Lecture 1 - Chemical Bonds and Macromolecules Flashcards

1
Q

What elements make up most of the mass of the human body and why are they significant?

A

CHON - lightest elements capable of forming one, two, three, or four covalent bonds (based on number of valence electrons)

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2
Q

What are the hydrogen bond donors?

A

A hydrogen atom which is bonded to an N, O, or F. They are highly electronegative and give a positive charge to H and a negative charge to the donor

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3
Q

What are noncovalent bonds? Are they readily reversible? What are the main types?

A

Bonds which make a difference in aggregate, 1/10-1/25 as strong as covalent bonds. They are readily reversible and do not involve sharing electrons.

  1. Ionic
  2. Hydrogen - NOF
  3. van der Waals
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4
Q

How is the energy of an ionic interaction calculated?

A

E= (kq1q2) / (Dr)

Where k is Coulomb’s proportionality constant, converting to kcal/mol

D = dielectric constant

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5
Q

What influences the dielectric constant?

A

D is proportional to ability of the medium to loosen electrovalent bonds of reversed molecules.

This is very high in water ~80, because the lattice can be hydrated stabilizing the dissolved ion pair since water is a dipole.

Nonpolar character -> less dipole moment -> lower dielectric constant.

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6
Q

Why are cell membranes impermeable to ions?

A

Dielectric constant of lipid bilayer is ~3 which is very low, it is quite nonpolar. Energy barrier required for charged species to exist in bilayer is too high to permit the action

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7
Q

What is the hydrogen bond acceptor?

A

Partially negatively charged atoms with high electronegativity in an uncharged but polar moleccule

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8
Q

How does water affect hydrogen bonding between other molecules?

A

Water can disrupt other hydrogen bonds by competing to form them

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9
Q

What causes van der Waals attraction / repulsion and what is van der Waals contact?

A

Attraction - A transient dipole around one nucleus induces a transient opposite dipole in the nearby atom, attracting them

Repulsion - nuclei approach too close and start to repel, overlying electron clouds repel

van der Waals contact - when net attraction is maximal

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10
Q

What defines molecular volume?

A

the distance for van der Waals contact with the molecule - repulsion starts to occur when electron clouds repel.

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11
Q

How can a spontaneous reaction be defined? Formula?

A

Any reaction with a negative gibbs free energy, favored if the final state of the molecule has lost the capacity to perform work and gained freedom to occupy multiple states

(negative entropy and positive entropy change)

State function: delta G = delta H - T * delta S

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12
Q

Why does the hydrophobic effect occur?

A

Spontaneous clustering of nonpolar group limits their exposure to aqueous solvent, decreasing the ordering of water molecules and restoring some solvent H-bonds that were lost. This limits the negative impact on water entropy

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13
Q

What is an amido group?

A

R-Carbonyl-amino

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14
Q

What is a sulfhydryl / thiol group?

A

Hydroxyl group which is made from sulfur rather than oxygen

R-S-H

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15
Q

What is an acyl group?

A

An R-Carbonyl-R

Very general term, could include amido, acetyl, carboxylic acid, ketone, aldehyde

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16
Q

What is an acetyl group?

A

any R-Carbonyl-Methyl

17
Q

How is an anhydride formed?

A

Two carboxylic acids react, and link together by an oxygen, they precipitate a water

18
Q

What is an example of a mixed anhydride?

A

Carboxylic acid reacts with phosphoric acid, makes an acyl phosphate

19
Q

Why are anhydrides and thioesters considered high energy?

A

The products released by cleavage of such bonds are stabilized through resonance

20
Q

Why does hydrolysis of the thioester bond yield more energy than cleavage of oxygen ester?

A

Only oxygen esters have a significant resonance contributor which stabilizes them. Sulfurs in thioesters don’t form double bonds with carbons will since they have such a size difference

21
Q

What are isomers?

A

Compounds with the same molecular formula but different structures - they have unique properties

22
Q

What is a structural isomer? Example?

A

Molecules that differ in the order the atoms are arranged. Glucose / Fructose. Glucose is an aldo-sugar, fructose is a keto-sugar

23
Q

What does an isomerase do?

A

Interconverts aldehydes + ketones

24
Q

What does a mutase do?

A

Moves a functional group to a different position in a molecule

25
Q

What is a configurational isomer?

A

Stereoisomer - differs in arrangement of substituents. Includes across a planar double bond and an asymmetric (chiral) carbon

26
Q

What does a racemase do?

A

Catalyzes the stereochemical inversion around the asymmetric carbon atom in a substrate with only one stereocenter

27
Q

What does an epimerase do?

A

Catalyzes the stereochemical inversion at a single assymetric carbon in a substrate with more than one stereocenter -> creating epimers. An epimer is a diastereomer with a difference at only one sterocenter

28
Q

What are the repeating subunits of lipids?

A

Acetate - two carbon units

The conjugate base of acetic acid, which is ethanoic acid

29
Q

What are the bases in DNA vs RNA?

A

nitrogenous bases

DNA - Adenine, Guanine, Thymine, Cytosine
RNA - Adenine, Guanine, Uracil, Cytosine

Uracil replaces Thymine in RNA, pairs with adenine all the same

30
Q

How does DNA differ from RNA in terms of structure?

A
DNA = double helix
RNA = single helix

Ribose has a 2’ hydroxyl group removed in DNA (deoxy)

31
Q

Why do fatty acids provide more energy than sugars / amino acids?

A

The fatty acid (carboxylic acid) is a more reduced molecule vs other two. Energy is derived from oxidation.

32
Q

What is primary vs secondary vs tertiary vs quaternary structure of proteins?

A

Primary - determined by amino acid sequence
Secondary - Alpha helices + beta sheets
Tertiary - Complete folding of a given chain of amino acids (a subunit)

First three are intramolecular interactions

Quaternary - multiple oligomeric proteins come together in intermolecular interactions