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CHAPTER 7 – COENZYMES AND VITAMINS CHAPTER SUMMARY Introduction 1. True or false? (circle one) The catalytic repertoire of an organism is limited to the amino acid side chains in an active site. 2. What can be used to convert inactive apoenzymes to active holoenzymes? 3. What type of essential ion is loosely bound? Tightly bound? 4. What type of coenzyme is loosely bound? Tightly bound? 7.1 5. Metal-activated enzymes either _______________ added metal ions, or are _______________ by the addition of metal ions. 6. Metalloenzymes contain _______________ bound metal ions at their active sites. 7. Some metal ions _______________ bonds by attracting electrons. Others undergo reversible _______________ and _______________ by transferring electrons. 7.2 8. Coenzymes are categorized into _______________ (which are actually substrates in enzyme-catalyzed reactions) and _______________ __________ (which remain bound to the enzyme during the reaction). They both supply _______________ groups that are not available on the side chains of amino acid residues. 9. Most species in the Kingdoms prokaryotes, protists, fungi, and plants are capable of _______________ their coenzymes from simple precursors. _______________ have lost this ability, and need to ingest nutrients called _______________ from plants, microorganisms, and some from meat. 10. A nutritional–deficiency _______________ results when a vitamin is deficient or absent in the diet of an animal (see table 7.1 on page 194). 11. Why are water-soluble vitamins required daily? 12. What happens when lipid vitamins are ingested excessively? 13. Draw the structure of the simplest vitamin, the antiscurvy agent. 7.3 14. Several nucleoside triphosphates are coenzymes, including the most abundant, _____. 15. What four groups can ATP donate? 16. ATP plays a central role in _______________ as a high-__________ cofactor. 17. ATP is the source of a number of other metabolite coenzymes, including _______________, which is required for the conversion of norepinephrine to epinephrine. 18. The most common nucleotide-sugar coenzyme is _______________, which can donate its glycosyl group. This releases UDP, which can regenerate the coenzyme above after a phosphoryl group transfer from ATP and a reaction with glucose 1-phosphate. 7.4 19. The nicotinamide coenzymes __________ and __________ were the first to be recognized. Nicotinic acid (or __________) and nicotinamide are essential precursors of these coenzymes. 20. NAD+ and NADP+ play a role in many __________ reactions in which they assist in the transfer of _______________ to and from metabolites. 21. NADH and NADPH are the __________ forms of the coenzymes, and are said to have __________ power (or are biological __________ agents). In mitochondria, the oxidation of NADH is coupled to the synthesis of _____, and most NADPH is used as a reducing agent in _______________ reactions. 7.5 22. The coenzymes _____ and _____ are derived from _______________ (vitamin B2). Bacteria, protists, fungi, plants and some animals synthesize riboflavin, but mammals obtain riboflavin from __________. 23. FAD and FMN are prosthetic groups for many _______________, called flavoenzymes or flavoproteins. FAD and FMN are reduced to __________ and __________, and can participate in one or two electron transfers, an important aspect of many electron transfer systems. 7.6 24. The oxidation of fuel molecules, and the biosynthesis of some carbohydrates and lipids depend on _______________. It is involved in __________-group transfer reactions in which the __________ group covalently binds the acyl groups to form _______________. A good example is _______________, an energy-rich compound that is involved in the metabolism of carbohydrates, fatty acids, and amino acids. 7.7 25. Vitamin B1 (or _______________) is an essential vitamin in mammals, and a deficiency leads to _______________. 26. The coenzyme is _______________ _______________ (TPP), which is required by about a half dozen _______________, is involved in the oxidative _______________ of -keto acids (other than pyruvate), and is a prosthetic group for _______________. The reactive center is the _______________ ring. 7.8 27. Pyridoxal or pyridoxamine (_______________) is widely available from plants and animals, so deficiencies in humans are rare. In the cell, it is phosphorylized by ATP to _______________ _______________ (PLP). 28. PLP is the prosthetic group for many enzymes that catalyze reactions with amino acids, including _______________, _______________ and side-chain _______________ or _______________ reactions. 7.9 29. __________ is a prosthetic group for enzymes that catalyze transfers of __________ groups, and ATP-dependent _______________ reactions. It is covalently linked to the end of a __________ residue, and participates as a carrier of CO2. 7.10 30. _______________ are the coenzyme forms of the vitamin folate, which is required in the diet of humans. One of tetrahydrofolate’s derivatives is an important component in the biosynthesis of _____. Another derivative is required by enzymes that catalyze biochemical transfers of several one-carbon units. 7.11 31. _______________ (vitamin B12) is the largest B vitamin, and was the last to be isolated. It is required as a _______________ by all animals and some bacteria and algae, and in animals, a deficiency can lead to pernicious anemia, in which there is a decrease in the production of __________ cells by bone marrow. 32. Adenosylcobalamin participates in several _______________ rearrangements, methylcobalamin helps in __________ group transfers, and B12-dependent reductive dehalogenases __________ chlorinated organic molecules (like PCBs). 7.12 33. _______________ is covalently anchored to a lysine residue of dihydrolipoamide acyltransferases. It functions as a swinging arm that carries acyl groups between __________ __________ in multienzyme complexes. 7.13 34. The four lipid vitamins (A, D, E and K) contain __________ and long aliphatic __________ chains, making them highly _______________ (even though they have at least one polar group on the molecule). a. Vitamin A (_______________) is produced through the oxidative cleavage of _______________, which is found in __________ and other __________ vegetables. The terminal functional group may be an __________ (retinol), an _______________ (retinal – absorbs a photon of light which triggers a neural impulse), or a _______________ acid (retinoic acid – a signal cmpd that binds to receptor proteins in cells, and the complex that forms can bind to chromosomes and can regulate gene expression during cell differentiation). b. Vitamin D is a group of __________ vitamins. Vitamin D3 (_______________) is formed in the skin when humans are exposed to sunlight. The active forms of these vitamins are hormones that help control __________ utilization – they regulate the _______________ absorption and its deposition in __________. c. Vitamin E (_______________) scavenges __________ and __________ __________, which may prevent damage to fatty acids in membranes. d. Vitamin K (_______________) is from plants and is required for the synthesis of some of the proteins involved in blood _______________. 7.14 35. Ubiquinone (coenzyme ___) is lipid soluble and synthesized by almost all species. Its long hydrophobic chain allows it to dissolve into _______________, and its function is the transport of _______________ between membrane-embedded enzyme complexes. 36. Coenzyme Q is responsible for moving __________ from one side of the membrane to the other through a process called the “Q Cycle”, which results in the proton gradient that drives _____ synthesis. 37. Plastoquinone, an analog of ubiquinone, functions similarly in _______________ electron transport in chloroplasts. 7.15 38. Some proteins act as _______________ as well. They don’t catalyze reactions themselves, but are required by certain enzymes. They participate in __________ transfer reactions or in __________ reactions (in which the transferred group is hydrogen or an electron). 39. Examples include __________ (which contain heme prosthetic groups), _______________ (reducing agents in the citric acid cycle and in photosynthesis), and _____ ( a component of all fatty acid synthetases that have been tested). 7.16 40. Cytochromes are _____-containing protein coenzymes. Their __________ ions undergo reversible one-electron reduction. 41. They are classified as ___, ___ and ___ based on their visible absorption spectra. Each of their heme groups is slightly different, and each has a different _______________ _______________ (ability to transfer an electron to another substance). The range of reduction potentials is an important feature of membrane-associated _______________ transport pathways, and of _______________.