. Rietschel, in Advances in Carbohydrate Chemistry and Biochemistry, 1994. 6.7) [99,100]. A total of 16 carbon atoms are contained in palmitic acid. When many phospholipids line up, they form a double layer that is characteristic of all cell membranes. The antibiotic chloramphenicol has a bitter taste. At some temperature below the melting point of the lipid, the fine structure disappears completely due to movement of the acyl chain. 6.7). Iridoids can be divided into four main groups: iridoid glucosides, simple iridoids, secoiridoids, and bisiridoids (Fig. However, it is very unstable in the presence of UV–vis irradiation and oxygen. For a small, spherical particles, the balance of electric and viscous forces results in an electrophoretic mobility (u, defined as the particle velocity per applied electric field strength) given by. Fig. Nucleotide monophosphates such as adenosine-5′-monophosphate (AMP), guanosine-5′-monophosphate (GMP), and cytidine-5′-monophosphate (CMP) and also deoxyribonucleotides (Herring testis DNA 100–2000 base pairs in length) have been successfully intercalated into MgAl-LDHs via ion-exchange reactions.15,17,41 Figure 2 shows schematic illustration of the interlayer orientation of DNA strands that have been intercalated into LDH and their circular dichroism (CD) spectra, which indicate that the anionic DNA strands are tightly bound to the positively charged LDH layers, thus forming stable structures. The carbonyl group at the bottom of the structure is bonded to a nitrogen atom. As shown in Figure 6(a), over 10 days, the active concentration of the free IAA molecules decreased gradually to 40% of the initial concentration. Clearly, an understanding of phosphate chemistry is central to the study of biological organic chemistry. Reproduced from Choy, J. H.; Jung, J. S.; Oh, J. M.; Reproduced from Yang, J. H.; Han, Y. S.; Park, M.; Park, T.; Hwang, S. J.; Choy, J. H. Atomistic Modelling of Phosphopeptide Recognition for Modular Domains, Annual Reports in Computational Chemistry. 6.7. The incorporated enzymes were shown to have improved thermal stability, with more than 50% of their activity preserved. It is possible that bacteria, depending on their physiological demands, are able to add or omit ionic head-groups and thereby regulate their net surface charge (113). Nucleoside analogues represent the basic structures of various important therapies, including antiviral and anticancer treatments [159]. Classes of iridoids have an important distribution within the Apocynaceae family, but they are concentrated in few genera, the most representative are Plumeria, Himatanthus, Allamanda, and Cerbera [148]. Yang et al.63 have recently demonstrated the intercalation of indole-3-acetic acid (IAA) into ZnAl-LDH and ZBS for safe preservation and controlled release. Free amine groups as present in phosphatidylserine or phosphatidylethanolamine show a single sharp absorption band at 1075 cm−l. If the ends of the restricted DNA are not identical, dephosphorylation is not necessary, since the noncomplementary ends of the vector should not be able to ligate one another. MS is a convenient technique to monitor such reactions because mass determination provides direct evidence of the enzyme catalyzed addition or removal of modifying groups [30,31]. In a phosphate diester, for example, the two non-bridging oxygens share a -1 charge, as illustrated by the two major resonance contributors below. The phosphate beds contain Eocene fossils derived from the underlying strata and many fragments of Pleistocene vertebrata such as mastodon, elephant, stag, horse, pig, &c. The phosphate occurs as lumps varying greatly in size, scattered through a sand or clay; they often contain phosphatized Eocene fossils (Mollusca, &c.). For example, glucose-6-phosphate and isopentenyl diphosphate are often depicted as shown below. However, the nitrogenous bases of phospholipids can be identified by their IR absorption spectra in the region of 900–1100 cm−1. The formation of higher-order structures by nucleic acids will cause considerable deviation from this behavior, and indeed electrophoresis is used to ascertain the physical form of DNA. However it is in the form of phosphate, rather than phosphine, that phosphorus plays its main role in biology. 6.11. (a) Schematic illustration of the interlayer orientation of DNA strands and (b) circular dichroism spectra for free DNA in solution and DNA-LDH. The X atom is typically O, C, NR, or S. It should be noted that relatively small changes in the structure can cause different biological, chemical (stability, reactivity), physical (solubility) effects, minor changes in the structure produce relevant, and diverse biological effects [99–101]. Due to their phosphate groups, nucleic acids are negatively charged at all but the most acidic of pH conditions. In inorganic chemistry, the phosphate ion combines one phosphorus atom with 3 or 4 oxygen atoms, forming the base for many different salts. Neplanocin A and aristeromycin A. It was notable that, in this chapter, molecular orientation and stabilization could be determined by the type of lattice (Figure 6B (a) and (b)). Therefore, it can be concluded that the intercalated DNA becomes more twisted than free DNA in order to fit into the available area in the LDH lattice (Figure 2(a)). Some examples of phosphate minerals are; Apatite, Carbonate Apatite, and Brushite. For each compound, specify the number of bridging and non-bridging oxygens in the phosphate group. Generally, the phosphate group (−PO42−) of the B-type DNA occurs every 3.4 Å, and the diameter of the double helix is ∼20 Å. Some nucleoside analogues have been isolated from bacteria, sponges, and marine organisms; neplanocin A (isolated from Ampullariella regularies) and aristeromycin (isolated from Streptomyces citricolor) are the most common natural carbocyclic nucleosides, which show antiviral and anticancer activity; indeed the first famous synthesis by using natural source involved these two natural products [159], Fig. As natural source of chiral cyclopentane ring, the iridoids result variously substituted, enantiomerically pure and pose good chemical flexibility for a suitable convergent synthesis to give carbocyclic nucleoside analogues in comparison with furan derivatives, which are the principal building blocks employed for the synthesis of nucleoside analogues [151–157]. of the polypeptide. Similar thermal stability was observed with GLA intercalates; the intercalated GLA preserved 50% of its fatty acid moieties after 28 days at 50 °C, whereas all unprotected GLA molecules were oxidized after 14 days in the same chamber. Most frequently, this is accomplished by electrophoresis through a sieving medium, i.e., a gel, through which small molecules will pass more easily and larger ones will pass more slowly, due to the combined effects of sampling a greater fraction of the gel space and hindered transport (volume exclusion) effects. The spectrum of a solid phospholipid may show fine structure at low temperatures, which disappears on heating. By comparing the slopes of the degradation curves, which indicate the velocity of degradation, it was found that degradation of the DNA-LDH complex was negligible, while degradation of the naked DNA could be observed within a few minutes. It was shown that the wave number difference between two stretching modes of carboxylate, Δνas-s = νas(COO−) − νs(COO−), became larger when it was coordinated to a metal.64–66 As described by Yang et al., the Δν value for Na+-IAA, IAA-LDH, and IAA-ZBS were determined to be 161, 162, and 179 cm−1, respectively. In the water treatment business, most of us use “phosphates” as a general term to describe them all…but sometimes that can be misleading. According to Model 2, what class of enzymes performs phosphorylation? The term is used both in inorganic chemistry and organic chemistry. Secoiridoids are a diffused group characterized by the cleavage of the 7,8-bond on cyclopentane ring (Fig. Identify the steps in Model 2 that represent reception, transduction, and response for the phosphorylation pathway. The pathway I is the main route which produces the carboxylic iridoid form in major yield; it starts from iridodial skeleton which is oxidized to iridotrial form and consequently transformed into a series of iridoid glycosides, secoiridoids, including indole alkaloids [98,107–109]. See more. Phostphate Group properties Contributes negative charge (-1 when positioned inside a chain of phosphates; -2 when at end). phosphate group: compound example. Looking at the location of phosphorus on the periodic table, you might expect it to bond and react in a fashion similar to nitrogen, which is located just above it in the same column. The phosphate group of phospholipids shows a strong PO stretching band at 1350–1250 cm−l, which is sometimes a doublet and may be shifted to lower frequencies with an increase in intensity. It is usually ionized and attached to the carbon skeleton by one of its oxygen atoms.Compounds with phosphate groups are called organic phosphates and they are frequently involved in energy transfer reactions. Gas phase results from UV photoelectron spectroscopy [115-118] and ab initio studies [115, 119] performed on various fragments of the DNA backbone with no counterions or hydration at the phosphate, show an artificially low ionization potential of the phosphate ion (ca 5eV). The two main synthetic strategies which produce carbocyclic nucleoside analogues are: a linear synthesis which uses a sequence of reactions leading to the synthesis of the heterocyclic base starting from a chemical function present on the cyclopentane C-1, a convergent synthesis which uses a sequence of reactions to obtain the cyclopentane derivative conveniently functionalized and then the heterocyclic base is linked on C-1 by a specific reaction, often a stereospecific nucleophilic substitution on the carbocyclic backbone in position C-1 activated by a heterocyclic amine, Robert J. Ouellette, J. David Rawn, in Principles of Organic Chemistry, 2015, Phosphoric acid, pyrophosphoric acid, and triphosphoric acid occur in living cells as esters. In this case the so-called Ferguson plot gives the relationship between the gel concentration and the electrophoretic mobility (sieving effect). The chemistry of different classes of nucleoside analogues is relatively well explored and modern organic synthesis methods allow the preparation of a large variety of them. Phosphates can be grouped as: primary phosphates that have crystallized from a liquid; secondary phosphates formed by the alteration of primary phosphates; and rock phosphates formed from phosphorous-bearing organic material. Regardless of whether a single or double restriction digest is done, the 5′ phosphate groups of the vector must be removed, if restriction digest provides identical termini, in order to prevent self-ligation (i.e., recyclization) of the vector from taking place during the subsequent ligation step. Other electrophoretic parameters, such as applied field strength and temperature, have an effect on the mobility of the different chain length nucleic acids and on the separation efficiency. A phosphate group functions as part of energy-storing molecules, has an important role in the regulation of cellular metabolism, and is even a constituent of DNA and RNA. Another folate derivative, methotrexate (MTX: (2 S)-2-[(4-{[(2,4-diamino-7,8-dihydropteridin-6-yl)methyl] (methyl)amino}phenyl)formamido] pentanedioic acid), is known to act as a folic acid antagonist and inhibits the proliferation of certain cancers by regulating the biosynthesis of thymidylate.56,57 Unfortunately, these are quite unstable in biosystems, with short plasma half lives of 6.2 h and 3–15 h (depending on dose) for folinic acid and MTX, respectively. Figure 2. 6.9. Recently, however, Desigaux et al.52 succeeded at intercalating DNA fragments of various sizes (100–500 and 6000–8000 bp) into an MgGa-LDH through coprecipitation. Nevertheless, the corresponding potential use of nucleosides in therapy is not simple due to several factors: Many nucleoside analogues are not effectively phosphorylated by cellular kinases during the hydrolysis of the nucleoside-base bond C1-base, consequently the C1–C6 bond of the furan ring opens, and the resultant metabolites (especially those not identified) can be potentially toxic. Throughout this book, phosphate groups will often be drawn without attempting to show tetrahedral geometry, and π bonds and negative charges will usually be shown localized to a single oxygen. If a 'bond order' of 1.0 is a single bond, and a bond order of 2.0 is a double bond, what is the approximate bond order of bridging and non-bridging \(P-O\) bonds? Shi et al.55 intercalated the large protein bromelain, a mixture of proteolytic enzymes derived from pineapples, into LDHs by utilizing a reconstruction method in which calcined MgAl-LDH was mixed with bromelain/phosphate buffered saline (PBS). General structure of nucleoside analogues is depicted in Fig. Each phospholipid is made up of two fatty acids, a phosphate group, and a glycerol molecule. analyses have shown (73) that, in the lipid A part of this LPS, both phosphate groups at positions 4′ and 1 are nonstoichiometrically substituted by Etn-P to a similar degree (85 vs 80%). Thus, the DNA strands require 34 Å2 of area per single negative charge. The minus 3 charge on a fully deprotonated phosphate ion is spread evenly over the four oxygen atoms, and each phosphorus-oxygen bond can be considered to have 25% double bond character: in other words, the bond order is 1.25. (da Silva and Williams). Infrared spectroscopy revealed that the IAA molecules are more tightly bound to a ZBS layer than to an LDH. Organic phosphates. Separate chapters list protection for the hydroxyl group, phenols and catechols, the carbonyl group, the carboxyl group, the thiol group, the amino group, and the phosphate group. The Phosphate Class is made up of minerals with a basic chemical unit of tetrahedral (AO4) groups with a negative three (-3) charge.The A can be either Phosphorus, Arsenic, Vanadium or Antimony. Phosphate is everywhere in biochemistry. phosphate group: functional properties. Thus, under constant applied electric field, the mobility is determined primarily by the pore size of the gel matrix. At physiological pH, the protons in the –OH groups of these esters are ionized. The extent of phosphate substitution is influenced by, for instance, the growth conditions (122–124). (B) Interlayer arrangement models of IAA in (a) IAA-ZBS and (b) IAA-ZnAl-LDH hybrids, and (c) molecular structure of IAA The dashed rectangle highlights coordination bonds between carbonyl groups of IAA and coordinatively unsaturated Zn(OH)3 units of the ZBS lattice. From a chemical point of view, iridoids are atypical monoterpenoids; as basic structure, in general they can be described as methylcyclopentane-[C]-pyran, in which a methylcyclopentane is fused to a six member oxygenated ring, forming a bicycle system with 10, 9, or rarely 8 carbon atoms (Fig. In the course of last decades, it was also constantly explored the conformational motion of sugars/pseudosugars or their moiety, putting it in correlation with their biological relevance; these efforts led to the interest in the conformationally locked nucleotides [160–169]. The truth about phosphates is something that needs to be clarified, because there are a lot of opinions out there—ours included. These could be inorganic phosphate, inorganic pyrophosphate, or organic monophosphates, all of which are weakly basic, especially when coordinated to metal cations such as \(Mg^{+2}\) in the active site of an enzyme. The VE molecules are arranged as J-like aggregates with a tilting angle of 62°. Extraction and isolation methods from plant organisms is well known for a good number of iridoid glycosides. An MS-based phosphatase or kinase assay using MALDI-MS or ESI-MS analysis of intact phosphoproteins is a simple and straightforward method for monitoring the state of PTM, particularly for abundant (recombinant) proteins [32,33]. Both phosphate groups of lipid A at C-1 and C-4′ may carry (polar) substituents, although examples in which the phosphate groups are free are known. Nucleoside analogues or their metabolites might interfere with important enzymes. Consider the biological compounds below, some of which are shown with abbreviated structures: Phosphoric acid is triprotic, meaning that it has three acidic protons available to donate, with \(pK_a\) values of 1.0, 6.5, and 13.0, respectively. Phosphate group Definition noun, plural: phosphate groups ( biochemistry ) A functional group or radical comprised of phosphorus attached to four oxygen , and with a net negative charge, thus represented as PO 4 – Supplement The phosphate group is important in living things in different ways. Luigi Ornano, ... Armandodoriano Bianco, in Studies in Natural Products Chemistry, 2018. A functional group can participate in specific chemical reactions. 6.10. Assignment of acylglycerol bands in infrared spectra. Since the tails are hydrophobic, they face the inside, away from the water and meet in the inner region of the membrane. Vibration of the P–OH group gives rise to absorption at 2700–2560 cm−l. Quaternary amines such as phosphatidylcholine or sphingomyelin have a doublet at 1087 and 1053 cm−1 and a sharp band at 961 cm−l. The ester carbonyl frequency and bands between 670 and 1050 cm−1 may shift due to the variations in the crystal structure arising from different polymorphs. Being a natural resource, this metabolite is enantiomerically pure, defined chiral template because it is synthesized by biosynthetic pathway employing enzymes. Structural variations of nucleosides and their analogues are briefly described later. 6). The phosphate group connects successive sugar residues by bridging the 5′-hydroxyl group on one sugar to the 3′-hydroxyl group of the next sugar in the chain. Draw all of the resonance structures showing the delocalization of charge on a (fully deprotonated) organic monophosphate. Just as alcohols react with carboxylic acids, they also react with phosphoric acid, pyrophosphoric acid, and. For analytical purpose, identification and quantification involve GC-FID and GC-MS, which identify a specific iridoid glycoside by using its original fragmentation pattern correlated with the relative retention time. The four oxygen substituents in phosphate groups are arranged about the central phosphorus atom with tetrahedral geometry, however there are a total of five bonds to phosphorus - four s bonds and one delocalized \(\pi \) bond. Phosphorus can break the 'octet rule' because it is on the third row of the periodic table, and thus has \(d\) orbitals available for bonding. Its palatability for children is improved by using a suspension of the palmitate ester. Despite this interesting method of resolution of mixtures of iridoids and the pharmaceutical interest addressed to iridoids, there are few scientific papers which face this kind of purification way [97–158]. From a chemical point of view, iridoid glycosides are constituted by a cyclopentane ring connected by means of cis'junction with a dihydropyran ring, C-1 result linked with a sugar moiety, Fig. A partial loss of phosphate (HPO3, 80 Da) is seen in MALDI reflector TOF MS in the case of tyrosine phosphorylated peptides [30,36]. LDHs can be utilized to encapsulate labile but bioactive substances like vitamins to protect them against rapid degradation by light, temperature, oxygen, alkali metals, etc.42,58,59 In fact, their fast degradation greatly limits their application as active ingredients in cosmetics and foods. The Phosphate Class is made up of minerals with a basic chemical unit of tetrahedral (AO4) groups with a negative three (-3) charge.The A can be either Phosphorus, Arsenic, Vanadium or Antimony. When attatched, confers on a molecule the ability to react with water, releasing energy (ATP / ADP) The degree of metastable decay in MALDI is matrix dependent, and is mostly observed when a ‘hot’ matrix, such as α-cyano-4-hydroxycinnamic acid is utilized. Two enzymes that are commonly used for dephosphorylation reactions are calf intestinal alkaline phosphatase (CIP)115 or bacterial alkaline phosphatase (BAP);116,117 in both cases, the reaction is typically allowed to proceed for 30 min at 37 °C. That is, the DNA is thought to reptate through the pores of the gel in a wriggling, snake-like manner. Chia-en A. Chang, Yu-ming M. Huang, in Annual Reports in Computational Chemistry, 2013. There are so many types of phosphates and they react differently. Below are a number of representations, labeled A-S, of molecules that contain phosphate groups. Despite the fact that drug resistance often emerges, some nucleoside analogues are used in combination treatment of various viral and retroviral diseases (hepatitis, HIV, etc.) Phosphate acid halides have been used to introduce phosphate groups into lead structures. Related terms: Phosphate group , diphosphate , triphosphate , pyrophosphate , nucleoside , nucleotide , adenylic acid , ATP , S … Reproduced from Oh, J. M.; Kwak, S. Y.; Choy, J. H. Chapter 1.115, Calcium Phosphates for Cell Transfection. The X-ray diffraction pattern of these LDHs suggests that the interlayer orientation of fatty acids forms a close zig-zag packing of linear molecules. Phosphates are usually used as compounds of phosphate ions in combination with one or more common elements, such as sodium, calcium, potassium, and aluminum. The fatty acid chains are the uncharged, nonpolar tails, which are hydrophobic. Nucleosides and nucleotides are evolutionary well-conserved molecules that are essential for living organisms. The phosphate group is the negatively-charged polar head, which is hydrophilic. J.H. Many biological activities are recognized on the basis of this type of compounds [150]. Similar to fatty acid intercalates, interlayer VA molecules appear to be arranged in a zig-zag orientation that maximizes their intermolecular π–π interactions. An enzyme called ATP synthase can use energy from the food we eat to attach the phosphate again. The carbon atom chain to the right of the carbonyl group is part of the acid. By continuing you agree to the use of cookies. BAP is more active than CIP and as a result is much more resistant to heat and detergent inactivation. If a phosphate group is attached at the 5'position, it becomes deoxyguanosine monophosphate. 6.7). Phosphorylation of proteins is important for several reasons. The biological stability of DNA in a DNA-LDH intercalate can be quantitatively evaluated using a DNase I resistance test. However, double-strand formation and counterion condensation serve to decrease the flexibility of the nucleic acid, and as a result the reptating nucleic acid behaves more as a stiffly jointed rod in its transport through a sieving gel. These replacements, though, often occur via a dehydration synthesis reaction such that, for example, a water molecule is removed from a combination of a hydroxyl group and the phosphate group to be. Thus, separation of very high (>60 kbp) molecular weight DNA requires other techniques, such as pulsed-field gradient electrophoresis. Similarly, removal of phosphate groups by the action of phosphatases results in a mass decrease of 79.97986 or multiples thereof. Iridoid glucosides (R = glucose), simple iridoids, secoiridoids, and bisiridoids. Common biological targets of antiviral nucleosides are reverse transcriptases or RNA and DNA polymerases. Finally, phosphates are excellent leaving groups in biological organic reactions, as we will see many times throughout the remainder of this book. Which contain one or more phosphate monoesters? General structure of nucleosides and nucleotides is illustrated in Fig. Apparently, negligible changes in bond lengths between C-1 and C-4 and the electronic properties of some atoms can lead to different conformational behaviors, which often play a significant role in the recognition and interaction between substrate and enzyme. These compounds are analogs of acid anhydrides of carboxylic acids. After entering the cells, these drugs are converted into the nucleotides by kinases or degraded. M.H. [97], the iridoids are found into Lamiids, which contain iridoids of Gentianales, Lamiales Gallyales order, and into Campanulids, which contain secoiridoids of Asterales and Dipsacales order. We write articles to share ideas and little-known facts. Anny-Odile Colson, Michael D. Sevilla, in Theoretical and Computational Chemistry, 1999. A Phosphate Group Nitrogenous bases include purine molecules (adenine and guanine) and pyrimidine molecules (cytosine, thymine, and uracil.) Phosphate minerals contain the tetrahedrally coordinated phosphate (PO 4 3−) anion along sometimes with arsenate (AsO 4 3−) and vanadate (VO 4 3−) substitutions. We use cookies to help provide and enhance our service and tailor content and ads. First, locate the ester functional group by examining the carbonyl carbon atoms. Phosphate mineral, any of a group of naturally occurring inorganic salts of phosphoric acid. In the resonance contributors in which the bridging oxygens are shown as double bonds (to the right in the figure below), there is an additional separation of charge - thus these contributors are minor and make a relatively unimportant contribution to the overall bonding picture. However, IAA molecules stabilized with either LDH or ZBS retained most of their active moieties over the same time period. These groups play an important role in the formation of molecules like DNA, proteins, carbohydrates, and lipids. Drug molecules and other biofunctional molecules require stabilization because they can easily be destroyed or expelled by various drug-resistant mechanisms in biological systems. The strong electrostatic interaction between folic acid species and the LDHs was also verified by infrared and UV–vis spectroscopy as well as thermogravimetric analyses. In particular, vitamin C oxidation is facilitated in the presence of oxygen and a small amount of metal ions. Legal. glycerol phosphate. This is similar to the behavior observed with soaps and is due to the flexing and twisting of the hydrocarbon group on heating. Lipids are molecules that include fats, waxes, and some vitamins, among others. The phosphate class of minerals is a large and diverse group, however, only a few species are relatively common. For example, the CH2 rocking band at 720 cm−1 of 2,3-dipalmitoyl-dl-1-phosphatidylethanolamine is split into a doublet at low temperatures but this band changes into a singlet at room temperature. The trans double bond of sphingosine derivatives gives an absorbance band at 970 cm−1, although another band occurs at this frequency in some sphingosine derivatives such as sphingomyelin and this interferes with the use of this band for quantitative determination of the trans unsaturated content. In addition, the range 1430–1820 cm−1 shows characteristic features. Phosphate group definition, the group or radical obtained by removal of one or more hydrogen atoms from phosphoric acid. Some of the important functional groups in biological molecules include: hydroxyl, methyl, carbonyl, carboxyl, amino, phosphate, and sulfhydryl groups. An organic diphosphate has two bridging oxygens (one in the phosphate ester linkage and one in the phosphate anhydride linkage) and five non-bridging oxygens: A single phosphate is linked to two organic groups is called phosphate diester. [171]. As suggested by Amaral et al. Given that the thickness of a brucite-like LDH sheet is 4.8 Å, the gallery heights are estimated to be 17.1, 14.3, and 15.1 Å for folic acid-, folinic acid- and MTX-LDH intercalates, respectively. The synthesis of carbocyclic nucleoside analogues which employ iridoid glycosides can be defined as a convergent type synthesis. It is noteworthy that most of the substituents on the phosphate, such as Etn, l-Arap4N, and GlcpN carry, at neutral pH, a positively charged amino group. In DNA and RNA, a phosphodiester group (in the black circle) joins the 3'-carbon on the ribofuranose of one nucleobase to the 5'-carbon on the next nucleobase. Recently, the intercalation procedure has been employed in food science to increase the stability and applicability of additives. The oxygen atom between the phosphorus atoms is part of the anhydride bond. Nucleosides, nucleotides, and analogues are interesting molecules for scientists in almost all natural sciences. phosphate: [noun] a salt or ester of a phosphoric acid.
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