanoparticles, such as carbon-based, polymeric, ceramic, and metallic nanomaterials can be incorporated within the hydrogel structure to obtain nanocomposites with tailored functionality. Nanocomposite hydrogels can be engineered to possess superior physical, chemical, electrical, and biological properties.[20]

Properties

Many gels display thixotropy – they become fluid when agitated, but resolidify when resting. In general, gels are apparently solid, jelly-like materials. By replacing the liquid with gas it is possible to prepare aerogels, materials with exceptional properties including very low density, high specific surface areas, and excellent thermal insulation properties.

Animal-produced gels

Some species secrete gels that are effective in parasite control. For example, the long-finned pilot whale secretes an enzymatic gel that rests on the outer surface of this animal and helps prevent other organisms from establishing colonies on the surface of these whales' bodies.[22]

Hydrogels existing naturally in the body include mucus, the vitreous humor of the eye, cartilage, tendons and blood clots. Their viscoelastic nature results in the soft tissue component of the body, disparate from the mineral-based hard tissue of the skeletal system. Researchers are actively developing synthetically derived tissue replacement technologies derived from hydrogels, for both temporary implants (degradable) and permanent implants (non-degradable). A review article on the subject discusses the use of hydrogels for nucleus pulposus replacement, cartilage replacement, and synthetic tissue models.[23]

Applications

Many substances can form gels when a suitable thickener or gelling agent is added to their formula. This approach is common in manufacture of wide range of products, from foods to paints and adhesives.

In fiber optics communications, a soft gel resembling "hair gel" in viscosity is used to fill the plastic tubes containing the fibers. The main purpose of the gel is to prevent water intrusion if the buffer tube is breached, but the gel also buffers the fibers against mechanical damage when the tube is bent around corners during installation, or flexed. Additionally, the gel acts as a processing aid when the cable is being constructed, keeping the fibers central whilst the tube material is extruded around it.

RNA Triple-helix hydrogels for cancer therapy

Recently, Conde et al. developed a self-assembled dual-color RNA triple-helix structure comprising two miRNAs, a miR mimic (tumor suppressor miRNA) and an antagomiR (oncomiR inhibitor) provides outstanding capability to synergistically abrogate tumors.[24] The authors hypothesized that efficacious delivery of the RNA triple-helix hydrogel nanoconjugates would be achieved by coating the breast tumor with the adhesive hydrogel scaffold that they have previously shown able to enhance the stability of embedded nanoparticles used for local gene and drug delivery using smart gold nanobeacons.[25]

Conjugation of RNA triple-helices to dendrimers allows the formation of stable triplex nanoparticles, which form an RNA-triple-helix adhesive scaffold on interaction with dextran aldehyde, the latter able to chemically interact and adhere to natural tissue amines in the tumor. The authors also show that the self-assembled RNA-triple-helix conjugates remain functional in vitro and in vivo, and that they lead to nearly 90% levels of tumor shrinkage two weeks post-gel implantation in a triple-negative breast-cancer mouse model. These findings suggest that the RNA-triple-helix hydrogels can be used as an efficient anticancer platform to locally modulate the expression of endogenous miRs in cancer.

The authors reported on a novel strategy for concomitant oncomiR inhibition and tumor suppressor miR replacement therapy using a RNA triple-helix hydrogel scaffold that affords highly efficacious local anticancer therapy. Self-assembled RNA triple-helix conjugates remain functional in vitro with high selective uptake and control over miR expression compared to their respective single-stranded or double-stranded forms. Hence, cancer gene delivery systems should provide potent, selective and specific treatment to tumor cells only, unlike the standard delivery of most conventional chemotherapeutic drugs. This approach can be implemented to design self-assembled triplex structures from any other miR combination, or from other genetic materials including antisense DNA or siRNA to treat a range of diseases.

See also

References

  1. ↑ Ferry, John D. (1980) Viscoelastic Properties of Polymers. New York: Wiley, ISBN 0471048941.
  2. ↑ Harper, Douglas. "Online Etymology Dictionary: gel". Online Etymology Dictionary. Retrieved 2013-12-09.
  3. ↑ Richard G. Jones, Edward S. Wilks, W. Val Metanomski, Jaroslav Kahovec, Michael Hess, Robert Stepto, Tatsuki Kitayama, ed. (2009). Compendium of Polymer Terminology and Nomenclature (IUPAC Recommendations 2008) ("The Purple Book") (2nd ed.). RSC. p. 464. ISBN 978-0-85404-491-7.
  4. ↑ Sing, K. S. W. (1985). "Reporting physisorption data for gas/solid systems with Special Reference to the Determination of Surface Area and Porosity". Pure and Applied Chemistry 57 (4): 603–619. doi:10.1351/pac198557040603.
  5. ↑ Alan D. MacNaught, Andrew R. Wilkinson, ed. (1997). Compendium of Chemical Terminology: IUPAC Recommendations (the "Gold Book") (2 ed.). Oxford: Blackwell Science. ISBN 0865426848.
  6. 1 2 Slomkowski, Stanislaw; Alemán, José V.; Gilbert, Robert G.; Hess, Michael; Horie, Kazuyuki; Jones, Richard G.; Kubisa, Przemyslaw; Meisel, Ingrid; Mormann, Werner; Penczek, Stanisław; Stepto, Robert F. T. (2011). "Terminology of polymers and polymerization processes in dispersed systems (IUPAC Recommendations 2011)". Pure and Applied Chemistry 83 (12): 2229–2259. doi:10.1351/PAC-REC-10-06-03.
  7. ↑ Richard G. Jones, Edward S. Wilks, W. Val Metanomski, Jaroslav Kahovec, Michael Hess, Robert Stepto, Tatsuki Kitayama, ed. (2009). Compendium of Polymer Terminology and Nomenclature (IUPAC Recommendations 2008) ("The Purple Book"). RSC. ISBN 978-0-85404-491-7.
  8. ↑ Alan D. MacNaught, Andrew R. Wilkinson, ed. (1997). Compendium of Chemical Terminology: IUPAC Recommendations (the "Gold Book") (2nd ed.). Blackwell Science. ISBN 0865426848.
  9. ↑ Kwon, Gu Han; Jeong, Gi Seok; Park, Joong Yull; Moon, Jin Hee; Lee, Sang-Hoon (2011). "A low-energy-consumption electroactive valveless hydrogel micropump for long-term biomedical applications". Lab on a Chip 11 (17): 2910–5. doi:10.1039/C1LC20288J. PMID 21761057.
  10. ↑ "Der Hydrogel und das kristallinische Hydrat des Kupferoxydes". Zeitschrift für Chemie und Industrie der Kolloide 1 (7): 213–214. 1907. doi:10.1007/BF01830147.
  11. ↑ Mellati, Amir; Dai, Sheng; Bi, Jingxiu; Jin, Bo; Zhang, Hu (2014). "A biodegradable thermosensitive hydrogel with tuneable properties for mimicking three-dimensional microenvironments of stem cells". RSC Adv. 4 (109): 63951–63961. doi:10.1039/C4RA12215A. ISSN 2046-2069.
  12. ↑ Discher, D. E.; Janmey, P; Wang, YL (2005). "Tissue Cells Feel and Respond to the Stiffness of Their Substrate". Science 310 (5751): 1139–43. Bibcode:2005Sci...310.1139D. doi:10.1126/science.1116995. PMID 16293750.
  13. ↑ AK Yetisen, I Naydenova, F da Cruz Vasconcellos, J Blyth and CR Lowe (2014). "Holographic Sensors: Three-Dimensional Analyte-Sensitive Nanostructures and their Applications". Chemical Reviews 114 (20): 10654–96. doi:10.1021/cr500116a. PMID 25211200.
  14. ↑ Terech P. (1997) "Low-molecular weight organogelators", pp. 208–268 in: Robb I.D. (ed.) Specialist surfactants. Glasgow: Blackie Academic and Professional, ISBN 0751403407.
  15. ↑ van Esch J., Schoonbeek F., De Loos M., Veen E.M., Kellog R.M., Feringa B.L. (1999) "Low molecular weight gelators for organic solvents", pp. 233–259 in: Ungaro R., Dalcanale E. (eds.) Supramolecular science: where it is and where it is going. Kluwer Academic Publishers, ISBN 079235656X.
  16. ↑ Visintin RFG, Lapasin R, Vignati E, D'Antona P, Lockhart TP (2005). "Rheological behavior and structural interpretation of waxy crude oil gels". Langmuir 21 (14): 6240–9. doi:10.1021/la050705k. PMID 15982026.
  17. ↑ Kumar, R; Katare, OP (2005). "Lecithin organogels as a potential phospholipid-structured system for topical drug delivery: A review". AAPS PharmSciTech 6 (2): E298–310. doi:10.1208/pt060240. PMC 2750543. PMID 16353989.
  18. ↑ Carretti E, Dei L, Weiss RG (2005). "Soft matter and art conservation. Rheoreversible gels and beyond". Soft Matter 1: 17. Bibcode:2005SMat....1...17C. doi:10.1039/B501033K.
  19. ↑ Pernetti M, van Malssen KF, Flöter E, Bot A (2007). "Structuring of edible oils by alternatives to crystalline fat". Current Opinion in Colloid & Interface Science 12 (4–5): 221–231. doi:10.1016/j.cocis.2007.07.002.
  20. 1 2 Gaharwar, Akhilesh K.; Peppas, Nicholas A.; Khademhosseini, Ali (March 2014). "Nanocomposite hydrogels for biomedical applications". Biotechnology and Bioengineering 111 (3): 441–453. doi:10.1002/bit.25160. PMC 3924876. PMID 24264728.
  21. ↑ Carrow, James K.; Gaharwar, Akhilesh K. (November 2014). "Bioinspired Polymeric Nanocomposites for Regenerative Medicine". Macromolecular Chemistry and Physics 216 (3): 248–264. doi:10.1002/macp.201400427.
  22. ↑ Dee, Eileen May; McGinley, Mark and Hogan, C. Michael (2010). "Long-finned pilot whale" in Saundry, Peter and Cleveland, Cutler (eds.) Encyclopedia of Earth. National Council for Science and the Environment. Washington DC.
  23. ↑ "Injectable Hydrogel-based Medical Devices: "There's always room for Jell-O"1". Orthoworld.com. September 15, 2010. Retrieved 2013-05-19.
  24. ↑ Conde, J; Oliva, N; Atilano, M; Song, HS; Artzi, N (2015). "Self-assembled RNA-triple-helix hydrogel scaffold for microRNA modulation in the tumour microenvironment". Nat Mater. doi:10.1038/nmat4497.
  25. ↑ Conde, J; Oliva, N; Artzi, N (Mar 2015). "Implantable hydrogel embedded dark-gold nanoswitch as a theranostic probe to sense and overcome cancer multidrug resistance". Proc Natl Acad Sci U S A. 112 (11): E1278–87. doi:10.1073/pnas.1421229112.

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