Surfactant

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Schematic diagram of a micelle of oil in aqueous suspension, such as might occur in an emulsion of oil in water. In this example, the surfactant molecules' oil-soluble tails project into the oil (blue), while the water-soluble ends remain in contact with the water phase (red).

Surfactants are compounds that lower the surface tension (or interfacial tension) between two liquids, between a gas and a liquid, or between a liquid and a solid. Surfactants may act as detergents, wetting agents, emulsifiers, foaming agents, and dispersants.

Etymology and definition[edit]

The word surfactant is a blend of surface-active agent.[1]

The United States National Library of Medicine's Medical Subject Headings (MeSH) vocabulary reserves surfactant for the meaning "pulmonary surfactant". For the more general meaning, surface active agent/s is the heading.

Schematic diagram of a micelle – the lipophilic tails of the surfactant ions remain inside the oil because they interact more strongly with oil than with water. The polar "heads" of the surfactant molecules coating the micelle interact more strongly with water, so they form a hydrophilic outer layer that forms a barrier between micelles. This inhibits the oil droplets, the hydrophobic cores of micelles, from merging into fewer, larger droplets ("emulsion breaking") of the micelle. The compounds that coat a micelle are typically amphiphilic in nature, meaning that micelles may be stable either as droplets of aprotic solvents such as oil in water, or as protic solvents such as water in oil. When the droplet is aprotic it is sometimes[when?] known as a reverse micelle.

Composition and structure[edit]

Surfactants are usually organic compounds that are amphiphilic, meaning they contain both hydrophobic groups (their tails) and hydrophilic groups (their heads).[2] Therefore, a surfactant contains both a water-insoluble (or oil-soluble) component and a water-soluble component. Surfactants will diffuse in water and adsorb at interfaces between air and water or at the interface between oil and water, in the case where water is mixed with oil. The water-insoluble hydrophobic group may extend out of the bulk water phase, into the air or into the oil phase, while the water-soluble head group remains in the water phase.

World production of surfactants is estimated at 15 Mton/y, of which about half are soaps. Other surfactants produced on a particularly large scale are linear alkylbenzene sulfonates (1700 kton/y), lignin sulfonates (600 kton/y), fatty alcohol ethoxylates (700 ktons/y), and alkylphenol ethoxylates (500 kton/y).[3]

Sodium stearate, the most common component of most soap, which comprises about 50% of commercial surfactants
4-(5-Dodecyl) benzenesulfonate, a linear dodecylbenzenesulfonate, one of the most common surfactants

Structure of surfactant phases in water[edit]

In the bulk aqueous phase, surfactants form aggregates, such as micelles, where the hydrophobic tails form the core of the aggregate and the hydrophilic heads are in contact with the surrounding liquid. Other types of aggregates can also be formed, such as spherical or cylindrical micelles or lipid bilayers. The shape of the aggregates depends on the chemical structure of the surfactants, namely the balance in size between the hydrophilic head and hydrophobic tail. A measure of this is the hydrophilic-lipophilic balance (HLB).Surfactants reduce the surface tension of water by adsorbing at the liquid-air interface. The relation that links the surface tension and the surface excess is known as the Gibbs isotherm.

Dynamics of surfactants at interfaces[edit]

The dynamics of surfactant adsorption is of great importance for practical applications such as in foaming, emulsifying or coating processes, where bubbles or drops are rapidly generated and need to be stabilized. The dynamics of adsorption depend on the diffusion coefficient of the surfactant. As the interface is created, the adsorption is limited by the diffusion of the surfactant to the interface. In some cases, there can exist an energetic barrier to adsorption or desorption of the surfactant. If such a barrier limits the adsorption rate, the dynamics are said to be ‘kinetically limited'. Such energy barriers can be due to steric or electrostatic repulsions. The surface rheology of surfactant layers, including the elasticity and viscosity of the layer, play an important role in the stability of foams and emulsions.

Characterization of interfaces and surfactant layers[edit]

Interfacial and surface tension can be characterized by classical methods such as the -pendant or spinning drop method. Dynamic surface tensions, i.e. surface tension as a function of time, can be obtained by the maximum bubble pressure apparatus

The structure of surfactant layers can be studied by ellipsometry or X-Ray reflectivity.

Surface rheology can be characterized by the oscillating drop method or shear surface rheometers such as double-cone, double-ring or magnetic rod shear surface rheometer.

Classification[edit]

The "tails" of most surfactants are fairly similar, consisting of a hydrocarbon chain, which can be branched, linear, or aromatic. Fluorosurfactants have fluorocarbon chains. Siloxane surfactants have siloxane chains.

Many important surfactants include a polyether chain terminating in a highly polar anionic group. The polyether groups often comprise ethoxylated (polyethylene oxide-like) sequences inserted to increase the hydrophilic character of a surfactant. Polypropylene oxides conversely, may be inserted to increase the lipophilic character of a surfactant.

Surfactant molecules have either one tail or two; those with two tails are said to be double-chained.

Surfactant classification according to the composition of their head: non-ionic, anionic, cationic, amphoteric.

Most commonly, surfactants are classified according to polar head group. A non-ionic surfactant has no charged groups in its head. The head of an ionic surfactant carries a net positive, or negative charge. If the charge is negative, the surfactant is more specifically called anionic; if the charge is positive, it is called cationic. If a surfactant contains a head with two oppositely charged groups, it is termed zwitterionic. Commonly encountered surfactants of each type include:

Anionic: sulfate, sulfonate, and phosphate, carboxylate derivatives[edit]

Anionic surfactants contain anionic functional groups at their head, such as sulfate, sulfonate, phosphate, and carboxylates. Prominent alkyl sulfates include ammonium lauryl sulfate, sodium lauryl sulfate (sodium dodecyl sulfate, SLS, or SDS), and the related alkyl-ether sulfates sodium laureth sulfate (sodium lauryl ether sulfate or SLES), and sodium myreth sulfate.

Others include:

Carboxylates are the most common surfactants and comprise the carboxylate salts (soaps), such as sodium stearate. More specialized species include sodium lauroyl sarcosinate and carboxylate-based fluorosurfactants such as perfluorononanoate, perfluorooctanoate (PFOA or PFO).

Cationic head groups[edit]

pH-dependent primary, secondary, or tertiary amines; primary and secondary amines become positively charged at pH < 10:[4] octenidine dihydrochloride.

Permanently charged quaternary ammonium salts: cetrimonium bromide (CTAB), cetylpyridinium chloride (CPC), benzalkonium chloride (BAC), benzethonium chloride (BZT), dimethyldioctadecylammonium chloride, and dioctadecyldimethylammonium bromide (DODAB).

Zwitterionic surfactants[edit]

Zwitterionic (amphoteric) surfactants have both cationic and anionic centers attached to the same molecule. The cationic part is based on primary, secondary, or tertiary amines or quaternary ammonium cations. The anionic part can be more variable and include sulfonates, as in the sultaines CHAPS (3-[(3-cholamidopropyl)dimethylammonio]-1-propanesulfonate) and cocamidopropyl hydroxysultaine. Betaines such as cocamidopropyl betaine have a carboxylate with the ammonium. The most common biological zwitterionic surfactants have a phosphate anion with an amine or ammonium, such as the phospholipids phosphatidylserine, phosphatidylethanolamine, phosphatidylcholine, and sphingomyelins.

Non-ionic[edit]

Non-ionic surfactants have covalently bonded oxygen-containing hydrophilic groups, which are bonded to hydrophobic parent structures. The water-solubility of the oxygen groups is the result of hydrogen bonding. Hydrogen bonding decreases with increasing temperature, and the water solubility of non-ionic surfactants therefore decreases with increasing temperature.

Non-ionic surfactants are less sensitive to water hardness than anionic surfactants, and they foam less strongly. The differences between the individual types of non-ionic surfactants are slight, and the choice is primarily governed having regard to the costs of special properties (e.g., effectiveness and efficiency, toxicity, dermatological compatibility, biodegradability) or permission for use in food.[3]

Ethoxylates[edit]

Fatty alcohol ethoxylates[edit]
Alkylphenol ethoxylates (APEs or APEOs)[edit]
Fatty acid ethoxylates[edit]

Fatty acid ethoxylates are a class of very versatile surfactants, which combine in a single molecule the characteristic of a weakly anionic, pH-responsive head group with the presence of stabilizing and temperature responsive ethyleneoxide units.[5]

Special ethoxylated fatty esters and oils[edit]
Ethoxylated amines and/or fatty acid amides[edit]
Terminally blocked ethoxylates[edit]

Fatty acid esters of polyhydroxy compounds[edit]

Fatty acid esters of glycerol[edit]
Fatty acid esters of sorbitol[edit]

Spans:

Tweens:

Fatty acid esters of sucrose[edit]
Alkyl polyglucosides[edit]

Amine oxides[edit]

Surfactants in biology[edit]

Phosphatidylcholine, found in lecithin, is a pervasive biological surfactant. Shown in redcholine and phosphate group; blackglycerol; greenmonounsaturated fatty acid; bluesaturated fatty acid.

The human body produces diverse surfactants. Pulmonary surfactant is produced in lungs in order to facilitate breathing by increasing total lung capacity, TLC, and lung compliance. In respiratory distress syndrome or RDS surfactant replacement therapy helps patients have normal respiration by using pharmaceutical forms of the surfactants. One example of pharmaceutical pulmonary surfactants is Survanta (beractant) or its generic form Beraksurf produced by Abbvie and Tekzima respectively. Bile salts play important role in digestion.[6]

Safety and environmental risks[edit]

Most anionic and non-ionic surfactants are nontoxic, having LD50 comparable to sodium chloride. The toxicity of quaternary ammonium compounds, which are antibacterial and antifungal, varies. Dialkyldimethylammonium chlorides (DDAC, DSDMAC) used as fabric softeners have low LD50 (5 g/kg) and are essentially non-toxic, while the disinfectant alkylbenzyldimethylammonium chloride has an LD50 of 0.35 g/kg. Prolonged exposure to surfactants can irritate and damage the skin because surfactants disrupt the lipid membrane that protects skin and other cells. Skin irritancy generally increases in the series non-ionic, amphoteric, anionic, cationic surfactants.[3]

Surfactants are routinely deposited in numerous ways on land and into water systems, whether as part of an intended process or as industrial and household waste. Some of them are known to be toxic to animals, ecosystems, and humans, and can increase the diffusion of other environmental contaminants.[7][8][9]

Anionic surfactants can be found in soils as the result of sludge application, wastewater irrigation, and remediation processes. Relatively high concentrations of surfactants together with multimetals can represent an environmental risk. At low concentrations, surfactant application is unlikely to have a significant effect on trace metal mobility.[10][11]

In the case of Deepwater Horizon oil spill, unprecedented amounts of Corexit were sprayed directly into the ocean at the leak and on the sea-water's surface. The apparent theory being that the surfactants isolate droplets of oil, making it easier for petroleum-consuming microbes to digest the oil. The active ingredient in Corexit is dioctyl sodium sulfosuccinate (DOSS), sorbitan monooleate (Span 80), and polyoxyethylenated sorbitan monooleate (Tween-80)).[12][13]

Biodegradation[edit]

Two major surfactants, linear alkylbenzene sulfonates (LAS) and the alkyl phenol ethoxylates (APE) break down under aerobic conditions found in sewage treatment plants and in soil to nonylphenol, which is thought to be an endocrine disruptor.[14][15]

Attracting much attention is the non-biodegradability of fluorosurfactant, e.g. perfluorooctanoic acid (PFOA).[16]

Applications[edit]

The annual global production of surfactants was 13 million tonnes in 2008.[17][18] In 2014, the world market for surfactants reached a volume of more than 33 billion US-dollars. Market researchers expect annual revenues to increase by 2.5% per year to around 40.4 billion US-dollars until 2022. The commercially most significant type of surfactants is currently the anionic surfactant alkyl benzene sulfonate (LAS), which is widely used in cleaners and detergents.[19]

Surfactants play an important role as cleaning, wetting, dispersing, emulsifying, foaming and anti-foaming agents in many practical applications and products, including detergents, fabric softeners, emulsions, soaps, paints, adhesives, inks, anti-fogs, ski waxes, snowboard wax, deinking of recycled papers, in flotation, washing and enzymatic processes, laxatives. Also agrochemical formulations such as Herbicides (some), insecticides, biocides (sanitizers), and spermicides (nonoxynol-9). Personal care products such as cosmetics, shampoos, shower gel, hair conditioners (after shampoo), toothpastes. Surfactants are used in firefighting and pipelines (liquid drag reducing agents). Alkali surfactant polymers are used to mobilize oil in oil wells.[20]

The displacement of air from the matrix of cotton pads and bandages so that medicinal solutions can be absorbed for application to various body areas; the displacement of dirt and debris by the use of detergents in the washing of wounds;[21] and the application of medicinal lotions and sprays to surface of skin and mucous membranes.[22]

Detergents in biochemistry and biotechnology[edit]

In solution, detergents help solubilize a variety of chemical species by dissociating aggregates and unfolding proteins. Popular surfactants in the biochemistry laboratory are sodium lauryl sulfate (SDS) and cetyl trimethylammonium bromide (CTAB). Detergents are key reagents to extract protein by lysis of the cells and tissues: They disorganize the membrane's lipidic bilayer (SDS, Triton X-100, X-114, CHAPS, DOC, and NP-40), and solubilize proteins. Milder detergents such as octyl thioglucoside, octyl glucoside or dodecyl maltoside are used to solubilize membrane proteins such as enzymes and receptors without denaturing them. Non-solubilized material is harvested by centrifugation or other means. For electrophoresis, for example, proteins are classically treated with SDS to denature the native tertiary and quaternary structures, allowing the separation of proteins according to their molecular weight.

Detergents have also been used to decellularise organs. This process maintains a matrix of proteins that preserves the structure of the organ and often the microvascular network. The process has been successfully used to prepare organs such as the liver and heart for transplant in rats.[23] Pulmonary surfactants are also naturally secreted by type II cells of the lung alveoli in mammals.

Quantum dot preparation[edit]

Surfactants are used with quantum dots in order to manipulate growth.[24] and assembly of the dots, reactions on their surface, electrical properties, etc., it is important to understand how surfactants arrange[25] on the surface of the quantum dots.

See also[edit]

References[edit]

  1. ^ Rosen MJ, Kunjappu JT (2012). Surfactants and Interfacial Phenomena (4th ed.). Hoboken, New Jersey: John Wiley & Sons. p. 1. ISBN 978-1-118-22902-6. Archived from the original on 8 January 2017.
  2. ^ "Bubbles, Bubbles, Everywhere, But Not a Drop to Drink". The Lipid Chronicles. 11 November 2011. Archived from the original on 26 April 2012. Retrieved 1 August 2012.
  3. ^ a b c Kurt Kosswig "Surfactants" in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, 2005, Weinheim. doi:10.1002/14356007.a25_747
  4. ^ Reich, Hans J. (2012). "Bordwell pKa Table (Acidity in DMSO)". University of Wisconsin.
  5. ^ Chiappisi, Leonardo (December 2017). "Polyoxyethylene alkyl ether carboxylic acids: An overview of a neglected class of surfactants with multiresponsive properties". Advances in Colloid and Interface Science. 250: 79–94. doi:10.1016/j.cis.2017.10.001. PMID 29056232.
  6. ^ Maldonado-Valderrama, Julia; Wilde, Pete; MacIerzanka, Adam; MacKie, Alan (2011). "The role of bile salts in digestion". Advances in Colloid and Interface Science. 165 (1): 36–46. doi:10.1016/j.cis.2010.12.002. PMID 21236400.
  7. ^ Metcalfe TL, Dillon PJ, Metcalfe CD (April 2008). "Detecting the transport of toxic pesticides from golf courses into watersheds in the Precambrian Shield region of Ontario, Canada". Environ. Toxicol. Chem. 27 (4): 811–8. doi:10.1897/07-216.1. PMID 18333674.
  8. ^ Emmanuel E, Hanna K, Bazin C, Keck G, Clément B, Perrodin Y (April 2005). "Fate of glutaraldehyde in hospital wastewater and combined effects of glutaraldehyde and surfactants on aquatic organisms". Environ Int. 31 (3): 399–406. doi:10.1016/j.envint.2004.08.011. PMID 15734192.
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  13. ^ Committee on Effectiveness of Oil Spill Dispersants (National Research Council Marine Board) (1989). "Using Oil Spill Dispersants on the Sea". National Academies Press. Retrieved 31 October 2015.
  14. ^ Mergel, Maria. "Nonylphenol and Nonylphenol Ethoxylates." Toxipedia.org. N.p., 1 Nov. 2011. Web. 27 Apr. 2014.
  15. ^ Scott MJ, Jones MN (November 2000). "The biodegradation of surfactants in the environment". Biochim. Biophys. Acta. 1508 (1–2): 235–51. doi:10.1016/S0304-4157(00)00013-7. PMID 11090828.
  16. ^ USEPA: "2010/15 PFOA Stewardship Program" Archived 27 October 2008 at the Wayback Machine Accessed October 26, 2008.
  17. ^ "Market Report: World Surfactant Market". Acmite Market Intelligence. Archived from the original on 13 September 2010.
  18. ^ Reznik GO, Vishwanath P, Pynn MA, Sitnik JM, Todd JJ, Wu J, et al. (May 2010). "Use of sustainable chemistry to produce an acyl amino acid surfactant". Appl. Microbiol. Biotechnol. 86 (5): 1387–97. doi:10.1007/s00253-009-2431-8. PMID 20094712.
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