Exam 3 Flashcards
Dihydroxyacetone
- is a ketose
- has the same atomic composition as glyceraldehyde and they are tautomers which can interconvert
Isoprenoids
- Biomolecules found in membranes that consist of terpenes (found in essential oils) and steroids
GM2, or Tay-Sachs ganglioside
- disease results from incomplete enzyme processing of the glycan portion of glycosphingolipids
- neural diseases
- Tay-Sachs lysomes cannot digest ganglioside GM2 due to mutation in HEXA gene
- HEXA responsible for breakdown of fatty acid substance GM2
- Accumulation of GM2 causes the lysosomes in the neuronal cells and the neuronal cells themselves to bulge and die causing the disease
- constituents of the ABO blood group antigens
Examples of Fatty Acids
- When the hydrophilic head is in ionic form, then the acid is just referred to as stearate or oleate
1. Stearic acid - saturated(all carbons have H’s, no double bonds) fatty acid
2. Oleic acid - unsaturated(double bonds) fatty acid
- one CIS double bond
How are fatty acids synthesized?
- by the sequential addition of 2-carbon precursors.
- fatty acids are synthesized stepwise from acetyl (2 C) building blocks
- this is why most fatty acids have an even number of carbon atoms
Glyscosides
- monosaccharide derivative
- elimination of water between the anomeric hydroxyl of a cyclic monosaccharide and the hydroxyl group of another compound yields O-glycoside
- O signifies the hydroxyl attachment
- newly formed bond is a glycosidic bond (ether like)
Tetroses
- monosaccharides where n=4
- The keto form of a tetrose is erythrulose, which only has one asymmetric carbon
Cyclization
- creates a new asymmetric center
- The new center is called an anomeric center and is designated as α (Oh group down) or β (Oh group is up/on the same side of CH2OH group)
- Anomers interconvert by mutarotation (center figure)
- These rings are shown in Haworth projection
- C1 is the anomeric carbon in ring structures
Ceramides
- sphingolipid derivatives
- consist of sphingosine and a fatty acid
- if a fatty acid is linked via an amide bond to the NH2 group that is on the C-2, it is called a ceramide
Compounds with >1 asymmetric carbon (chiral carbons)
- may be enantiomers (mirror images) or diastereomers
Anomers
- stereoisomers that differ in conformation at the anomeric carbon
- The carbon in a cyclic sugar that is the carbonyl carbon in the open-chain (acyclic) form
- start counting here
Cholesterol
- Bulky, rigid structure disrupts regular fatty acid chain packing in membranes
- weakly amphipathic because of –OH (hydroxyl group)
- Fatty acid esters of cholesterol are extremely apolar
- precursor to all steroids
- major sterol in animal tissues
- really no such thing as “good” or “bad”
What do the numeric abbreviations for fatty acids tell you about their composition? 18:3cΔ9,12,15
- 18 = Number of carbons
- 3 = number of unsaturated double bonds
- c = cis orientation
- Δ#= carbons at which double bonds occur
Alditol
- monosaccharide derivative
- reduction of the sugar carbonyl yields alditol
- The reduction of glucose yields D-glucitol, also called sorbitol
Example of a Triaglycerol
- Tristearin
- the triglyceride form of stearic acid
Oligosaccharide
- Compound formed by linking several monosaccharides together (example, disaccharide, with 2)
Galactosylceramide
- is found on brain cell membranes
Furanose
- A five-member closed chain form of a monosaccharide
- one of the ribose carbons cannot fit in the ring
- heterocyclic compound is furan
Reducing and nonreducing sugars
- Free anomeric carbon = reducing end (OH group on anomeric carbon)
- Sucrose has no free anomeric carbons(no OH group on anomeric carbon), thus no reducing ends. It is a nonreducing sugar.
- lactose is a reducing sugar
Niemann-Pick disease
- Sphingomyelin accumulation
- an individuals deficient in acid sphingomyelinase
- Niemann-Pick is similar in pathology to Gaucher’s.
Lactones and Acids
- monosaccharide derivative
- oxidation of monosaccharides forms these, proceeds in several diff ways depending on oxidizing agent
ex: D-gluconic acid. - Oxidation at C1 forms an aldonic acid
- The aldonic acid is in equilibrium with the lactone (cyclic ester) form
ex: β-D-glucuronic acid - Oxidation at C6 forms a uronic acid
Enantiomers
- optical isomers that are non-superimposable mirror images of eachother
Glyceraldehyde
- is an aldose
- has the same atomic composition as dihydroxyacetone and they are tautomers which can interconvert
- contains a chiral carbon thus it has two stereoisomers otherwise known as enantiomers. (R=D, L=S)
Diastereomers
- are optical isomers that are not mirror images
- with 2 enantiomers each
Soaps
- Soaps are formed by the treatment of fatty acids with strong bases(NaOH or KOH), saponification
- water soluble
- Soaps form micelles around oils, emulsifying the oil
- the hydrophobic heads of soap molecules on the outside allow the micelle to be suspended in water
- In hard water, soap reacts with calcium and magnesium ions to form a precipitate (scum)
Sphingolipids
- unique because they are built on the amino alcohol sphingosine, rather than glycerol
- major component of membranes
- includes a long-chain hydrophobic tail, so it only requires only the addition of one fatty acid to make it a suitable membrane protein.
- If a fatty acid is linked to the sphingosine via a AMIDE bond to the NH2 group on C-2, it is called a ceramide
How is cholesterol beneficial
- Cholesterol cannot be metabolically degraded and as such is returned to the liver for excretion
- High Density Lipoprotein is considered “good” because high levels of HDL counteract atherogenesis.
Monosaccharide
- Simple sugars and derivatives with 3 to 9 carbon atoms
- A single sugar
- A carbohydrate that cannot be broken down into a simpler carbohydrate
- presence of a carbonyl group (aldehyde or ketone) and one or more hydroxyl group, and a sugar
- two major classes: aldoses and ketones
Major classes of membrane forming lipids/Structural
- they differ in the nature of the head group
1. Glycerophospholipids
2. Sphingolipids
3. Glycosphingolipids
4. Glycoglycerolipids
Anomeric carbon
- The carbon in a cyclic sugar that is the carbonyl carbon in the open-chain (acyclic) form
- start counting here
Sphingolipids
- Another type of membrane forming lipid bearing an amine group on the polar ”head”
Cerebrosides
- are monoglycosyl ceramides
saturated fatty acids
- contain no C-C double bonds
- Fats that are rich in saturated fatty acids are solid at room temperature more solid (butter)
- most stable arrangement of saturated fatty acids is the very close packing of the side chains of the lipid
Eicosanoids
- diverse class of signaling molecules derived from lipids
- derived from arachidonic acid
- potent activators of wide range of physiological function, including inflammation, blood clotting, blood pressure regulation and reproduction
R/S in relation to D/L
- what do D and L refer to
- R=D, clockwise
- S=L, counterclockwise
- D and L refer to configuration about the asymmetric carbon farthest from the carbonyl carbon (C=O)
- forms of a monosaccharide that are nonsuperimposable mirror images (enantiomers)
Glycans
- are metastable and their formation is unfavorable
Adipocytes
- fat storage cells
Nonreducing sugar
- do not have an OH group attached to the anomeric carbon, so they cannot reduce other compounds
- without a hemiacetal
ex: sucrose
Hexoses
- prefer the pyranose ring structure when in aqueous solutions, but this depends on the structure of the sugar and its environment
Reducing sugar
- any sugar that is capable of acting as a reducing agent because it has a free aldehyde group or a free ketone group
- any sugar containing a hemiacetal
ex: maltose and lactose
Phosphate esters
- monosaccharide derivative
- Sugar phosphates are important intermediates in metabolism
- functioning as activated compounds in syntheses
- very acidic
- under physiological conditions exist as a mix of dianions and monoanions
Beta-anomer
- when OH and C2OH groups are present on the same side of haworth projection
D-sugars vs L-sugars
- D-sugars are preferred in nature
- L-sugars have certain specialized roles in nature
The four most common hexoses
- Fructose (Furanose form)
- Glucose
- Mannose
- Galactose
Properties of lipids
- limited solubility in aqueous media
- unlike macromolecules, they do not form covalently linked polymers, instead, they associate via noncovalent interactions
- most are amphipathic (contain both hydrophobic and hydrophilic regions)
Glycosphingolipids
- have glycans attached to sphingosine
- head group contains saccharides
- Constituents of ABO blood antigens
- Includes cerebrosides and gangliosides, common in the membranes of brain and nerve cells
- Several human diseases (including Tay-Sachs, Gauchers disease) result from incomplete enzymatic processing of the glycan portion of glycosphingolipids.
Wax Esters
- Complex mixtures of nonpolar lipids
- Form the protective coatings of leaves/stems/fruits
- long chain fatty acid esterified to a long chain alcohol
- firmness of waxes increase with chain length and degree of hydrocarbon saturation
- Because of the extremely small polar region, waxes are completely water insoluble
Aldotetroses and ketotroses are _______
- tautomers
Functions of fat storage
- Energy Production
- Heat Production
- Insulation
Simple fats
- Triacylglycerols with the same fatty acid esterified at each position
- most are mixed fats with a mixture of different fatty acids
Formula: (CH2O)n
- When n = 1: formaldehyde
- When n = 2: acetaldehyde
- n = 3-9 gives compounds with properties of sugars
Glycerophospholipid
- the major class of naturally occurring phospholipids
- glycerol is prochiral
- have an ester bond
- plays major role in metabolis, minor membrane constituent
- only has 2 fatty acid chains, the third chain contains a phosphate group unlike triaglycerol
- Names of glycerophospholipids are derived from phosphatidic acid
Writing the structure of Disaccharides
- The sequence is written starting with the nonreducing end at the left, using the abbreviations in table 9.1
- Anomeric and enantiomeric forms are designated by prefixes (e.g. α- D-)
- The ring conformation is indicated by a suffix (p for pyranose, f for furanose)
- The atoms between which the glycosidic bonds are formed are indicated by numbers in parentheses between residue designations
ex: 1->4 means a bond from carbon 1 of the residue on the left to the carbon 4 of the residue on the right
Complete abbreviation for sucrose: α-D-Glcp(1->2)-β-D-Fruf
Ketopentoses
- have two chiral centers, so they have 2^2=4 stereoisomers in 2 pairs of enantiomers
- the same logic can be used to describe ketohexoses
Phospholipids
- One type of membrane forming lipid bearing a phosphate group in the hydrophilic “head” group.
Linolenic acid
- a polyunsaturated fatty acid or PUFA
- indicates multiple double bonds
Chiral carbons
- has two stereoisomers, otherwise known as enantiomers
4-carbon ketoses (ketotroses)
- only have one pair of enantiomers because there is only one chiral carbon, C3.
- Usually the names of ketoses are derived from the corresponding aldose name with the addition of ”ul”
ex: Erythrose (aldose)->Erythrulose(ketose)
Ketose
- A polyhydroxy ketone(C=O, two R groups)
ex: a carbohydrate containing a ketone functional group
Aldose
- A polyhydroxy aldehyde (C=O, connected an H and R gp)
ex: a carbohydrate containing an aldehyde functional group.
Uncommon Fatty Acid characteristics
- some have odd numbers of C atoms
- Some (unnatural) fatty acids have trans double bonds
Four major features of disaccharides
- The sugar monomers involved and their stereochemistry
- The carbons involved in the linkage
- The order of sugars (note whether the sugar is reducing; the free anomeric carbon can undergo oxidation)
- The configuration of the anomeric carbon (α or β)
- vary in anomeric configuration among other features
Epimers
- isomers differing only in configuration about one carbon, other than the anomeric carbon
ex: mannose and glucose or glucose and galactose
Hemiacetal formation
- results from reaction of an aldehyde with an alcohol
- any carbon with an OH and OR group attached
- with pentoses and hexoses(5/6 C)
- monosaccharides with 5 or 6 carbons exist in this structure
Fischer Projection
- A way of representing an acyclic (open chain) carbohydrate structure
- Vertical lines point away from the viewer(dash) and horizontal lines point toward the viewer(wedge)
- the most compact way to represent stereochemistry
Polysaccharide
Polymer formed from multiple saccharide units
- may be homopolysaccharide or heteropolysaccharide
Chair Conformation
- the most stable conformation of cyclohexane that resembles a chair
- lowest energy form, most stable bc sub on axial bonds in boat form tend to be crowded
- axial (up and down/parallel to axis)
- equatorial (side to side/perpendicular to axis)
The fluidity of fatty acids
- decreases as the chain length increases and the number of cis double bonds decreases
Glycan
- Generic term for oligosaccharides and polysaccharides
Chair Form
- the lowest energy, or most stable, form
- The chair form is more stable because the substituents on axial bonds tend to be more crowded in boat form
6 Classes of Lipids
- Fatty Acids
- Triaglycerols
- Wax esters
- Phospholipids
- Sphingolipids
- Isoprenoids
Fat storage
- The process of esterification of fatty acids into fats causes partial loss of the hydrophilicity of the polar head
- as a result triacylglycerols are not water-soluble
- This insolubility leads to oily droplets that are stored in “fat cells” or adipocytes.
Unsaturated fatty acids
- contain one or more cis C-C double bonds
- fats that are rich in unsaturated fatty acids are liquid at room temperature (olive oil)
- the kink caused by the double bond does not allow for the tightly packing of fatty acid chains
Bonds to substituents on ring carbons can be defined as:
- axial or equatorial depending on whether or not they are parallel or perpendicular to the axis
Gaucher’s diease
- Glucocerobroside accumulation
- an individuals deficient in glucocerebrosidase
- Gaucher’s disease causes enlarged livers and spleens in the affected.
How is cholesterol bad
- Low Density Lipoprotein (LDL) is considered ”bad” because its oxidation leads to atherosclerosis.
Glycoglycerolipids
- Mostly found in plant(chloroplasts) and archaea membranes
- most abundant of all polar lipids
- major membrane components
Glycan biosynthesis
- activated monomers are required
- These monomers are usually nucleotide linked sugars
- Glycans are never copied from template molecules, a different enzyme is employed to catalyze the addition of each monomer (unlike polynucs. and polypeps.)
Amphiphathic nature of lipids
- form monolayers, micelles, or bilayers
- the structure formed when a lipid is in contact with water depends on the structure of the hydrophobic and hydrophilic groups
Fatty acids
- basic structure: hydrophilic group attached to a hydrophobic tail, has hydrocarbon chains
- Carry a negative charge
- the simplest lipids
- WEAK acids
- mostly cis in nature
- Most common fatty acids have an “even-numbered tail”
Why are Glycerophospholipids prochiral?
- Glycerol alone does not contain any stereocenters but the glycero-derivatives will generate an asymmetric center at C2
- causes them to be prochiral
Aldopentoses
- have three chiral centers, so they have 2^3=8 stereoisomers in 4 pairs of enantiomers
- same logic can be used to describe aldohexoses
Lipids that form bilayers
- tend to contain 2 hydrocarbon tails per polar head group
- The cylindrical shape promotes packing into a parallel array