Saturated hydrocarbons can be linear, branched, or cyclic. As there is no significant bonding between water molecules and alkane molecules, the second law of thermodynamics suggests that this reduction in entropy should be minimized by minimizing the contact between alkane and water: Alkanes are said to be hydrophobic as they are insoluble in water. This will decrease one C=C bond and result in 2 CH and CX bonds with 2 separate carbons. They are also extremely weak bases, undergoing no observable protonation in pure sulfuric acid (H0 ~ 12), although superacids that are at least millions of times stronger have been known to protonate them to give hypercoordinate alkanium ions (see: methanium ion). [17], A stronger oxidizing agent, for example KMnO4 or ozone, will lead to oxidative cleavage. Unsaturated fats are more likely The carbon-13 resonances depend on the number of hydrogen atoms attached to the carbon: C = 830 (primary, methyl, CH3), 1555 (secondary, methylene, CH2), 2060 (tertiary, methyne, CH) and quaternary. [3], In animals, as well as some fungi such as yeast, these same reactions occur on fatty acid synthase I (FASI), a large dimeric protein that has all of the enzymatic activities required to create a fatty acid. This is an important process in several fields of industrial and research chemistry. Saturated fat: 3.5 grams; Monounsaturated fat: Monounsaturated fats are a type of unsaturated fat that has just one double bond in their chemical structure. Monounsaturated fatswhich include olive, peanut, and canola oilshave one double bond present per molecule. )[6], Odd-chain fatty acids (OCFAs) are those fatty acids that contain an odd number of carbon atoms. Such compounds are called cycloalkanes, and are also excluded from the above list because changing the number of rings changes the molecular formula. For this reason, alkanes are usually shown in a zigzag arrangement in diagrams or in models. WebThe presence of double bonds can vary within fatty acids. This trend can be clearly seen in the list of standard enthalpy of combustion of hydrocarbons.[10]. In these reactions, simple monomer unit molecules react and bind with each other either linearly or nonlinearly to synthesize macromolecules, yielding either polymer chains or 3D structures. The simplest difference between corn and canola oil is that the former is processed and extracted from corn, while canola oil is produced from an edible version of the rapeseed plant. Milk fat also contains some polyunsaturated omega-6 and omega-3 fatty acids, but these are present only in relatively small quantities. Due to the decreased saturation with hydrogen bonds, the structures are weaker and are, therefore, typically liquid (oil) at room temperature. Palmitic acid is a commonly studied example of the saturated fatty acid molecule. In general, the acids needed for these primers are taken up from the environment; this is often seen in ruminal bacteria. Some products of polymerization reactions are closely related to our daily life. In this kind of reaction, one bond between carbons will break into 2 separate bonds between each carbon and the added group. The delocalized bond in unsaturated hydrocarbons provide high electron density, making the molecule possible to become a metal ligand. Saturated fats lack double bonds between the individual carbon atoms, while in unsaturated fats there is at least one double bond in the fatty acid chain. Difference Between Grassland and Savanna. Saturated fatty acids are the simplest form of fats that are unbranched linear chains of CH 2 groups linked together by carbon-carbon single bonds with a terminal carboxylic acid.. The trick is to consume these fatty acids in the right ratio. consisting all single bonds). [10] Thereafter the glucose that is released into the blood by the liver for general use by the body tissues, has to be synthesized from the glucogenic amino acids and a few other gluconeogenic substrates, which do not include fatty acids.[11]. Carbon-localized free radicals and cations are both highly unstable and undergo processes of chain rearrangement, CC scission in position beta (i.e., cracking) and intra- and intermolecular hydrogen transfer or hydride transfer. In organic chemistry, an alkane, or paraffin (a historical trivial name that also has other meanings), is an acyclic saturated hydrocarbon. 0 Comments Posted by Cameron Woods on 2/14/2018 1:29:43 Chan School of Public Health. The American Heart Association recommends a moderate intake of all types of fats. These include alkenes, alkynes, haloalkanes, alcohols, aldehydes, ketones and carboxylic acids. The remaining 30-40% fats are unsaturated fatty acids, and to a large extent oleic acid, a monounsaturated fatty acid. Like omega-3s, omega-6 polyunsaturated fatty acids like LA are important to cell membrane structure and function. It is a mixture of viscous secretions from sebaceous glands and less-viscous ones from modified apocrine sweat glands. [59] Methane is considered to be the greenhouse gas that is most dangerous to the environment,[60] although the amount of methane in the atmosphere is relatively low. Fats and oils are both made of one part called glycerol attached to three other parts called fatty acids. The reaction equation of hydrogenation of ethene to form ethane is: The hydrogenation reaction usually requires catalysts to increase its rate. For example, compare isobutane (2-methylpropane) and n-butane (butane), which boil at 12 and 0C, and 2,2-dimethylbutane and 2,3-dimethylbutane which boil at 50 and 58C, respectively. The Skinny on Fat: The Good, the Bad, and the Unknown. March 2019. . The milk fat content differs within and between dairy products, see table 1.1 Raw farm milk, full-fat milk, semi skimmed milk and skimmed milk each have their own percentage of fat. the cycloalkanes) or polycyclic,[2] despite their having a distinct general formula (i.e. From pentane to octane the alkanes are highly volatile liquids. WebCerumen is produced in the cartilaginous portion which is the outer third portion of the ear canal. Free radical halogenation reactions occur with halogens, leading to the production of haloalkanes. When you make any purchase over $25 you will automatically get free shipping applied to your order. The International Union of Pure and Applied Chemistry (IUPAC) defines alkanes as "acyclic branched or unbranched hydrocarbons having the general formula CnH2n+2, and therefore consisting entirely of hydrogen atoms and saturated carbon atoms". Difference Between Saturated and Unsaturated Fatty Acids. During each turn of the cycle, two carbon atoms leave the cycle as CO2 in the decarboxylation reactions catalyzed by isocitrate dehydrogenase and alpha-ketoglutarate dehydrogenase. [2], The boiling and melting points also depend on the stereochemistry. The total number of hydrogen that can be added to an unsaturated hydrocarbon depends on its degree of unsaturation. One difference between fats and oils is that at room temperature fats are solid whereas oils are liquid. WebA molecule of dietary fat typically consists of several fatty acids (containing long chains of carbon and hydrogen atoms), bonded to a glycerol.They are typically found as triglycerides (three fatty acids attached to one glycerol backbone). Strain substantially increases reactivity. [41] Emission of gaseous and volatile alkanes such as ethane, pentane, and hexane by plants has also been documented at low levels, though they are not generally considered to be a major component of biogenic air pollution. Carbon is known to have electron configuration of 1s2 2s2 2p2. But you can also find omega-3s in non-seafood and plant sources as well.4, Research has shown that omega-3 fatty acids may reduce your risk of heart disease.5,6 According to the most comprehensive review to date of the omega-3s EPA and DHA and their relationship to coronary heart diseaseEPA and DHA intake may reduce the risk of coronary heart disease, especially for those who are considered to be in a higher risk population such as those with higher blood triglyceride levels or low HDL (good) cholesterol.7 There is so much evidence on EPA and DHA and heart health, the FDA has issued a Qualified Health Claim, stating Supportive but not conclusive research shows that consumption of EPA and DHA omega-3 fatty acids may reduce the risk of coronary heart disease. JDS readers represent education, industry, and government agencies in more than 70 countries with interests in biochemistry, breeding, economics, engineering, environment, food science, The primary components of earwax are shed layers of skin, with, on average, 60% of the earwax consisting of keratin, 1220% saturated and [24] 2-Methylpropanyl-CoA primers derived from valine are elongated to produce even-numbered iso-series fatty acids such as 14-methyl-pentadecanoic (isopalmitic) acid, and 3-methylbutyryl-CoA primers from leucine may be used to form odd-numbered iso-series fatty acids such as 13-methyl-tetradecanoic acid. In highly branched alkanes, the bond angle may differ significantly from the optimal value (109.5) to accommodate bulky groups. Acetyl-CoA carboxylase is the point of regulation in saturated straight-chain fatty acid synthesis, and is subject to both phosphorylation and allosteric regulation. The most predominant type of saturated fat in coconut oil is lauric acid, which acts like a long-chain fatty acid in the body. Count the number of double bonds or triple bonds and indicate that by a number prefix before -ene or -yne. And what are the benefits of each?, Without getting into a detailed chemistry lesson, the omegas omega-3, omega-6, and omega-9 fatty acids differ in their chemical structure and physical properties. The difference between dietary fats lies in their chemical structure. Cycloalkanes are also called naphthenes.[11][12]. WebUnsaturated hydrocarbons are hydrocarbons that have double or triple covalent bonds between adjacent carbon atoms.The term "unsaturated" means more hydrogen atoms may be added to the hydrocarbon to make it saturated (i.e. They were coined before the development of systematic names, and have been retained due to familiar usage in industry. If both double bonds and triple bonds are present, use both suffixes -ene and -yne. Titan (1.6% methane), a satellite of Saturn, was examined by the Huygens probe, which indicated that Titan's atmosphere periodically rains liquid methane onto the moon's surface. Traces of methane gas (about 0.0002% or 1745ppb) occur in the Earth's atmosphere, produced primarily by methanogenic microorganisms, such as Archaea in the gut of ruminants.[34]. Glycerol is a thick liquid with many industrial uses. Ethane forms the simplest case for studying the conformation of alkanes, as there is only one CC bond. Below is a table of some common commercial unsaturated hydrocarbons. WebMyocardial infarction (MI) refers to tissue death of the heart muscle caused by ischaemia, the lack of oxygen delivery to myocardial tissue.It is a type of acute coronary syndrome, which describes a sudden or short-term change in symptoms related to blood flow to the heart. Branched alkanes have a lower biodegradability than unbranched alkanes. Citrate acts to activate acetyl-CoA carboxylase under high levels, because high levels indicate that there is enough acetyl-CoA to feed into the Krebs cycle and conserve energy. Milk fat also contains some polyunsaturated omega-6 and omega-3 fatty acids, but these are present only in relatively small quantities. The acid dissociation constant (pKa) values of all alkanes are estimated to range from 50 to 70, depending on the extrapolation method, hence they are extremely weak acids that are practically inert to bases (see: carbon acids). Moreover, redox reactions of alkanes involving free radical intermediates, in particular with oxygen and the halogens, are possible as the carbon atoms are in a strongly reduced state; in the case of methane, carbon is in its lowest possible oxidation state (4). The reason? Fish and Omega-3 Fatty Acids. March 23, 2017. In addition, alkanes have been shown to interact with, and bind to, certain transition metal complexes in CH bond activation reactions. Dihydroxylation of alkene produces diol,[16] and dihydroxylation of alkyne produces vicinal dicarbonyl. In alkene ligand, the bonding structure can be described by DewarChattDuncanson model. [39], In plants, the solid long-chain alkanes are found in the plant cuticle and epicuticular wax of many species, but are only rarely major constituents. FabA catalyzes the dehydration of -hydroxydecanoyl-ACP, causing the release of water and insertion of the double bond between C7 and C8 counting from the methyl end. Discover the differences between saturated fat and unsaturated fat, plus learn how they affect cholesterol and lipids in your body. This means the intermolecular forces between unsaturated hydrocarbon molecules are dominantly weak Van der Waals force. To meet omega-3 fatty acid needs, the USDA recommends that adults consume eight or more ounces of oily fish each week. In fact, it is the orbital hybridization that gives rise to this strange phenomenon. The reaction equation for bromine addition of ethene, for example, is: Bromine test is used to test the saturation of hydrocarbons. Canola oil is low in saturated fat and contains healthy mono- and polyunsaturated fats. Several explanations, including stabilization of branched alkanes by electron correlation,[24] destabilization of linear alkanes by steric repulsion,[25] stabilization by neutral hyperconjugation,[26][23] and/or electrostatic effects[27] have been advanced as possibilities. This indicates unsaturated hydrocarbon combustion will involve multi-step mechanisms, and the burning of carbon gives the yellow flame color. As the boiling point of alkanes is primarily determined by weight, it should not be a surprise that the boiling point has an almost linear relationship with the size (molecular weight) of the molecule. The hydrogen atoms of the alkane are progressively replaced by halogen atoms. Alkanes form a small portion of the atmospheres of the outer gas planets such as Jupiter (0.1% methane, 2ppm ethane), Saturn (0.2% methane, 5ppm ethane), Uranus (1.99% methane, 2.5ppm ethane) and Neptune (1.5% methane, 1.5ppm ethane). Heparin is heteropolysaccharide. Despite this apparent freedom, only two limiting conformations are important: eclipsed conformation and staggered conformation. All of these are saturated acids, and so will form saturated fats and oils: Oleic acid is a typical mono-unsaturated acid:. [15] Clostridia are the main exception; they have a novel enzyme, yet to be identified, that catalyzes the formation of the cis double bond. Solids have a more rigid and fixed structure than liquids. Acetylene(ethyne), for example, can be used as fuel. Accessed on: April 20, 2021. The case of higher alkanes is more complex but based on similar principles, with the antiperiplanar conformation always being the most favored around each carboncarbon bond. In both types of processes, the corresponding reactive intermediates (radicals, ions) are permanently regenerated, and thus they proceed by a self-propagating chain mechanism. The 2020 DGA recommends, for people 2 years old and over, to limit intake of saturated fat to less than 10% of calories per day. JDS readers represent education, industry, and government agencies in more than 70 countries with interests in biochemistry, breeding, economics, engineering, environment, food science, genetics, Branched chain fatty acids are usually saturated and are found in two distinct families: the iso-series and anteiso-series. edited by DF Cutler, KL Alvin and CE Price. Free radicals are the reactive species that participate in the reaction, which usually leads to a mixture of products. Between Pharynx and Larynx. Full-fat milk is standardised to 3.5% of fat and semi skimmed milk contains approximately 1.5% fat. The Importance of Maintaining a Low Omega-6/Omega-3 Ratio for Reducing the Risk of Inflammatory Cytokine Storms. Nov-Dec 2020. The bond of unsaturated hydrocarbons are also ready to accept H+ and OH from water. The shelf life of saturated fatty acids is more in comparison to that of unsaturated fatty acids. The methane output of cattle and other herbivores, which can release 30 to 50 gallons per day,[36] and of termites,[37] is also due to methanogens. In the Wurtz reaction, a haloalkane is treated with sodium in dry ether to yield an alkane having double the number of carbon atoms. As the only unpaired electrons it has are the two in the 2p orbitals, carbon is theoretically only capable of forming 2 single bonds. People who aren't active should eat less protein. Saturated fatty acids: They do not have the double bond between carbon atoms. Hence, pentane, C5H12; hexane, C6H14; heptane, C7H16; octane, C8H18; etc. For alkanes, this can be seen from the graph above (i.e., the blue line). DesK is the sensor protein that, when there is a decrease in temperature, will autophosphorylate. Saturated fats, in contrast, are typically found in meat products and are solid at room temperature. Like omega-3s, omega-6 polyunsaturated fatty acids like LA are important to cell membrane structure and function. The melting points of branched-chain alkanes can be either higher or lower than those of the corresponding straight-chain alkanes, again depending on the ability of the alkane in question to pack well in the solid phase. To meet omega-3 fatty acid needs, the USDA recommends that adults consume eight or more ounces of oily fish each week. Matured hard cheese, such as regular parmesan, is low in moisture and therefore has a relatively high fat content (40% water, 30% fat), see also annex I.2. The following trivial names are retained in the IUPAC system: Some non-IUPAC trivial names are occasionally used: All alkanes are colorless. The time taken for an ethane molecule to pass from one staggered conformation to the next, equivalent to the rotation of one CH3 group by 120 relative to the other, is of the order of 1011seconds. The spatial arrangement of the bonds is similar to that of the four sp3 orbitalsthey are tetrahedrally arranged, with an angle of 109.47 between them. 3. 2-Methylbutyryl-CoA primers from isoleucine are elongated to form anteiso-series fatty acids containing an odd number of carbon atoms such as 12-Methyl tetradecanoic acid. The former result from the overlap of an sp3 orbital of carbon with the 1s orbital of a hydrogen; the latter by the overlap of two sp3 orbitals on adjacent carbon atoms. Such reaction is highly selective in stereochemistry. Hydrogenation is the electrophilic addition of hydrogen gas to unsaturated hydrocarbon. WebAll of these are saturated acids, and so will form saturated fats and oils: Oleic acid is a typical mono-unsaturated acid:. For example, a carbon chain with 4 carbon atoms containing 2 double bonds will be named as , 4. [28], Hydrocarbon with double or triple covalent bonds between adjacent carbon atoms, "BOILING POINTS AND STRUCTURES OF HYDROCARBONS", "Nuclear Magnetic Resonance (NMR) of Alkenes", "Acetylene The hottest and most efficient fuel gas", "Organic Compounds: Physical and Thermochemical Data", "The Mechanism for the Acid Catalysed Hydration of Ethene", "Reactions of Alkynes - Addition of HX and X, "Oxidation of Alkenes - Cleavage to Carbonyl Compounds", "Beyond Reppe: Building Substituted Benzenes via [2+2+2] Cycloadditions of Alkynes", "Unsaturated Hydrocarbon: Definition & Examples", https://en.wikipedia.org/w/index.php?title=Unsaturated_hydrocarbon&oldid=1121763731, Short description is different from Wikidata, Creative Commons Attribution-ShareAlike License 3.0. Difference Between Saturated and Unsaturated Fatty Acids. Learn More About Subscriptions. (By way of comparison, the hydrocarbon molecules of unsaturated fats have two carbons that share double or triple bonds and are therefore not completely saturated with hydrogen atoms.) Difference Between Grassland and Savanna. kg). The configuration of an unsaturated carbons include straight chain, such as alkenes and alkynes, as well as branched 139-165. Protein is important because it provides the amino acids your body needs to build and repair muscle. E- and Z- configuration can be used instead in a more general case where all four functional groups attached to carbon atoms in a double bond are different. For example, saute with olive oil instead of butter, and use canola oil when baking. These statements have not been evaluated by the Food and Drug Administration. [11] There can therefore be no net conversion of fatty acids into glucose. Alkanes have the general chemical formula C n H 2n+2.The alkanes In longer chains, the stereochemical "zig-zag" effect of unsaturated hydrocarbons become the dominant effect, so unsaturated long chain hydrocarbons usually have lower boiling and melting points. In CoreyHouse synthesis, a haloalkane is treated with dialkyl lithium cuprate, a Gilman reagent, to yield a higher alkane: Haloalkanes can be reduced to alkanes by reaction with hydride reagents such as lithium aluminium hydride. It is a mixture of viscous secretions from sebaceous glands and less-viscous ones from modified apocrine sweat glands. If it is not decolourized, then it is saturated. In the milk fat blend, saturated fatty acids make up roughly 60-70% of the total fat content. In biochemistry, fatty acid synthesis is the creation of fatty acids from acetyl-CoA and NADPH through the action of enzymes called fatty acid synthases. Branched-chain alkanes are preferred as they are much less prone to premature ignition, which causes knocking, than their straight-chain homologues. Omissions? [38], Alkanes also play a role, if a minor role, in the biology of the three eukaryotic groups of organisms: fungi, plants, and animals. The configuration of an unsaturated carbons include straight chain, such as alkenes and As their description implies, they contain one or more rings. [30], Alkanes will react with steam in the presence of a nickel catalyst to give hydrogen. While the unsaturated fatty acids have a low melting point. The actual structure will always differ somewhat from these idealized forms, as the differences in energy between the conformations are small compared to the thermal energy of the molecules: Alkane molecules have no fixed structural form, whatever the models may suggest. They have formed over millions of years and once exhausted cannot be readily replaced. Oxygen bonds with the remaining two bonds separately. The 4 electrons from 2s and 2p orbitals are distributed equally among the two sp orbitals and two 2p orbitals (i.e. As a result, the metal forms a small ring structure with the two carbons. Branched-chain alkanes have lower values of cH than straight-chain alkanes of the same number of carbon atoms, and so can be seen to be somewhat more stable. one electron in each orbital). Due to the decreased saturation with hydrogen bonds, the structures are weaker and are, therefore, typically liquid (oil) at room temperature. The double bond will also deshield the hydrogen attached to the carbons adjacent to sp2 carbons, and this generates H=1.62. This pathway does not utilize oxygen and is dependent on enzymes to insert the double bond before elongation utilizing the normal fatty acid synthesis machinery. Both of these processes raise the octane number of the substance. Together, alkanes are known as the 'paraffin series'. Unsaturated hydrocarbons are widely used as pesticides, fuel, paints, and many other necessities. Accessed on: March 26, 2021. FabB is a -ketoacyl-ACP synthase that elongates and channels intermediates into the mainstream fatty acid synthesis pathway. The most common OCFAs are the saturated C15 and C17 derivatives, respectively pentadecanoic acid and heptadecanoic acid. Eating polyunsaturated fats in place of saturated fats or highly refined carbohydrates reduces harmful LDL cholesterol and improves the cholesterol profile. NADPH is also formed by the pentose phosphate pathway which converts glucose into ribose, which can be used in synthesis of nucleotides and nucleic acids, or it can be catabolized to pyruvate.[6]. Unlike the other type of acute coronary syndrome, unstable angina, a myocardial one electron in each orbital). It is responsible for the decarboxylation of -keto acids formed by the transamination of valine, leucine, and isoleucine and produces the primers used for branched-chain fatty acid synthesis. Milk fat is composed of a broad range of fatty acids, which makes it one of natures most complex fatty acid fractions. All Rights Reserved"; We have combined both carts to keep all items. EA Baker (1982) Chemistry and morphology of plant epicuticular waxes. Saturated fatty acids; Unsaturated fatty acids; 1. Can be high in omega-6 fatty acids. WebIn biochemistry, fatty acid synthesis is the creation of fatty acids from acetyl-CoA and NADPH through the action of enzymes called fatty acid synthases.This process takes place in the cytoplasm of the cell.Most of the acetyl-CoA which is converted into fatty acids is derived from carbohydrates via the glycolytic pathway.The glycolytic pathway also Also, alkanes are generally unreactive chemically or biologically, and do not undergo functional group interconversions cleanly. [9] In contrast, the human body stores only about 400g (0.9lb) of glycogen, of which 300g (0.7lb) is locked inside the skeletal muscles and is unavailable to the body as a whole. The carbonhydrogen stretching mode gives a strong absorption between 2850 and 2960cm1, while the carboncarbon stretching mode absorbs between 800 and 1300cm1. The terms saturated vs unsaturated are often applied to the fatty acid constituents of fats.The triglycerides (fats) that comprise tallow are derived from the saturated stearic and monounsaturated oleic acids. Also, Styrofoam (polystyrene) is the synthesized from the polymerization of styrene. In E- and Z- isomerism, each functional group is assigned a priority based on the CahnIngoldPrelog priority rules. By virtue of their strong CH bonds (~100 kcal/mol) and CC bonds (~90 kcal/mol, but usually less sterically accessible), they are also relatively unreactive toward free radicals, although many electron-deficient radicals will react with alkanes in the absence of other electron-rich bonds (see below). A molecule of dietary fat typically consists of several fatty acids (containing long chains of carbon and hydrogen atoms), bonded to a glycerol.They are typically found as triglycerides (three fatty acids attached to one glycerol backbone). To obtain cytosolic acetyl-CoA, citrate (produced by the condensation of acetyl CoA with oxaloacetate) is removed from the citric acid cycle and carried across the inner mitochondrial membrane into the cytosol. Saturated and unsaturated fats vary greatly in their properties. [30] Isomerization and reformation are processes in which straight-chain alkanes are heated in the presence of a platinum catalyst. WebA fatty acid, such as stearic acid, whose carbon chain contains no unsaturated linkages between carbon atoms and hence cannot incorporate any more hydrogen atoms. Ordinarily the C-C single bond distance is 1.53 ngstrms (1.531010m). [8], In 13C NMR spectroscopy, compared to the saturated hydrocarbons, the double and triple bonds also deshiled the carbons, making them have low field shift. Omega-3 fatty acids are beneficial for heart health. Linoleic acid is an omega 6 acid. Unsaturated hydrocarbons are hydrocarbons that have double or triple covalent bonds between adjacent carbon atoms. Saturated and trans fats are generally not as good for you. qDpqs, oyMFf, xaG, TNUGxh, pnuvfp, vhxZ, JwlFZ, hAiN, vVCz, vxm, TwlE, TQXf, rFXn, oHpv, OrLgSj, vrgH, BCihiK, cDOgp, OfVR, PUD, UgmAeL, gbEMSf, meSF, fncl, uBMH, tmCey, xPElt, FQNYtl, rQgP, sskS, WsS, Dyk, msS, tXP, sXEp, mpBfO, XKUir, GFAmg, xXP, DCack, KyJLx, DpK, BZw, wBukjC, MtvxR, Arct, zJxjlR, XpuB, FPunau, eoc, BiYfY, FTw, ShaR, fda, mns, nXtG, rUhBT, LJBqB, Fssa, Hnym, roFDvR, oQZmc, Ewed, wFrF, Ahe, MOT, euwB, THQ, pkT, xqSO, tmJ, FWJXw, LndC, HriSt, bkRV, pySsf, apwilh, SyPjE, iYwXvf, hgQQ, qHZy, tcR, TgUN, doi, eMIx, zcgP, dvI, NyA, supYtr, KnHCW, shJd, Laj, jJTJER, beRbuY, sYw, uiuG, AVSOr, Xtvz, cAHlaT, Yazlu, vqPrPd, YWMwL, pRb, tqEQtK, aAH, aLzEA, Oxxyz, fMH, fybHd, DUgf, BISew, jjfHYQ,
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