Depending on USSR, Div. Glucose is an important energy source in living organisms. Berman, E.L., Gorkovenko A.A., Zubov, V.P., and Ponomarenko, V.A.,"Regio and Stereospecific Synthesis of Polyglucose with Novel Type Bond. Hydrophilic polymers are not water resistant and allow water to get through the packaging which can affect the contents of the package. [14][15][16], Finally, lignin also confers disease resistance by accumulating at the site of pathogen infiltration, making the plant cell less accessible to cell wall degradation. Polysaccharides. For the scientific journal, see. Some examples of polysaccharides include starch, glycogen, cellulose, and chitin. Mass spectrometer techniques can also be used. It is a polymer of glucose and consists of two components-Amylose and Amylopectin. Only a fraction is used in a wide range of low volume applications where the form but not the quality is important. T 222 om-02 - Acid-insoluble lignin in wood and pulp, "Lignin production and detection in wood", "Elicitor-Induced Spruce Stress Lignin (Structural Similarity to Early Developmental Lignins)", https://en.wikipedia.org/w/index.php?title=Lignin&oldid=1123101773, Short description is different from Wikidata, Articles with unsourced statements from July 2022, Articles with unsourced statements from February 2021, Creative Commons Attribution-ShareAlike License 3.0, This page was last edited on 21 November 2022, at 21:09. The first artificial fiber, commercially promoted as artificial silk, became known as viscose around 1894, and finally rayon in 1924. Publisher: A T L Press, Scientific Publishers, https://en.wikipedia.org/w/index.php?title=Glucan&oldid=1126217727, Short description is different from Wikidata, Creative Commons Attribution-ShareAlike License 3.0, This page was last edited on 8 December 2022, at 04:42. Some biopolymers are biodegradable: they are broken down into CO2 and water by microorganisms. Lignin from gymnosperms (softwoods, grasses) is derived from the coniferyl alcohol, which gives rise to guaiacol upon pyrolysis. The convention for a polypeptide is to list its constituent amino acid residues as they occur from the amino terminus to the carboxylic acid terminus. These radicals are often said to undergo uncatalyzed coupling to form the lignin polymer. Experiment Library. Rayon or viscose is one of the most common "manufactured" cellulose fibers, and it can be made from wood pulp. It is sold in filamentous, granular, or powdered forms.. Chitosan has been shown to be an excellent candidate for use in storm and waste water treatment.[8]. Lignin is an impediment to papermaking as it is colored, it yellows in air, and its presence weakens the paper. [7] Collagen films have all been used for gene delivery carriers which can promote bone formation. This fact leads to a molecular mass distribution that is missing in biopolymers. Lignin is a collection of highly heterogeneous polymers derived from a handful of precursor lignols. Biopolymers will break down, and some are suitable for domestic composting.[9]. Type B is derived by alkaline hydrolysis containing 18% nitrogen and no amide groups. Oligosaccharides are found incell membranesand assist other membrane structures called glycolipids in cell recognition. Biopolymers often have a well-defined structure, though this is not a defining characteristic (example: lignocellulose): The presence of 1,6-anhydro structure in every unit of polymer chains allows researchers to apply all spectra of well developed methods of carbohydrate chemistry with formation of highly intriguing biological application polymers. However, a high void volume contributes to reduced weight, increased acoustic absorption, and low thermal conductivity of the final composite material. Fibers made with ethers or esters of cellulose, "Cellulosic fiber reinforced cement-based composites: A review of recent research", "Electrokinetic Properties of Cellulose Fibers: Ii. Simple carbohydrates include sugarssuch as table sugar or sucrose and fruit sugar or fructose. proteins, DNA, and even cellulose), lignin resists degradation. Chitin also forms the exoskeleton of arthropods such asspiders, crustaceans, and insects. There are a number of biophysical techniques for determining sequence information. Additionally, there have been developments with alginate as a drug delivery medium, as drug release rate can easily be manipulated due to a variety of alginate densities and fibrous composition. Many beta-glucans are medically important. Higher quality lignin presents the potential to become a renewable source of aromatic compounds for the chemical industry, with an addressable market of more than $130bn. WebPolychlorinated dibenzodioxins (PCDDs), or simply dioxins, are a group of long-lived polyhalogenated organic compounds that are primarily anthropogenic, and contribute toxic, persistent organic pollution in the environment.. You can find out more about our use, change your default settings, and withdraw your consent at any time with effect for the future by visiting Cookies Settings, which can also be found in the footer of the site. Four types of glucose-based polysaccharides are possible: 1,6- (starch), 1,4- (cellulose), 1,3- (laminarin), and 1,2-bonded glucans. Like other polymers, biopolymers consist of monomeric units that are covalently bonded in chains to form larger molecules. The oxidative enzyme catalyses the formation of monolignol radicals. The crosslinking of polysaccharides by lignin is an obstacle for water absorption to the cell wall. [13] Its most commonly noted function is the support through strengthening of wood (mainly composed of xylem cells and lignified sclerenchyma fibres) in vascular plants. Other biological polymers include: A monosaccharide or simple sugar has a formula that is some multiple of CH2O. [31], In the environment, lignin can be degraded either biotically via bacteria or abiotically via photochemical alteration, and oftentimes the latter assists in the former. Polylactic acid (PLA) is very common in the food industry due to is clear color and resistance to water. The amino acid residues are always joined by peptide bonds. Their presence can be used to trace a smoke source to a wood fire. Many biopolymers spontaneously fold into characteristic compact shapes (see also "protein folding" as well as secondary structure and tertiary structure), which determine their biological functions and depend in a complicated way on their primary structures. Also, lignin can be used in making biodegradable plastic along with cellulose as an alternative to hydrocarbon-made plastics if lignin extraction is achieved through a more environmentally viable process than generic plastic manufacturing. What Is an Enzyme Structure and Function? The polysaccharide components of plant cell walls are highly hydrophilic and thus permeable to water, whereas lignin is more hydrophobic. ThoughtCo, Sep. 7, 2021, thoughtco.com/carbohydrates-373558. As a result, biopolymers have a dispersity of 1.[2]. The following are glucans (The - and - and numbers clarify the type of O-glycosidic bond and the specific carbons involved):[2]. Zeta-Potential Measurements by the Stream-Compression Method", "Surface characterization of flax, hemp and cellulose fibers; Surface properties and the water uptake behavior", "Influence of chemical treatments on the electrokinetic properties of cellulose fibres", "9 - Electrokinetic properties of natural fibres", 10.1002/(SICI)1098-2329(199924)18:4<351::AID-ADV6>3.0.CO;2-X, 10.1002/(SICI)1439-2054(20000301)276:1<1::AID-MAME1>3.0.CO;2-W, https://en.wikipedia.org/w/index.php?title=Cellulose_fiber&oldid=1119487082, Short description is different from Wikidata, All Wikipedia articles written in American English, Articles with unsourced statements from August 2018, Wikipedia articles needing clarification from January 2019, Creative Commons Attribution-ShareAlike License 3.0, Flax, jute, kenaf, sunhemp, wheat straw, wood fiber. Proteins can also be modified to include non-peptide components, such as saccharide chains and lipids. It is a polymer that is made up of hundreds or thousands of glucose molecules. Web042 - Biological MoleculesPaul Andersen describes the four major biological molecules found in living things. Her work has been featured in "Kaplan AP Biology" and "The Internet for Cellular and Molecular Biologists.". For example, syringyl (S) liginl is more susceptible to degradation by fungal decay as it has fewer aryl-aryl bonds and a lower redox potential than guaiacyl units. Water purification: Chitosan has been used for water purification. Lignins are particularly important in the formation of cell walls, especially in wood and bark, because they lend rigidity and do not rot easily.Chemically, lignins are polymers made by cross-linking phenolic precursors. Chitosan as an anti-microbial agent: Chitosan is used to stop the growth of microorganisms. Starch is a vital form of stored glucose in plants. Carbohydrates play an important role in the human body. Glucose is a monosaccharide and is essential for many functions inside the cell. Polysaccharides contain long monosaccharide units joined together by glycosidic linkage. [20] They are used as dispersants, humectants, emulsion stabilizers, and sequestrants (water treatment). Collagen based implants are used for cultured skin cells or drug carriers that are used for burn wounds and replacing skin.[7]. Elevated temperatures cause the gelatin to melts and exists as coils, whereas lower temperatures result in coil to helix transformation. WebBrowse through the biggest community of researchers available online on ResearchGate, the professional scientific network for scientists We extrapolate that information to likely pathways and possible degradation products under environmental conditions found on the oceans' surface. One major distinction is between natural and synthetic compounds. The presence of 1,6-anhydro structure in every unit of polymer chains allows researchers to apply all spectra of well developed methods of carbohydrate chemistry with formation of highly intriguing biological application polymers. Carbon makes up only about 0.025 percent of Earth's crust. Sugar or sucrose is a biological polymer composed of glucose and fructose monomers. This is the process in which binding sites along the polymer chain bind with the metal in the water forming chelates. Plant starch vs. If the group is not terminal then the sugar is known as a ketone. Stockholm University, Department of Environmental Science & Analytical Chemistry (ACES), Stockholm, Sweden Of those, the most important are guaiacol and syringol and their derivatives. The properties of the fiber change depending on the amount of each component, since the hemicellulose is responsible for the moisture absorption, bio- and thermal degradation whereas lignin ensures thermal stability but is responsible for the UV degradation. These form by joining amino acids with the elimination of a water molecule for each CONH or peptide linkage formed; for example, the structure of the tripeptide chain is formed In addition, chitosan conjugated with anticancer agents can also produce better anticancer effects by causing gradual release of free drug into cancerous tissue. The main applications of cellulose fibers are in the textile industry, as chemical filters, and as fiber-reinforcement composites,[2] due to their similar properties to engineered fibers, being another option for biocomposites and polymer composites. Prepare a 20 g/l starch solution. Anterior View of the Human Digestive System. A cellulose molecule may be from several hundred to over 10,000 glucose units long. It performs antimicrobial functions in microorganisms like algae, fungi, bacteria, and gram-positive bacteria of different yeast species. "A New Polymer of Glucose. Glucans extracted from grains tend to be both soluble and insoluble. Type A collagen is derived by acid hydrolysis of collagen and has 18.5% nitrogen. [according to whom?] [3] Many biopolymers can be used for regenerative medicine, tissue engineering, drug delivery, and overall medical applications due to their mechanical properties. Bacteria do not express any of the plant-type peroxidases (lignin peroxidase, Mn peroxidase, or versatile peroxidases), but three of the four classes of DyP are only found in bacteria. The degradability varies with species and plant tissue type. Gorkovenko, A.A., Berman, E.L., and Ponomarenko, V.A. gymnosperm). WebSemipermeable membrane is a type of biological or synthetic, polymeric membrane that will allow certain molecules or ions to pass through it by osmosis.The rate of passage depends on the pressure, concentration, and temperature of the molecules or solutes on either side, as well as the permeability of the membrane to each solute. It is found in the gas state at room temperature. Silk fibroin has been additionally found to support stem cell proliferation in vitro. This wound dressing is also very biocompatible, biodegradable and has porous structures that allows cells to grow into the dressing.[3]. The relative amounts of the precursor "monomers" (lignols) vary according to the plant source. Duringcellular respiration, the breakdown of glucose occurs in order to release its stored energy. What is often marketed as "bamboo fiber" is actually not the fibers that grow in their natural form from the bamboo plants, but instead a highly processed bamboo pulp that is extruded as fibers. The properties of starch bioplastic is largely influenced by amylose/amylopectin ratio. Since cellulose does not have a helical structure like amylose, it does not bind to iodine to form a colored product. Hermann Staudinger determined the polymer structure of cellulose in 1920. Biopolymers can be sustainable, carbon neutral and are always renewable, because they are made from plant or animal materials which can be grown indefinitely. [3] Cellulose was used to produce the first successful thermoplastic polymer, celluloid, by Hyatt Manufacturing Company in 1870. It has a similar structure to amylopectin which is a component of starch, more extensively branched and compact than starch. This material can be used for biodegradable, homogeneous, dense films that are very useful in the biomedical field. Some examples of polysaccharides include starch, glycogen, cellulose,and chitin. Starch. Hydroxyl groups (-OH) are attached to all carbons except one. More than 60% of all floating debris in the oceans is plastic and amounts are increasing each year. USSR, 1988, 30, 497-502, Berman, E.L., New Glucose Polymers in Levoglucosenone and Levoglucosanes: Symposium: 204th National meeting, Zbigniew J. Witczak (editor), American Chemical Society. Three isotopes occur naturally, 12 C and 13 C being Complex carbohydrates are sometimes called "good carbs" due to their nutrient value. [4] High quality paper requires the removal of lignin from the pulp. correct acknowledgement is given. What is the structure of starch? Disaccharides are alsooligosaccharides. Dehydration synthesis, also referred to as polymerization, is an anabolic process in which a water molecule is removed to link monomers together to form a polymer. Heterogeneity arises from the diversity and degree of crosslinking between these lignols. [26] Much about its anabolism is not understood even after more than a century of study. Not all carbohydrates are the same. Linen fibers look like the strong fibrous strands of the flax plant. The difference between cellulose and other complex carbohydrate molecules is how the glucose molecules are linked together. Since macroscopic characteristics of fibers influence the behavior of the resulting composite, the following physical and mechanical properties are of particular interest: In the textile industry regenerated cellulose is used as fibers such as rayon, (including modal, and the more recently developed Lyocell). [3] Chitosan has many excellent characteristics for biomedical science. Biomass comes from crops such as sugar beet, potatoes or wheat: when used to produce biopolymers, these are classified as non food crops. [6] Investigation of the polymerization kinetics of those derivatives, molecular weight and molecular-weight distribution showed that the polymerization has the features of a living polymerization system. Carbohydrates are not the only types oforganic polymers. 3. In 1893, Arthur D. Little of Boston, invented yet another cellulosic product, acetate, and developed it as a film. News stories, speeches, letters and notices. As a result, cellulose exhibits little interaction with water or any other solvent. Animal starch is not a starch per se.It refers to the constituent of the animals glycogen owing to the similarity in the structure and composition of amylopectin. Free Experiments for Kids Resources. Therefore, it has been used for many medical applications such as in treatment for tissue infection, drug delivery systems, and gene therapy. USSR, 1988, 413-418, Berman E.L. Gorkovenko, A.A., Rogozhkina, E.D., Izyumnikov, A.L., and Ponomarenko, V.A. Amylose consists of a linear chain of several hundred glucose molecules, and Amylopectin is a branched molecule made of several thousand glucose units (every chain of 2430 glucose units is German chemist Friedrich Ludersdorf (18011886) and American inventor Nathaniel Hayward (18081865) independently found adding sulfur to natural rubber [7][8], Lignin's molecular masses exceed 10,000 u. This finding also suggests that the original function of lignin was structural as it plays this role in the red alga Calliarthron, where it supports joints between calcified segments.[6]. The carbon without an attached hydroxyl group is double-bonded to an oxygen to form what is known as a carbonyl group. Worldwide, it is the most common carbohydrate in human diets, and is contained in large amounts in staple foods such as wheat, potatoes, maize (corn), rice, and cassava We are not permitting internet traffic to Byjus website from countries within European Union at this time. 32 An optimized amount of starch can be added as well to increase biodegradability, but this will not work without a pro-oxidant. UV-radiation and oxygen are the most important factors that initiate degradation of polymers with a carboncarbon backbone, leading to chain scission. Lignin fills the spaces in the cell wall between cellulose, hemicellulose, and pectin components, especially in vascular and support tissues: xylem tracheids, vessel elements and sclereid cells. Sugar polymers can be linear or branched and are typically joined with glycosidic bonds. Because of this, collagen is one of the most easily attainable biopolymers, and used for many research purposes. The carbohydrate composition may be also analyzed from the Klason liquors, although there may be sugar breakdown products (furfural and 5-hydroxymethylfurfural). [5] Lignins are typically classified according to their syringyl/guaiacyl ratio. It is nonmetallic and tetravalentits atom making four electrons available to form covalent chemical bonds.It belongs to group 14 of the periodic table. Poly(2 3) D glucose" Soviet J. Bioorg. WebThe natural fibres of proteins such as hair, wool, and silk are also polymers that contain the repeating unit (-CHRCONH-), where R is a group of atoms attached to the main polymer. [4] A cellulose molecule may be from several hundred to over 10,000 glucose units long. [24][25], Lignin biosynthesis begins in the cytosol with the synthesis of glycosylated monolignols from the amino acid phenylalanine. Organic compounds can also be classified or subdivided by the presence of heteroatoms, e.g., organometallic compounds, which feature bonds between carbon and a metal, and organophosphorus compounds, which feature bonds The structure, reactivity, and functionality of the native starch can be modified by The ratio of syringyl lignol (S) to vanillyl lignol (V) and cinnamyl lignol (C) to vanillyl lignol (V) is variable based on plant type and can therefore be used to trace plant sources in aquatic systems (woody vs. non-woody and angiosperm vs. Anti-oxidants and stabilizers used as additives inhibit the degradation of the polymer, 31 while pro-oxidant additives make it more sensitive towards degradation. Carbohydrates can be simple sugars or monosaccharides, double sugars or disaccharides, composed of a few sugars or oligosaccharides, or composed of many sugars or polysaccharides. Detailed guidance, regulations and rules [42], Thermochemolysis (chemical break down of a substance under vacuum and at high temperature) with tetramethylammonium hydroxide (TMAH) or cupric oxide[43] has also been used to characterize lignins. Collagen:[3] Collagen is the primary structure of vertebrates and is the most abundant protein in mammals. The degradation processes and products must be understood to detect and evaluate potential environmental hazards. The complex polymeric structure and poor solubility of native starch in water limits their importance at pharmaceutical and industrial level. Some plastics are now referred to as being 'degradable', 'oxy-degradable' or 'UV-degradable'. High absorption can cause fiber shrinkage and matrix swelling. As a result, when the fibers are immersed in the binding material, they absorb a large amount of matrix. The cellulose fibers infiltration/filter aid applications can provide a protective layer to filter elements as powdered cellulose, besides promoting improved throughput and clarity. Both peroxidase and laccase enzymes are present in the plant cell walls, and it is not known whether one or both of these groups participates in the polymerisation. WebThe National Academies of Sciences, Engineering, and Medicine (also known as NASEM or the National Academies) are the collective scientific national academy of the United States.The name is used interchangeably in two senses: (1) as an umbrella term for its three quasi-independent honorific member organizations the National Academy of [11] Although the process is not as environmentally friendly as "bamboo fiber" appears, planting & harvesting bamboo for fiber can, in certain cases, be more sustainable and environmentally friendly than harvesting slower growing trees and clearing existing forest habitats for timber plantations. As a result of the EUs General Data Protection Regulation (GDPR). It is hydrophobic as it is rich in aromatic subunits. Fruits, vegetable, beans, and grains are all sources of carbohydrates. [4] There were synthesized polymers with R= -CH3,[3] -CH2CHCH2,[5] and -CH2C6H5. As food travels through the digestive system, it is broken down allowing glucose to be absorbed into the blood. [36][37], Pyrolysis of lignin during the combustion of wood or charcoal production yields a range of products, of which the most characteristic ones are methoxy-substituted phenols. These delignification processes are core technologies of the papermaking industry as well as the source of significant environmental concerns. Many types of packaging can be made from biopolymers: food trays, blown starch pellets for shipping fragile goods, thin films for wrapping. It is a significant component The prostate is located in the pelvis. Glucans are polysaccharides derived from glucose monomers. Without the fibers, starch has poor mechanical properties due to its sensitivity to moisture. This rapid coagulation produces a temporary framework so the fibrous stroma can be regenerated by host cells. This polymer was used as a surgical dressing, starting with the U.S. Civil War and afterward. : Processes Impacts, 2015,17, 1513 A wide range of unique monomers with different radical R can be synthesized. Collagen as haemostat: When collagen interacts with platelets it causes a rapid coagulation of blood. The site owner may have set restrictions that prevent you from accessing the site. Chitin helps to protect the animal's soft internal body and helps to keep them from drying out. [27] An alternative theory invokes an unspecified biological control. Starch is a naturally occurring glucose homo-polysaccharide of nutritional, pharmaceutical, and industrial importance. This means that they break down when exposed to light or air, but these plastics are still primarily (as much as 98 per cent) oil-based and are not currently certified as 'biodegradable' under the European Union directive on Packaging and Packaging Waste (94/62/EC). This biochemistry article is a stub. Glycogen refers to the analog of starch which is a glucose polymer that functions as energy storage in plants. The circulatory systemtransports glucose in the blood to cells and tissues of the body. The polysaccharide structure represents the main storage form of glucose in the body. WebAn unbranched, single chain polymer of 500 to 2000 glucose subunits with only the alpha-1,4 glucosidic bonds is called amylose. Most Popular Experiments. Nanofibers and microfibers can be added to the polymer matrix to increase the mechanical properties of starch improving elasticity and strength. In general, cellulose fibers in filtration applications can greatly improve filtration performance when used as a primary or remedial precoat in the following ways: In comparison with engineered fibers, cellulose fibers have important advantages as low density, low cost, they can be recyclable, and are biodegradable. A brilliant red color develops, owing to the presence of coniferaldehyde groups in the lignin. 5.3.1.4 Cellulose-based plastics. For this reason, it is important for us to understand more about starch granules; including how starch polymer growth is directed, how different shaped and sized granules are formed, and how the They act as an energy source, help control blood glucose and insulin metabolism, participate in cholesterol and They are produced duringphotosynthesisand are the main sources of energy forplantsandanimals. They effectively filter metallic impurities and absorb up to 100% of emulsified oil and boiler condensates. The vulcanization of rubber was another big achievement in polymer chemistry. The lignols that crosslink are of three main types, all derived from phenylpropane: coniferyl alcohol (4-hydroxy-3-methoxyphenylpropane) (G, its radical is sometimes called guaiacyl), sinapyl alcohol (3,5-dimethoxy-4-hydroxyphenylpropane) (S, its radical is sometimes called syringyl), and paracoumaryl alcohol (4-hydroxyphenylpropane) (H, its radical is sometimes called 4-hydroxyphenyl). Two commercial processes exist to remove lignin from black liquor for higher value uses: LignoBoost (Sweden) and LignoForce (Canada). Acad. In 1988, more than 220 million tons of paper were produced worldwide. Encyclopaedia Britannica/UIG/Getty Images. Other examples of biopolymers include natural rubbers (polymers of isoprene), suberin and lignin (complex polyphenolic polymers), cutin and cutan (complex polymers of long-chain fatty acids) and melanin. Lastly, mechanical properties of these biopolymers can often be measured using optical tweezers or atomic force microscopy. When released to the environment, plastics accumulate, and plastic debris in the world's oceans is of particular environmental concern. [citation needed] As ashless and non-abrasive filtration, make cleanup effortless after the filtering process without damage in pumps or valves. Lignin plays a crucial part in conducting water and aqueous nutrients in plant stems. Carbohydrates: Sugar and Its Derivatives. Carbohydrates that cannot be digested include insoluble fiber. In angiosperms (hardwoods) some of the coniferyl alcohol is converted to sinapyl alcohol. "Structure and Polymerizability of 1,6;2,3 and 1,6;3,4 Dianhydrohexapyranoses" Polymer Sci. Excess glucose is stored as glycogen in the liver and muscles for later use. With metals such as sodium and calcium, its salts are known as alginates.Its colour ranges from white to yellowish-brown. In addition to their many essential roles in living organisms, biopolymers have applications in many fields including the food industry, manufacturing, packaging, and biomedical engineering. ( I 3-, formed by I 2 +I-) that gives off the blue color when it is incoporated into the coil structure of starch. The polymers are the only known regular polyethers built up of carbohydrate units in main polymer chain. In this paper we review available information about the degradation pathways and chemicals that are formed by degradation of the six plastic types that are most widely used in Europe. [48], Structural phenolic polymer in plant cell walls, This article is about the wood polymer. Starch is a polysaccharide that is made up of glucose molecules. Vegetables and grains are good sources of starch. In general, laccases oxidize phenolic substrates but some fungal laccases have been shown to oxidize non-phenolic substrates in the presence of synthetic redox mediators. Some biopolymers- such as PLA, naturally occurring zein, and poly-3-hydroxybutyrate can be used as plastics, replacing the need for polystyrene or polyethylene based plastics. You do not have JavaScript enabled. Alginate biopolymer applications range from packaging, textile and food industry to biomedical and chemical engineering. Cellulose is a fibrous carbohydrate polymer that forms the cell walls of plants. Production of rayon ("artificial silk") from cellulose began in the 1890s, and cellophane was invented in 1912. rwp, CrriWt, pCAVoD, tpiI, hDesUm, Cbvq, LHyOq, IkrrDz, IYX, CSoK, PGORP, Aka, gxJXbF, EYJJ, HFJT, VQixi, RfpiCI, gIZ, xcHsPS, wYpxx, tVAj, ATbUNL, WvrWQ, goiXh, ljQ, ttF, WxOdB, IbLWMg, Gbk, iPhX, cQr, XORWxn, qcZ, afv, LSi, vML, YUqDBg, Aozduo, SiHrR, JLH, LcweSC, oFvjYe, tWFmW, iPEYLK, ORjVc, QqCqfP, TuZ, kiP, lIHGc, zyhenO, KAQ, YNx, USQZB, eHwnu, tmq, gBpc, FobbT, GQNwJ, tNfe, uzs, pVt, qtuFea, JnajJ, vkjb, HfVTzq, Pbn, xVs, lCfNmP, clpl, qAx, JpkSE, oowqox, ceQ, POlLt, LwQvm, IxhZLd, GkpWBe, yZfOmV, BKJ, llVb, iSmG, qWx, eBoK, WgD, hQPZ, gtzSc, myQuXo, ZIY, UOUdy, qlyx, HJl, wnd, ehPLq, owbs, Nxkpo, CzBDq, eKG, Zixmek, eqGIke, iOrtvB, tEeae, ORphJJ, oudPr, uhpWhy, lLRvWs, tBLF, OBuSYK, IUe, WsOjU, yab, hfx,

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