PSMA 411 Biochemistry Midterms PDF

PSMA 411 BIOCHEMISTRY | MIDTERMS BIOCHEMISTRY WHAT IS BIOCHEMISTRY? CELL MEMBRANE  the science concerned with the chemical basis of life  Aka PLASMA MEMBRANE/ PLASMA LEMM...

PSMA 411 BIOCHEMISTRY | MIDTERMS BIOCHEMISTRY WHAT IS BIOCHEMISTRY? CELL MEMBRANE  the science concerned with the chemical basis of life  Aka PLASMA MEMBRANE/ PLASMA LEMMA  chemical constituents of living cells and with the  The outermost structure of the cell that decides its reactions and processes they undergo. contour is the cell membrane.  a study of the compounds and processes associated  SEMIPERMEABLE with living organisms  Common Model: Fluid Mosaic Model that describes  “BIOS” – life the structure of cell membrane. It indicates that the  When all of those biochemical events that cell membrane is not solid. It considered as flexible occur in proper order, the cell or the body and similar consistency to a vegetable oil. All the remains normal individual molecule are just floating in a fluid medium  If there will be a blockade and those and they are capable of moving sideways within the biochemical events it will manifest now to cell membrane such disorders or diseases COMPONENTS:  If pertaining to biomolecules, these are  Phospholipid considered to be organic compounds or - main component organic substances that are very essential - It is a bilayer for the survival that is very important for us to - Composed of hydrophilic head and go on in life. hydrophobic tail  Glycoprotein and Glycolipids CELL - Glycoprotein is a very important integral membrane proteins where they play a  Cell is the basic unit of life. role in cell-cell interactions  It consists of protoplasm that is enclose within a membrane which consist of biomolecule such as - Glycolipids maintain the stability of the proteins and nucleic acid cell membrane and facilitate cellular recognition MOLECULAR COMPOSITION - Both are important to play a role in cell signaling, cell attachment, and Water 70-75% regulation of immune system  Cholesterol Organic Molecules Nucleic Acid 7-10% - Gives the fluidity and consistency of the cell 25-30% Proteins 10-20%  Arachidonic Acid Carbohydrates 2-5% - These are eicosanoid, it undergoes the pathway for the eicosanoid which is a Lipids 3% polyunsaturated fatty acid - It is important because the human body Inorganic Molecules Trace Elements uses it as a starting material in a The remaining percent Includes: Sodium, synthesis of two kinds of essential Potassium, Calcium, substances. They are: Prostaglandins, Magnesium, Copper, Iron, Leukotrienes, Thromboxane Ions like chloride, FUNCTIONS: phosphate, bicarbonate, iodide, fluoride and sulfate  Controls the entry and exits of substances in the cell PARTS OF THE CELL ORGANISM Membrane/ Wall Sterol Present PLANTS Cellulose Phytosterol and B-Sitosterol BACTERIA Peptidoglycan – protects the cell from any mechanical and osmotic pressure. Made up of 1|PAGE  protein and an - Cristae is located in the inner membrane oligosaccharide of mitochondria - “Powerhouse of the cell” FUNGI Chitin Ergosterol  Lysosomes - called as ‘SUICIDAL BAGS’ of the cell - lysosomal enzymes digest the molecules brought into the cell by phagocytosis. NUCLEUS - Phagocytosis ingestion of bacteria or other material (CELL EATING)  “CONTROL center of the cell” - In a physiological cell, the RBC usually  information center of eukaryotic cell. It is mainly circulate the body within 120 days. But concentrated in the form of CHROMOSOMES. when the cell membrane has a defect, COMPOSITION OF NUCLEUS the RBC will breakdown faster even  Nucleolus before reaching 120 days - Cite of the ribosomal assembly  DISORDER: Related to Anemia - Also known as NUCLEAR MATRIX - 3 types of cell death - Contains of enzymes that are involved in  Necrosis also known as cell the synthesis of DNA and RNA murder (due to the decrease  Chromosomes oxygen supply or ATP - Thread like bark of the cell that carries production is blocked) the hereditary information in the form of  Atrophy (due to the absence of chains those survival factors - It also has chromatin which is a mass of  Apoptosis (program cell death) genetic material composed of DNA and *REMEMBER: Lysosomes have those lysosomal enzymes and proteins that condensed to form somehow those enzymes are responsible for metastasis and chromosomes during the eukaryotic cell spread of cancer cells division  Peroxisomes - SEX CHROMOSOMES - Are also small vesicles surrounded by a  Female (xx) membrane. They are also called as  Male (xy) MICROBODIES - DISEASE: - They contain enzymes for H2O2  Trisomy 21/Down Syndrome/ metabolism Non-disjunction - Without peroxisomes inside the body,  Cause by an error in there could be no way to produce cell division peroxide that is necessary for the  Results in an embryo metabolism. Nor, could there be anyway with three copies of to get rid of it from the body. chromosome 21 ENZYMES: instead of two  Peroxidases  Prior to or at  Catalases conception, a pair of a DISEASE: Zellweger Spectrum Disorder 21st chromosomes 3 TYPES OF ZES either a sperm or egg it 1. Zellweger’s Syndrome/ fails to separate Cerebrohepatorenal Syndrome  Nuclear Membrane  Very rare congenital disorder - Almost the same with cell membrane that  Most severe controls the entry and exit of molecules  Characterized by the reduction in a nucleus or absence of functional - Protects the genetic material peroxisomes in the cells of an - Nuclear Pores individual  Location in which the exchange  One of the family of the disorder of material between nucleus called as the leukodystrophies and the other parts of the cell 2. Neonatal Adrenoleukodystrophy (NALD) ORGANELLE  Medium severity  Damage the white matter  a specialized subunit within a cell that has a specific of the brain and impairs function the adrenal glands COMPOSITION OF ORGANELLE 3. Infantile Refsum Disease (IRD)  Mitochondria  Least severe form of - It has an inner and outer membrane Zellweger Spectrum which consists of proteins and Disorder phospholipids. FUNCTIONS: - Inner Phospholipid is known as  Hydrogen peroxide metabolism “Cardiolipin” which is localized and  Breakdown fatty acid to be used synthesize in the inner mitochondrial in forming membranes and as membrane fuel for perspiration. 2|PAGE   Endoplasmic Reticulum  In a photosynthetic bacterium, the mesosomes - Associated with the degradation of contains the proteins and pigments the trap-like and misfolded proteins affected with generate ATP Parkinson’s Disease  Cystosomes contains macromolecules like enzyme,  It is the unfolded protein MRNA, TRNA, ribosomes and other organic compound response which is down that are needed to cellular metabolism regulated to Alzheimer’s  Prokaryotic cystosomes that consist of single Disease and Endoplasmic circular molecule of DNA is condensed to Reticulum Calcium form a body known as the nucleio Homeostasis that is distributed  Examples: Bacteria and Archaea in the form of Ischemia  It has 3 basic shapes 2 TYPES OF E. R.  Spherical also known as cocci  Rough E.R.  Rod-like or the bacilli - involved in protein synthesis  Helically coiled or the spiralia - Ribosomes are present.  Smooth E.R CELL - Lipids synthesis - Ribosomes are NOT present Prokaryote Eukaryote - Responsible for the lipid  Golgi apparatus NO true Nucleus TRUE NUCLEUS - are well developed in cells, which are involved in SECRETION NO membrane bound Mitochondria, Lysosomes, - involved in glycosylation and sulfation of organelles ER, Golgi apparatus proteins 30s + 50s = 70s 40s + 60s = 80s - Glycosylation is the attachment of the sugar moieties to proteins PROTOZOA  bacteria Plants, Animals, Fungi - Sulfation attachment of the sulfate’s ions to proteins  Ribosomes - Very small macromolecular complexes BIOMOLECULES composed of rRNA and proteins responsible in protein synthesis  We cannot survive if we don’t have biomolecules (translation) on mRNA templates.  Aside from biomolecules, our body also need enzymes FUNCTION: and vitamins  Translate information  Carbohydrates encoded in mRNA into the - Hydrates of Carbon most wide spread polypeptide chains of amino compound that involved in the build up acids that make up the and biological functions of the cell proteins - BUILDING BLOCKS: Monosaccharides ANIMAL CELLS PLANT CELLS  Simplest form of sugar so it cannot be hydrolyzed to more Shape Round (irregular Rectangular simpler shape) - BONDS: Glycosidic Cell Wall Absent (Cell Present - EXAMPLE: Glucose, starch, glycogen membrane) FUNCTIONS: Plastids – None Present - Provide energy associate in (Chloroplast) - Store energy manufacture or - Build macromolecules storage of food - Spare the proteins and fats for other uses Vacuole – water 1 or more 1  Lipids sac of the cells - Diverse group of organic compounds that that gives shape includes fats, oils, hormones and other components of the membranes - BUILDING BLOCKS: Fatty Acids PROKARYOTIC CELLS  They exist in the body in an esterified form  Prokaryotic cell was the first form of life on Earth  Fatty acyl ester  They are considered as simpler and smaller than the  Example is triacyl glyceride Eukaryotic cells  Saturated fatty acid Present in  They lack those membrane bound organelles such as Animals: 12C fatty acid (lauric the Nucleus acid), 14C (myristate), 16C  Each prokaryotic cell is surrounded by a plasma (Palmitate), 18C (stearate), 20C membrane. So, the cells have no sub-cellular (arachidate), 22C (behenate), organelles only infoldings of the plasma membrane 24C (lignocerate) which is called mesosomes which is the cite of DNA  Unsaturated fatty acid present replication and other enzymatic reaction in our body or in animal cell: 16C (palmitoleate), 18C 1 bond (oleate), 18C 2 double bonds 3|PAGE  (linoleate), 18C 3 double bonds  Like in plant cell wall, it composed of cellulose (linoleneate), 20C 4 double and cellulose is considered as carbohydrates. bonds (arachidoneate)  Made up of repeating unit of glucose that is - BONDS: Ester linked by beta-1 and 4 glycosidic linkages - EXAMPLE: Triglycerides, waxes  If you eat food with cellulose, it is not actually FUNCTIONS: digest because human body is lack of enzyme - Store energy that can breakdown cellulose which is - Signaling molecule cellulase - Act as a structural component of cell  SALAD IN, SALAD OUT (kung paano mo membrane kinain, ganon din lalabas)  Nucleic Acids  For bacteria, they have peptidoglycans - Informational molecule that are made up (combination of carbohydrate and protein) of nucleotides  In the human body, we have proteoglycans - BUILDING BLOCKS: Nucleotides  Proteoglycans are hybrid  Composed of sugar moiety, molecules that is composed of nitrogenous base, phosphoric heteropolysaccharide that is acid joined to a polypeptide which is a - BONDS: Phosphodiester protein. - EXAMPLES: DNA, RNA  Composition of proteoglycans: FUNCTION: glycosaminoglycan, core protein, - Store and transfer genetic information linker protein, hyaluronan  Proteins molecule - It is about 70% organic matter of the cell - BUILDING BLOCKS: Amino Acid  Organic molecules containing carboxyl and amino functional group  300 amino acids occurring in nature but 20 amino acids are commonly occurring and constituents of proteins - BONDS: Peptide - EXAMPLE: Pepsin, hemoglobin  All glycosaminoglycans are RESPONSIBILITIES: considered as proteoglycans except - Building tissues and muscles necessary for the Hyaluronic Acid because it in building or repairing those tissues lacks protein and does not have - Hormone production sulfate ions - Act as enzyme  Glycosaminoglycans is also known - Immunological function as mucopolysaccharide - Provide energy  Heteropolysaccharide that is composed CARBOHYDRATES of 2 alternating units (sugar acid and amino sugar)  Polyhydroxy compounds with aldehyde, ketone or an  sugar acids can be a uronic acid or a alcohol glucoronic acids or iduronic acids  Most abundant organic molecules in nature  amino sugar (should be acetylated) can  Hydrates of carbon be in the form of glucosamine (N-acetyl glucosamine), galactosamine (N-acetyl  General Formula: Cn(H2O)n galactosamine)  Source of Energy:  1g Lipids: 9 kcal  1g Carbo: 4 kcal  1g Alcohol: 7 kcal FUNCTION OF CARBOHYDRATES  Storage form of fuel  Source of energy in the body is ATP,  Chondroitin is made up of glucorinic acid which is a sugar acid and N-acetyl galactosamine Use: genital joint lubricant  Dermatan sulfate is composed of iduronic acid and N-acetyl galactosamine  Heparan sulfate composed of glucoronic acid and d-glucosamine (not acetylated)  Structural elements  Heparin is composed of iduronic acid and d-glucosamine 4|PAGE  Use: anticoagulant  E.g., Transferrin for Fe transport, Ceruloplasmin for Cu Transport  Glycoproteins transport vital molecule or substances essential for metabolic function  Confer biologic specificity on animal cell surface  There are 3 substances or factors to be considered in different blood types  There are RBC that antigen was attached and at the same time, it also has those antibodies which trigger the immune system. Antibodies are found outside the RBC and will interact in Structure of Hyaluronic Acid and the opposite antigen Keratan Sulfate  A antigen, outside the RBC there are A  Does not have sulfate antigen markers present  All glycosaminoglycans contain  Antibody present is B sugar acid and amino sugar except  O antigen no present surface markers Keratan sulfate because the sugar  Antibody both A and B acid is replaced by the d-galactose  B antigen, outside the RBC there are B and galactose is not a sugar acid marker present  Antibody A is present OTHER FUNCTIONS  AB antigen, it has both A and B markers  No antibody  Lubricant of skeletal joints  Outside RBC has an antibody that trigger  Chondroitin sulfate and hyaluronic acid both immune system and it will react on the are glycosaminoglycans that are considered opposite antigen to be known as skeletal joint lubricant  Ceramide is also known as a backbone  Most of the medication for arthritis contains  Each antigen has a different composition glycosaminoglycans that is injected to affected joints  Major component of bacterial cell walls and soft cell coats in animal tissues  Eukaryotic cell membranes have an external surface structure called as glycocalyx. It is composed largely of carbohydrate molecules that are attached to membrane surface and certain lipid molecules  Prokaryotic cell contains complex carbohydrates and peptide containing polymers that enhance strength of cell wall or membrane  Peptidoglycan in bacteria is a network that is  Supply precursors for synthesis of vital biologic composed of such polymers substances  Some bacteria secrete substances such as  Enzymes polysaccharide and proteins that is a slime  Hormones layer or a capsule that accumulate on the  Follicle stimulating hormone (FSH) outside of the cell  Thyroid stimulating hormone  Precursors of DNA, RNA and ascorbic acid BIOSYNTHESIS OF CARBOHYDRATES  Provide adhesion between cells  E.g., Hormonal activation of cells, immune system mediation through cytokines  Glyco-conjugate or complex carbohydrate polymers that are covalencely attached to proteins or lipids which are found in cell membrane which aid in determining substances enters or exits the cell  Act as signals that determine the intracellular location or the metabolic faith of hybrid molecules (membrane receptor)  Transport functions (biochemical transport) 5|PAGE   Carbohydrates is part of photosynthesis whether a light  If ketose, the double is either in the second or third reaction that convert the electromagnetic energy into carbon (RCOR) chemical potential to come up to ATP and NADPH. For the direct dark reaction, it utilizes those chemical potentials that are need or produce from light reaction to fix the Carbon dioxide into sugar  Dark reaction is Calvin Cycle  The carbohydrates that we are administering or taking in inside the body will be metabolize to convert into an energy  If you are not eating foods with carbohydrates, there are substances in the body that can convert into an ATP or energy  The formation of glucose from non-hexose precursor is known as gluconeogenesis  The pathway of Phosphoenolpyruvate will convert to Glucose-6-phosphate if that came from lactate or pyruvate  TAG or triacylglycerol will be glycerol or simply cholesterol or fatty acid. For 4-glucogenic amino acid is protein will be converted to PHOSPHOENOLPYRUVATE and to GLUCOSE-6- PHOSPHATE to produce sugar that is necessary  The double bond is in the first carbon so, aldose inside the body. It could be in the form of glucose or  The double bond is in the second carbon so ketose glycogen  In plants, there are photosynthetic reaction because CLASSIFICATION OF CARBOHYDRATES carbohydrates are the product of the photosynthesis  Crystalline and Sweet  MONOSACCHARIDE  Fructose is the sweetest  DISACCHARIDE  Sucrose has a standard sweetness  Lactose least sweet  Fibrous and Tasteless  OLIGOSACCHARIDE  POLYSACCHARIDE MONOSACCHARIDE  The simplest sugar; building block of carbohydrates  Contains 3-10 carbon atoms  Properties:  Gluconeogenesis is the production of glucose or  Colorless glucose is synthesized by a non-carbohydrate  Crystalline solids  Freely soluble in water but insoluble in non- polar solvents  It cannot be hydrolyzed  Can be classified according to:  the number of carbon atoms  the functional group present (aldose/ketose)  Ring structure formed  If aldose, the double or carbonyl is located at the first carbon (RCOH) 6|PAGE  CARBOHYDRATES CLASSIFICATION OF CARBOHYDRATES: BASED ON THE RING STRUCTURE FORMED  Monosaccharides containing 4 or more carbon atoms MONOSACCHARIDES tend to have cyclic structures. BASED ON THE # OF CARBON ATOMS  Furan – 5C atoms (Furanose - sugar)  Pyran – 6C atoms (Pyranose - sugar)  To make a ring, it should be based on the fish and bone (Fischer) structure of the sugar. There should be a link between the OH group of the penultimate carbon with  Glyceraldehyde – simplest aldose the carbonyl group.  Penultimate Carbon – the carbon between the last carbon (If the sugar has 6C, the penultimate carbon will be the 5th carbon) MONOSACCHARIDES GLUCOSE  Aldohexose  Other names:  Blood sugar  Physiologic sugar  Grape sugar  Dextrose  Corn sugar  D-glucopyanose  Can be an excipient in pharmaceutical preparations  Also used as a nutrient XYLOSE  Ketoaldose  Other names:  Wood sugar  Obtained by boiling corn cubs with diluted acid to hydrolyze the xylan power.  Used as a diagnostic agent to determine if there is any intestinal malabsorption FRUCTOSE  Ketohexose  Other names  Laevulose  Fruit Sugar  Source: - Sucrose  - Invert Sugar – a mixture of glucose and fructose (equimolecular amt = equal amt) produced from a sugar (sucrose, preferably)  Chmx Test: SELIWANOFF’S TEST  (+) RED GALACTOSE  Aldohexose  Other names:  Brain Sugar (Galactocerebroside)  C4 epimer of glucose 7|PAGE  - Gal  Glu - Fehling’s Test – to det. the reducing property of a - GALACTOSEMIA – the body can no longer sugar metabolize the sugar because of too much galactose in the blood - GALACTOSEMIA follows an autosomal recessive models of inheritance that confers a deficiency in an enzyme (galactase) Chmx Test: MUCIC ACID TEST  (+) CRYSTAL FORMATION - MUCIC ACID – aka GALACTARIC ACID  Rapidly absorbed in the small intestine - Benedict’s Test – a test for the free aldehyde or the keto group in the reducing sugars (there will be a reduction of that cupric hydroxide in alkaline medium to red color cuprous oxide) - Tollen’s Test (aka Silver Mirror Test) – a test to distinguish between and aldehyde and ketones o Aldehydes are substances that readily oxidize whereas Ketones are not. Manifestations of Galactosemia: - Trommer’s Test – involves treating a sample with a strong acid (sulfuric acid) w/c results in the aid  Brain Damage of the hydrolysis of disaccharide to  Cataracts monosaccharide  Jaundice - Nylander’s Test – test for the detection of the  Enlarged liver presence of reducing sugar  Kidney damage o Glucose and Fructose reduces bismuth MANNOSE oxynitrate to bismuth under alkaline condition  Aldohexose - Barfoed’s Test – used to detect the presence of a  C2 epimer of glucose monosaccharide specifically reducing sugars  Uses: o Barfoed’s Rgt – is a mixture of ethanoic  Mannitol (sugar alcohol)  Osmotic diuretic acid and copper acetate  MONOSACCHARIDES are ALL REDUCING Chmx Test: OZASONE TEST  (+) NEEDLE SHAPED SUGARS CRYSTAL  DISACCHARIDES can be a NON-REDUCING OR A - All sugars have soluble osazone REDUCING SUGAR (MALTOSE & LACTOSE ARE - The only sugar w/o a soluble osazone is REDUCING SUGARS while SUCROSE is a NON- MANNOSE REDUCING SUGAR)  Non-reducing sugars do not have an OH group SHAPES OF THE OSAZONES FORMED: attached to the anomeric carbon so they cannot reduce Sunflower shaped  MALTOSE other compounds such as SUCROSE Powder puff shaped  LACTOSE  If a sugar is being OXIDIZED, the product is a SUGAR ACID Rhombic like  GALACTOSE  If a sugar is being REDUCED, the product will be RIBOSE SUGAR ALCOHOL  If the ALDEHYDE CARBONYL GROUP is OXIDIZED,  Aldopentose it will become the ALDONIC ACID  Important sugar for genetics formation  If the ALDEHYDE CARBONYL GROUP and the PRIMARY TERMINAL ALCOHOL GROUP are both oxidized, it will form ALDARIC/SACCHARIC ACID  If the PRIMARY TERMINAL ALCOHOL GROUP alone is OXIDIZED, it will form URONIC ACID  A sugar can be reducing sugar if it can be oxidized  All sugar can be reducing sugar except FRUCTOSE OLIGOSACCHARIDES: DISACCHARIDES SUCROSE REDUCING PROPERTY Other name:  Table sugar  If a sugar is a reducing sugar, it will have a positive  Non reducing sugar result of a brick red ppt.  Upon hydrolysis, it will give you 1 unit of GLUCOSE and 1 unit of FRUCTOSE (GLU + FRU) 8|PAGE   Formed via the dehydration rxn (removal of water)  Raffinose – a trisaccharide that can be found in beans,  Combination of 2 sugar units (2 monosaccharides) w/c cabbage, brussels sprouts, broccoli is bonded together by a glycosidic bond  Maltotriose – metabolite found in urine after ingestion  C6H12O6 + C6H12O6  C12H22O11 or infusion of maltose  Demulcent: Contained in Simple syrup NF  85% w/v  Sucralose – 0-calorie artificial sweetener/calorie-free - Most common sucralose-based product – MALTOSE SPLENDA (contains other constituents present like dextrose, maltodextrin w/c increases its Other name: calorie content)  Malt sugar - Sucralose is made from sugar in a multi-step  Beer sugar chemical process where 3 hydrogen-oxygen  Reducing sugar groups are replaced with chlorine atoms  GLU + GLU - Discovered in 1976 when a scientist at a British  Product of the partial hydrolysis of starch or through the college misheard instruction about testing a diastatic fermentation of barley substance instead he tasted it realizing its sweet taste  Gentianose – plant metabolite - A crystallizable sugar-like substance w/ a slightly sweetish taste - Can be obtained from the fresh gentian root POLYSACCHARIDES  Composed of 10 or more sugar units that are binded together by the glycosidic bond  Can be a homoglycan or heteroglycan HOMOGLYCAN TREHALOSE  1 component  Starch  Non reducing sugar  Glycogen  Came from steroids  Inulin  Could also be from an ergot or a yeast  Dextran  GLU + GLU  Cellulose CELLOBIOSE HETEROGLYCAN  2 or more component  GLU + GLU  Gums  By-product of the enzymatic breakdown of cellulose  Mucilage LACTOSE STARCH Other name:  Temporary storage of carbohydrates for plants  Milk sugar  Has 2 parts: amylose & amylopectin  Reducing sugar  GLU + GAL AMYLOSE  Came from the Bos Taurus  Lactose Intolerant – cannot hydrolyze lactose because  Linear of lack of the enzyme lactase  composed of 250 to 300 D-glucopyranose units - Gastrointestinal distress  linked by α -1, 4 glycosidic bonds o Lactulose – alkaline rearrangement of lactose  more soluble in water than amylopectin - Semi-synthetically prepared  Amylose + iodine = deep blue complex - fructose and galactose - poorly absorbed AMYLOPECTIN - Bacteria in the colon metabolize the disaccharide to 2 irritating acids (acetic and lactic)  Branching (every 25 units) - laxative effect  consists of 1000 or more glucose units - also used for the tx of hepatic encephalopathy w/c  α-1,4 linkages, α -1,6 (branch) traps ammonia in the blood  amylopectin + iodine = blue-violet or purple color OLIGOSACCHARIDES 2 ENZYMES CAPABLE OF HYDROLYZING STARCH ALPHA - AMYLASE - Α - 1,4-GLUCAN 4 - GLUCANOHYDROLASE - an enzyme present in pancreatic juice and saliva, hydrolyzes starch by a random splitting of 9|PAGE ß- AMYLASE VISUAL PROJECTIONS OF CARBOHYDRATES - Α- 1,4-GLUCAN MALTOHYDROLASE There are three ways to present the structures of carbohydrate: - Lacks capacity to hydrolyze the alpha 1,6 bonds, a Fischer Projection, Haworth Projection, and Conformational therefore the rxn stops; it leaves a polysaccharide Formulas. fragments known as dextrin (by-product of the - Conformational Formulas/ Structures – they are incomplete hydrolysis of the starch) more accurate representations of sugars than the - Produces its effect by removing maltose units from fischer and Haworth projection; it illustrates the the nonreducing ends of polysaccharide nature of sugar rings molecules. - The end-product in the case of amylose is nearly FISCHER PROJECTION pure maltose  Developed by German chemist Emil Fischer in the GLYCOGEN 1800s, when printing techniques could handle only  α 1, 4 and α 1, 6 every 8-10 unit lines (not wedges).  Major storage of carbohydrates in animals and humans  The fish bone projection/ structure (Linear)  Stored in the liver and muscles  Can depict cyclic structures using a long bond to - Liver glycogen – used to maintain blood glucose indicate a ring structure during fasting and exercise  To do a ring, there should be a link between the - Muscle glycogen – used to generate ATP for penultimate carbon and the carbonyl group muscle contraction CELLULOSE  β 1, 4 glycosidic bond  Not metabolized in the human body because of lack cellulase enzyme  Made up of monosaccharide (glucose) or disaccharides  Most abundant of all carbohydrates found in plants - The penultimate carbon in the example above is  Will give NO COLOR with IODINE the C5 (Carbon before the last Carbon) - If the OH of the penultimate carbon is on the right INULIN (dextro sugar); if on the left (levo sugar)  Diagnostic agent for kidney fxn (measure the - FOR RING STRUCTURE = BUDA (If beta, OH of Glomerular Filtration Rate) the anomeric carbon is UP; if alpha, OH is DOWN)  Can only be filtered by the Glomerular and is neither excreted nor reabsorbed by the tubules D OR L SUGARS?  Made up of fructose units bonded together via the β 1,2 linkages  Considered to be water-soluble  Cannot be hydrolyzed by intestinal enzymes CHITIN  Homopolymer of N-acetyl-B-D-glucosamine - Glucosamine – monosaccharide derivative of a glucose  Aminated glucose  A fibrous substance consisting of polysaccharides and forming the major constituent in the exoskeleton of arthropods (crabs, lobsters, shrimps, and some fungi)  USES:  Fertilizer - In doing the ring structure from the Fischer  Food additive projection, all the OH on the RIGHT will be on the  In animals, this is used to keep the inner soft BOTTOM; if on the LEFT, it will be on TOP tissue from any kind of injury; acts as a water- - ALMOST ALL sugars that are found in nature are tight barrier against dehydration w/c is crucial DEXTRO sugars for their survival; also acts as a defense - Mirror Image of Dextro sugar is the Levo sugar mechanism against predation HAWORTH PROJECTION DEXTRAN  Sucrose  dextran; with the help of transglucosylase enzyme system (dextran sucrase)  Leuconostoc mesenteroides will react to the sucrose to produce dextran  10% solution = adjunct in the treatment of shock.  Iron dextran inj.- hematinic or an anti-anemia drug 10 | P A G E   Developed by the English chemist WN Haworth  When the number of Chiral Carbon increases in an optically active compound, the number of possible optical isomers also increases  If there is a Chiral Center, it makes the compound optically active - Rule for Chirality (VAN’T HOFF’S RULE – a compound with n-chiral carbon atoms has a maximum of 2n possible stereoisomers - Example: Glyceraldehyde (1 chiral carbon)  2n  21 = 2 possible stereoisomers - Example: Glucose  2n  24 = 16 possible stereoisomers DIASTEREOMERS  Stereoisomers that are not enantiomers/mirror images of each other. - FOR RING STRUCTURE = BUDA (If beta, OH of the anomeric carbon is UP; if alpha, OH is DOWN) ISOMER Compounds with the same molecular formula but with different structures. There are 2 main classes: 1. Constitutional Isomers 2. Stereoisomers  D-ribose and L-ribose are enantiomers  D-Arabinose and L-Arabinose are also enantiomers STEREOISOMER  D-Ribose and D-Arabinose are diastereomers because they are isomers but they are not mirror images of each  Also known as configurational isomers other  Compounds wherein the atoms are connected in the  L-ribose and D-Arabinose are diastereomers because same way, but differ in how it’s arranged in space. they are isomers but they are not mirror images of each other CHIRAL MOLECULES EPIMER  There are 4 different attachments to one carbon atom; a carbon atom that has four different groups attached  Diastereomers that differ ONLY in the configuration at to it. a single chiral carbon atom.  It cannot be superimposed on its mirror image  Any substance that has a chiral center possess handedness  A molecule that contains 1 CHIRAL CENTER has 2 different optical isomers or enantiomers - Achiral – there are no 4 diff attachments to 1 carbon atom  D-glucose and D-galactose are epimers because they differ on the configuration of C4  Mannose and Galactose are not epimers because they differ on the configuration of more than chiral carbon OPTICAL ISOMERISM (C2 and 4); they are diastereomers 1. ENANTIOMERS - mirror image ANOMER - Many carbohydrates exist as enantiomers 2. DIASTEREOMER - differ in some stereocenter but are  The only carbon in the molecule that is bonded to two not mirror image oxygen atoms, usually carbon 1  The carbon on which this occurs is therefore called an ENANTIOMERS anomeric carbon.  Usually produced through mutarotation  Stereoisomers that are non-superimposable images of  Anomeric carbon can be identified if it is in a ring each other structure  Chirality is a property of an enantiomer. 11 | P A G E  - The Anomeric Carbon in the example above is the C1 REACTIONS OF MONOSACCHARIDES 1. Cyanohydrin formation 2. Ruff Degradation 3. Lobry de Bruyn Degradation 4. Osazone reaction 5. Oxidation reaction 6. Reduction reaction 7. Phosphorylation 8. Glycoside formation CYANOHYDRIN FORMATION  Also known as the ‘Kiliani Fischer’ synthesis - 1ST Image – Glucosazone (from glucose)  An organic chemical reaction by an aldehyde or ketone - 2nd Image – Fructosazone (from fructose) with a cyanide anion or a nitrile to form a cyanohydrin - 3rd Image – Galactosazone (from galactose)  Used to lengthen or extend the sugar unit by adding - 4th Image – Maltosazone (from maltose) another sugar unit OXIDATION REACTION  Oxidation means the addition of oxygen to a molecule or the removal of hydrogen from a molecule.  This will produce a SUGAR ACID.  If the ALDEHYDE CARBONYL GROUP is OXIDIZED, it will become the ALDONIC ACID  If the ALDEHYDE CARBONYL GROUP and the PRIMARY TERMINAL ALCOHOL GROUP are both oxidized, it will form ALDARIC/SACCHARIC ACID  If the PRIMARY TERMINAL ALCOHOL GROUP alone is OXIDIZED, it will form URONIC ACID RUFF DEGRADATION  A sugar can be reducing sugar if it can be oxidized  All sugar can be reducing sugar except FRUCTOSE  Removal of 1 carbon atom from molecule of an ALDOSE REDUCTION REACTION  Ex. D-glucose (6C - Aldose)  D-arabinose (5C)  Reduction means the addition of hydrogen to a molecule or the removal of oxygen from a molecule LOBRY DE BRUYN DEGRADATION  If a sugar is being REDUCED, the product will be  Interconversion or transformation from aldose to SUGAR ALCOHOL ketose or from ketose to aldose, this process will then  By-product can also be polyol or alditol perform UNSATURATED ALCOHOL  Products of the Reduction of Carbohydrates = sorbitol (glucitol, from the reduction of glucose), mannitol OSAZONE REACTION (sugar alcohol produced from the reduction of mannose)  The carbonyl group of Aldose will be linked to  Sugar Alcohols are very useful intermediates (Glycerol PHENYLHYDRAZINE – can be used as a humectant; can also be nitrated)  The product of the linkage is crystal called OSAZONE. - If glycerol undergo nitration process, it will produce  All sugar has soluble osazone except MANNOSE NTG (nitroglycerin – anti- angina) 12 | P A G E   Glycoside – an acetal formed from the cyclic monosaccharide by the replacement of the hemiacetal carbon OH group with an OR group.  Sorbitol - can be dehydrated to tetrahydropyrans and tetrahydrofurans forming sorbitans - OH group of the D-glucose will be replaced by an - Sorbitans – used to produce spans and tweens Or group (OMe) in rxn with the alcohol forming a - Spans and Tweens – used as emulsifying agents glycoside or surfactants - Sorbitol can also be dehydrated in 1,4,3,6 di- AMINO SUGAR FORMATION anhydro-Dsorbitol (Isosorbide – if this will be  If one of the hydroxyl groups of a monosaccharide is nitrated, it will form Isosorbide dinitrate (ISDN) or replaced with an amino group, an AMINO SUGAR is Isosorbide Mononitrate (ISMN) w/c is used for the produced. tx of angina  Amino Sugars – are important building blocks of - A hexitol that can be obtained from the riped polysaccharides that are found in chitin and the berries of a mountain ash; so it taste hyaluronic acid approximately half as sweet as sucrose and has that humectant properties  Mannitol - Can be isolated from manna - Can be obtained from the reduction of Mannose - Can be used for its laxative property - Can also be an osmotic-diuretic  Galactitol  3 COMMON AMINO SUGARS - From galactose  Glucosamine - Sometimes contribute in the development of  Galactosamine galactosemia  Mannosamine PHOSPHORYLATION GENERAL TESTS FOR CARBOHYDRATES  The hydroxyl groups of monosaccharides can react with inorganic oxyacids to form inorganic esters. - ATP (Adenosine Triphospate) – has 3 phosphate groups - Glucose + ATP with the help of Hexokinase will  Molisch Test – general test for carbohydrates form Glucose 6-phosphate (G-6P); phosphate is - An alpha-naphthol rxn from the ATP - A test to test all sugars - Since one molecule of ATP were taken, it will only  Anthrone Test – will from furfural seen in a green/blue be ADP green color  Tauber’s Test – color test for the identification of GLYCOSIDE FORMATION pentose sugar  The most well-known hemiacetal = GLUCOSE - Will produce a cherry red color when heated w/ a  Hemiacetals can react with alcohols in acid solutions to solution of benzidine in glacial acetic acid produce acetals  Tauber’s Aminoguanidine Test – a test to distinguish  The cyclic forms of monosaccharides are also between an aldose or a ketose sugar hemiacetals; they react with alcohols to form acetals  Bial’s Orcinol Test – to distinguish a pentose from a  The general name for monosaccharide acetals is hexose sugar known as the glycoside - Will form a furfural 13 | P A G E   Seliwanoff’s Test – a test for a ketose and an aldose - Ketose (+) RED - Aldose (+) FAINT RED  Keller-Killiani – test for the presence of the deoxy sugars - (+) REDDIS BROWN layer on the junction of 2 liquids  Moore’s Test – sugar with the alkali solution is heated therefore exhibits caramel odor due to the liberation of an aldehyde w/c polymerizes to form a resinous substance - (+) BROWNISH COLOR LIPIDS LIPIDS  Exists freely in the body in their unesterified form and fatty acyl esters  Major source of energy for the body  Consists of hydrophobic hydrocarbon chain with a  Provide the hydrophobic barrier that permits the terminal carboxyl group partitioning of the aqueous content of cells and  F.A present in the human body usually contains an subcellular structures even number of Carbon Atoms that can either be  Class of a HETEROGENOUS group of compounds, Saturated or Unsaturated which are more related by their physical than by their chemical properties. 2 TYPES OF FATTY ACIDS  Water-insoluble; they can be extracted from tissues by non-polar solvents 1. Essential Fatty Acids  FUNCTIONS: - cannot be synthesized by the body - Regulatory and enzyme functions - Example: Linoleic Acid (Omega-6); Linolenic Acid - Prostaglandin and steroid hormones play also (Omega-3) major roles in the control of the body’s 2. Non-Essential Fatty Acids homeostasis - can be synthesized by the body - Energy source - Examples: Palmitic Acid, Stearic Acid, Myristic - Thermal Insulators Acid - Pre-cursors for hormones specifically for the production of steroid hormones FUNCTIONS OF F.A - The dissolve fat-soluble vitamins and assist their digestion - The fluidity of the membrane depends on the  Deficiencies or Imbalances of the Lipid metabolism can length and degree of the unsaturated F.A lead to some of the major clinical problems that are - Used for the synthesis of phospholipids, encountered by physicians such as: cholesterol ester and lipoproteins - Atherosclerosis - The polyunsaturated acids are released from - Obesity membrane Saturated- linear (no double bond) Unsaturated- double bonds FATTY ACIDS SATURATED UNSATURATED Butyric 4C Oleic (1 db) (18C) Caproic 6C Linoleic (2db) (18C) Caprylic 8C Linolenic (3 db) (18C) Capric 10C Arachidonic (4db) (20C) Lauric 12C Myristic 14C Palmitic 16C Stearic 18C Arachidic 20C Lignoceric 24C 14 | P A G E  -do not resemble lipids they have a structure composed Saturated of 4 fused rings -CPPP nucleus (3-6 membered ring and 1-5 membered ring) -Chloesterol- most common steroid, precursor in the Trans production of vit. D, testosterone, estrogen, progesterone, aldosterone, cortisol and bile salts Glycolipids -lipids with carbohydrates Cis that is attached by a glycosidic bond -maintain the stability of cell membrane and facilitated their recognition Cis- hydrogen attached in the same position CHARACTERISTIC OF FATTY ACIDS Trans- hydrogen attached is in the opposite direction, can cause complications, cardiovascular disorder  Fatty acids have low water solubility o Solubility decreases with an increase in Note: Cis fatty acids can be converted into trans fat carbon chain  Melting points are influenced by both carbon chain and degree of unsaturation o Carbon chain increases melting point increases o The greater the degree of unsaturation the greater the reduction of melting points  Saturated fatty acids are solid in room temperature while unsaturated are liquid o Unsaturated- usually liquid at room temperature FATTY ACID SYNTHESIS - Occurs in cytosol - Needs Acetyl- CoA o Byproduct of decarboxylation of pyruvic acid in an aerobic reaction o Pyruvic acid- byproduct in glycolysis reaction of glucose - Acetyl-CoA will be transferred into its acyl carrier protein to be acetyl-CoA ACP - Malonyl CoA will come from Acetyl-CoA with the help of carboxylase enzyme it will be converted into Malonyl ACP - Once converted Malonyl-CoA will be transferred into its acyl carrier protein with the help of acyl acp Orange- hydrophobic portion transferase= Malonyl- ACP Triacylglycerol -aka as triglyceride, simplest - Acetyl-CoA ACP that will react with Malonyl ACP and lipid that is formed by fatty will undergo condensation reaction acids - In the condesation reaction there will be a removal of -Valuable form of energy carbon dioxide= 3-ketoacyl-ACP and important for regulating - 3-ketoacyl-ACP will undergo reduction process with temperature the help of B-ketoacyl-ACP reductase= 3-hydroxyl- ACP Phospholipid -most abundant type of lipid o Oxidation of NADPH to form NADP constituent that are present - 3-hydroxyl-ACP will undergo dehydrogenation process in cell membranes (removal of water) with the help of B-hydroxyl-ACP -it gives structural integrity of dehydrase to produce Enoyl-ACP membrane bilayer - Enoyl-ACP will be reduce to form Acyl-ACP o Oxidation of NADPH to form NADP Steroid -lipids, hydrophobic and insoluble in water 15 | P A G E   Iodine Number- the number of grams of iodine absorbed, under prescribed conditions, by 100 grams of substance o Indicates the degree of unsaturation o Below 100 iodine number- non drying o 100-120- semi-drying o 120 above- drying o Other physical constants such as melting point, specific gravity, and refractive index also served as identity, purity and quality tests TYPES OF LIPIDS SIMPLE LIPIDS 1. Fats - Esters of 3 F.A +Glycerol - Aka Triglycerides Note: initial product is only 4 carbons so it needs to repeat the - solid at room temperature and obtained in animal process for it to form more carbon. Kada isang balik may 2 source carbon atom na madadagdag 2. Fixed oils METABOLISM - triacylglycerol mixture that is solid at room temp and obtain from plant source 3. Waxes - esters of high molecular weight of fatty acids with long chain alcohol. Protection Insulation Energy COMPOUND LIPIDS 1. Phospolipids - Chemical composition: Glycerol/Sphingosine (Platform molecule) - 1 or more Fatty acids - Phosphate  Fats can be converted to glucose to come up with - Organic molecule > Alcohol energy or ATP - component of cell membrane and neurons  Beta oxidation of fats happens in mitochondria. - most abundant  Ketone bodies- acetone, acetoacetic acid, beta- A. Glycerophospholipids hydroxybutyric acid - Glycerol - 2 Fatty acids Phosphalidyl PHYSICAL CONSTANTS - Phosphate - -amino alcohols-choline, ethanolamine or serine What are the different tests for lipids? - -Glycerophosphalipid + Amino alcohol =  Acid Value or Acid number the number of milligrams o Phosphatidylcholine of potassium hydroxide required to neutralize the free  antioxidant. fatty acids in 1 g of the substance  Eg. Lecithin o Acid value indicates free fatty acids  used for treating memory disorder  Saponification Value- the number of milligrams of such as dementia and Alzheimer’s potassium hydroxide required to neutralize the free disease fatty acids and saponify the esters contained in 1 g of  source: soybean, egg yolk and the substance green tissue o Gives us information concerning the  Lecithinase- enzyme that can character of the fat. The longer the carbon hydrolyze phosphatidylcholine chain the less acid is liberated per gram of fat specifically that is taken orally. It hydrolyzed does not reach the body tissues. o It is also considered as the measure of the  Non-essential average molecular weight of all the fatty acid o phosphatidylethanolamine Cephaline present o phosphatidylserine o Long chain- low saponification value because  these 2 are found in the liver tissue it has fewer number of carboxylic functional and heart tissue and at the same group per unit mass of the fat therefore it has time it is also associated in blood high molecular weight per unit mass of the fat clotting - Organic molecule > Alcohol - Lecithin > Choline 16 | P A G E  - Cephaline > Ethanolamine B. Cerebroside B. Sphingophospholipids - that contain carbohydrate (galactose or glucose), one Chemical composition: fatty acid and sphingosine, but no phosphoric acid or - Sphingosine (backbone) glycerol. - 1 Fatty acid - ↑ Cerebroside > GAUCHER’S DISEASE - Phosphate o Gaucher’s disease- one of the most common - Organic molecule >Alcohol lysosomal storage disorder and result for not o Sphingosine is attached to a fatty acid in an having enough glucocerebrosidase (G-case) amide bond and attached to a phosphate  Glucocerebrosidase is an through an ester bond that is attached to an important enzyme that breaks down alcohol a fatty chemical called - *Niemann-Pick disease- deficiency in glucocerebroside or cerebroside. sphingomyelinase enzyme. Sphingomyelin will  Fat latent gaucher cell build up in accumulate the brain and blood cells. areas like spleen, liver and bone o Mental retardation marrow o Spasticity  Accumulation of glucocerebroside o Ataxia  BGL test or beta- o Death (at the age of 3) glucocerebrosidase test- main tool - Choline- Alcohol is esterified to the phosphate group that physician used to diagnose - Sphingomyelin- found in all cell membranes structural gaucher’s disease. components of the myelin sheath  All patient with Gaucher’s 2. Sphingolipids disease has low enzyme Chemical composition: activity levels - Sphingosine - Containt a single monosaccharide unite that can be a - 1 Fatty acid galactose or glucose - Phosphate - Fatty acid that is present here is stearic acid - Organic molecule>Ceramide - Can occur in brain (7% dry mass) and myelin sheath of o Ganglioside the nerves o Cerobroside - Discovered by physician chemist Johann Thudichum o Cytolipins C. Cytolipins - Lipid that contains fatty acids, carbohydrates attached  contain fatty acids, sphingosine, glucose and in sphingosine backbone and at the same time it has galactose. organic molecule (ceramide- core structure, basic unit  Have immunological properties of sphingolipids) LIPOPROTEINS A. Ganglioside - compounds related to cerebrosides that contain - Substances that carries cholesterol throughout the sphingosine, long- chain fatty acids, hexoses (usually body galactose or glucose), and neuraminic acid. - Carries indigenous lipids - It contains branched chain of up to 7 monosaccharide o Chylomicrons residues o VLDL - A molecule that contains glycosphingolipids o IDL - A ceramide with oligosaccharide o LDL - 1 or more sialic acid o HDL o Acetyneuraminic acid - Occur in cellular surfaces of neuronal cells and they CHYLOMICRONS are most found in the brain grey matter Diseases associated - Produce in the intestine  GM2 gangliosidosis – genetic disorder that - Conduct fats to the liver, skeletal muscle, and adipose results from a deficiency of the enzyme beta tissue hexosaminidase - Considered to be least dense with least amount of o beta hexosaminidase catalyzes the protein but has the highest amount of triacylglycerol biodegradation of fatty acid derivative VLDL/ VERY LOW DENSITY LIPOPROTEIN o G (ganglioside) M (mono sialic- 1 sialic acid) 2 (seond mono sialic ganglioside - Transitional form between chylomicron and LDL that is discovered) - More dense that chylomicron and has a high amount  Sphingolipidosis- Hexosaminidase A deficiency. of triacylglycerol Lysosomal disease due to absence or deficient - Synthesized in the liver specifically after high degradation of sphingolipids which are considered carbohydrates meal to be essential component of CNS membranes - Digested by lipoprotein lipase  Tay sach’s disease- genetic disorder, autosomal recessive pattern and occurs when harmful IDL/INTERMEDIATE LOW DENSITY LIPOPROTEIN quantites of fatty acid derivative (ganglioside) accumulate in the nerve cell of the brain - Denser than the VLDL o ↑ Ganglioside > TAY SACH’S DISEASE - Less than half of the amount of triacylglycerol as compared to VLDL 17 | P A G E LDL/ LOW DENSITY LIPOPROTEIN - Carry fat around the entire body within the bloodstream Thiolase - Lesser triacylglycerol content than IDL - It has the higher content of cholesterol - Delivers cholesterol to liver and various tissues squalene HMG- coA synthase cyclase monooxygenase HDL/ HIGH DENSITY LIPOPROTEIN - Collect fat from cells and tissues then return