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Unsaturated fat
Unsaturated fat
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Unsaturated fats are a class of dietary characterized by the presence of one or more carbon-carbon double bonds in the chains of their constituent fatty acids, which distinguishes them from saturated fats that contain only single bonds between carbon atoms. These double bonds are typically in the cis configuration in natural unsaturated fats, though trans configurations also exist and have different properties. This structural feature renders unsaturated fats typically liquid at and more susceptible to oxidation compared to their solid, saturated counterparts. Found predominantly in plant-derived oils, nuts, seeds, avocados, and fatty fish, unsaturated fats serve as a primary energy source and play essential roles in structure and function. Unsaturated fats are broadly categorized into monounsaturated fatty acids (MUFAs), which contain a single double bond, and polyunsaturated fatty acids (PUFAs), which have two or more double bonds. Common sources of MUFAs include , canola oil, avocados, and nuts like almonds and , while PUFAs are abundant in , , walnuts, flaxseeds, and oily fish such as and . Among PUFAs, omega-3 (e.g., alpha-linolenic acid or ALA) and omega-6 (e.g., linoleic acid or LA) fatty acids are deemed essential nutrients, as the lacks the enzymes to synthesize them and they must be obtained through diet to support physiological processes like inflammation regulation and neurological development. From a health perspective, monounsaturated and polyunsaturated fats are associated with beneficial effects on cardiovascular , including lowering (LDL) cholesterol levels and potentially raising (HDL) cholesterol when they replace saturated fats in the diet. Epidemiological and clinical evidence supports that higher intake of PUFAs, particularly omega-3s, correlates with reduced risk of coronary heart disease and inflammation-related conditions, with recommendations from bodies like the to replace saturated fats with polyunsaturated fats in the diet. Additionally, omega-3 PUFAs like (EPA) and (DHA) contribute to health and may lower triglyceride levels, though their conversion from plant-based ALA is inefficient in humans.

Fundamentals

Definition

Unsaturated fats are a class of in which the fatty acid chains contain one or more carbon-carbon double bonds (C=C), distinguishing them from saturated fats whose chains have only single bonds between carbon atoms. This structural feature allows unsaturated fatty acids to theoretically bind additional hydrogen atoms, hence the designation "unsaturated." Unsaturated fats typically exist as triglycerides, esters formed from and three unsaturated molecules. The general formula for an unsaturated fatty acid is \ceCH3(CH2)m(CH2CH=CH)n(CH2)pCOOH\ce{CH3(CH2)_m(CH2CH=CH)_n(CH2)_pCOOH}, where mm, nn, and pp are non-negative integers that account for variations in chain length and position, with n1n \geq 1 indicating at least one double bond. This notation captures the linear hydrocarbon backbone terminating in a carboxylic acid group, with the double bonds introducing kinks in the chain. The term "unsaturated" originated in the 19th century, applied to organic compounds capable of adding hydrogen across double bonds without disrupting the carbon skeleton, a property first systematically explored in fatty acid studies. Pioneering work by French chemist in the 1810s laid the groundwork, as he analyzed the saponification of animal fats—breaking them into and fatty acids like —revealing their compositional complexity. While unsaturated fats focus on triglycerides with unsaturated fatty acids, they differ from other categories such as phospholipids, which incorporate groups, or sterols like , which feature a rigid ring structure rather than long-chain fatty acids.

Chemical Structure

Unsaturated fatty acids are long-chain carboxylic acids featuring one or more carbon-carbon double bonds (C=C) within the chain, typically spanning 12 to 24 carbon atoms in length. These double bonds introduce unsaturation by reducing the number of atoms compared to saturated fats, and they occur primarily in the cis configuration in natural sources. The double bonds in unsaturated fatty acids exist as geometric isomers: cis and trans. In the cis isomer, the two hydrogen atoms attached to the carbons of the double bond lie on the same side, creating a kink or bend in the chain that disrupts straight alignment. Conversely, the trans isomer has the hydrogens on opposite sides, resulting in a straighter chain similar to that of saturated fatty acids. This restricted rotation around the C=C bond, due to the overlap of p-orbitals forming the pi bond, enforces these fixed geometries. Nomenclature for unsaturated fatty acids uses two primary systems to denote double bond positions. The delta (Δ) notation numbers the carbons from the carboxyl end, indicating the position of the double bond by the lower-numbered carbon involved (e.g., Δ9 for a double bond between carbons 9 and 10). The omega (ω) or n- notation counts from the methyl (ω) end of the chain, useful for classifying essential fatty acids like ω-3, where the first double bond starts at the third carbon from the methyl terminus. The C=C double bonds are shorter (approximately 1.34 ) and stronger (bond dissociation energy of 614 kJ/mol) than single C-C bonds (1.54 and 348 kJ/mol), contributing to the rigidity and reactivity of unsaturated chains. This strength arises from the additional , while the shorter length affects molecular packing. A representative example is , denoted as 18:1 cis-9 or (9Z)-octadec-9-enoic acid, with the structure CH₃(CH₂)₇CH=CH(CH₂)₇COOH, where the cis double bond is between carbons 9 and 10 from the carboxyl end. The cis configuration leads to poorer intermolecular packing due to the chain kink, which lowers the of cis isomers compared to their trans counterparts or saturated analogs. Partial of unsaturated fats, a process that adds across some double bonds, can convert cis isomers to trans, producing trans fats with straighter chains.

Classification

Monounsaturated Fats

Monounsaturated fatty acids (MUFAs) are a class of unsaturated fatty acids characterized by the presence of exactly one carbon-carbon (C=C) in their aliphatic chain, distinguishing them from saturated fatty acids that lack such bonds and polyunsaturated fatty acids that contain multiple double bonds. This single double bond results in the loss of two atoms compared to their saturated counterparts, typically leading to a cis configuration that imparts a slight bend in the molecular structure. In standard notation, these fatty acids are designated by the total number of carbon atoms followed by the number of double bonds, such as 18:1 for an 18-carbon chain with one double bond. The most prevalent monounsaturated in nature is , denoted as 18:1 ω-9 or cis-9-octadecenoic acid, where the is located between the ninth and tenth carbon atoms from the carboxyl end (or ω-9 from the methyl end). constitutes the majority of MUFAs in many biological systems due to its via the stearoyl-CoA desaturase, which introduces the cis into . Another common example is , or 16:1 ω-7 (cis-9-hexadecenoic acid), featuring a 16-carbon chain with the between carbons 9 and 10; it is less abundant but plays roles in cellular signaling and membrane fluidity. Structurally, the single cis in MUFAs creates a modest kink in the otherwise linear chain, reducing van der Waals interactions and lowering the compared to saturated fats, though this effect is less pronounced than in polyunsaturated fats with multiple kinks. These fatty acids are typically liquids at and solidify upon , reflecting their intermediate packing efficiency. Monounsaturated fats are major components in various natural sources, with comprising 70-80% of the fatty acids in , approximately 50-70% in avocados, and around 45% of the total fat in . Due to their single , MUFAs exhibit lower susceptibility to oxidative degradation than polyunsaturated fats, as fewer sites are available for radical-initiated peroxidation reactions. also featured prominently in pioneering studies; in 1901, chemist Wilhelm Normann demonstrated the catalytic hydrogenation of its to form using , laying the groundwork for industrial fat processing.

Polyunsaturated Fats

Polyunsaturated fatty acids (PUFAs) are a class of characterized by the presence of two or more carbon-carbon double bonds in their chain, distinguishing them from monounsaturated fatty acids that contain only one such bond. These double bonds are typically in the cis configuration, and the fatty acids are denoted using a shorthand notation that indicates the total number of carbon atoms followed by the number of double bonds, such as 18:2 for an 18-carbon chain with two double bonds. PUFAs play critical roles in cellular membranes and signaling pathways due to their structural flexibility. Prominent examples of PUFAs include linoleic acid (18:2 ω-6), an essential omega-6 fatty acid; alpha-linolenic acid (18:3 ω-3), an essential omega-3 fatty acid; arachidonic acid (20:4 ω-6), a precursor to eicosanoids; eicosapentaenoic acid (EPA, 20:5 ω-3), involved in anti-inflammatory processes; and docosahexaenoic acid (DHA, 22:6 ω-3), crucial for neural development. The omega (ω) nomenclature classifies PUFAs based on the position of the first double bond from the methyl (omega) end of the chain: ω-3 fatty acids have their initial double bond between carbons 3 and 4, while ω-6 fatty acids have it between carbons 6 and 7. Both ω-3 and ω-6 families are essential for humans because the body lacks the enzymes to insert double bonds at these specific positions, necessitating dietary intake of precursors like linoleic and alpha-linolenic acids. The multiple cis double bonds in PUFAs enhance by introducing kinks that prevent tight packing of chains, contributing to cellular adaptability. However, these same structural features make PUFAs particularly susceptible to , as the allylic hydrogens adjacent to the double bonds are easily abstracted by , leading to oxidative chain reactions. The essentiality of PUFAs was first demonstrated in the late through experiments on rats fed fat-free diets, which developed scaly skin, growth retardation, and reproductive failure; supplementation with reversed these symptoms, establishing fatty acids as vital nutrients. Furthermore, the dietary ratio of ω-6 to ω-3 PUFAs is significant for , with modern Western diets often exceeding 10:1—far higher than the ancestral 1:1 to 4:1—potentially promoting and chronic disease risk, whereas a lower ratio supports balanced production and effects.

Properties

Physical Properties

Unsaturated fats are characteristically liquid at , a physical state attributable to the kinks introduced by cis double bonds in their chains, which disrupt molecular packing and inhibit . This contrasts with saturated fats, which tend to be solid due to their straight chains allowing tighter alignment. For example, , predominantly composed of monounsaturated fats, exhibits a of approximately -6°C, while , rich in saturated fats, melts around 32°C. The of unsaturated fats typically ranges from 0.91 to 0.93 g/cm³ at °C, rendering them less dense than but comparable to or marginally lower than many saturated fats owing to the irregular chain conformations. These fats are hydrophobic and insoluble in , yet they dissolve readily in nonpolar organic solvents like and , facilitating their extraction and analysis in settings. Viscosity in unsaturated fats decreases with increasing unsaturation, promoting greater fluidity and ease of flow, which is advantageous in industrial processing and culinary applications. , for instance, displays a dynamic viscosity of about 84 mPa·s at 20°C, lower than that of more saturated counterparts like . Additionally, the rises with the number of double bonds, generally falling between 1.46 and 1.47 for vegetable oils such as and sunflower, serving as an optical indicator of unsaturation levels. The quantifies unsaturation by measuring iodine absorption capacity, expressed as grams of iodine per 100 g of fat; higher values indicate greater presence. , with significant polyunsaturated content, has an iodine value of 107–128, compared to oil's low 6–11 due to its saturated profile. Thermally, polyunsaturated fats exhibit lower smoke points from enhanced volatility and oxidative instability at heat. , highly polyunsaturated, smokes at approximately 107°C (225°F), limiting its use in high-temperature cooking.

Chemical Properties

Unsaturated fats exhibit significant chemical reactivity primarily due to their carbon-carbon s, which make them prone to addition reactions and oxidation es. One of the most important reactions is auto-oxidation, a free radical mechanism that leads to the degradation of these . This begins with , where (ROS), such as hydroxyl radicals (.OH), abstract a from a (-CH₂-) adjacent to a in the , generating a radical (L•). The s weaken these adjacent C-H bonds, facilitating radical formation, and the radical quickly reacts with molecular oxygen to form a peroxyl radical (LOO•). follows, in which the peroxyl radical abstracts a from another , producing a (LOOH) and regenerating a radical, creating an autocatalytic that propagates oxidation. This step is enhanced by trace metals like iron or . Termination occurs when two radicals combine to form non-radical products, such as stable dimers (LOOL) or when antioxidants intervene to break the . Polyunsaturated fats are particularly susceptible to auto-oxidation because of bis-allylic positions (s flanked by two s), which have even weaker C-H bonds, leading to faster radical formation and ultimately rancidity characterized by off-flavors and odors from products. Hydrogenation is another key reaction involving the addition of across the double bonds of unsaturated fats, converting them to saturated fats. This process typically requires a catalyst, such as finely divided , and elevated temperatures around 150°C under pressure to facilitate the reaction. Complete saturates all double bonds, producing fully saturated fats with increased stability and higher points, while partial stops at monounsaturated intermediates and can generate trans fats due to of cis double bonds to trans configurations during the process. The general equation for of an in a chain is: RCH=CHR+H2Ni, 150°CRCH2CH2R\mathrm{R-CH=CH-R' + H_2 \xrightarrow{\text{Ni, 150°C}} R-CH_2-CH_2-R'}
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