Lecture 1 Flashcards

Aqueous Chemistry (74 cards)

1
Q

The scale of biochemistry?

A

Biology = large scale items like ecosystems
Chemistry = tiny subatomic particles
Biochemistry = Everything in between!

From plant cell to atoms, including animal cells, bacterium, virus, ribosomes, globular proteins, small molecules.

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2
Q

Our focus?

A

Cells -> Organelles (mitochondria) -> items within organelles (ribosomes) -> proteins -> amino acids -> atoms

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3
Q

Units used in biochemistry?

A

mega (M) 10^6
kilo (k) 10^3
milli (m) 10^-3
micro (u) 10^-6
nano (n) 10^-9
angstom (A) 10^-10

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4
Q

Most common units used in biochemistry?

A

milli (m) 10^-3
micro (u) 10^-6
nano (n) 10^-9
angstom (A) 10^-10

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5
Q

Angstrom (A)?

A

1nm = 10 Angstroms or A

1 angstrom is 1/10 the length of a nanometer.

1 A = 10^-10 meters.

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6
Q

What is biochemistry?

A

The scientific discipline that seeks to explain life at the molecular level.

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7
Q

Living things obey..?

A

The laws of thermodynamics

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8
Q

For any reversible process?

A

where A <=> B can proceed spontaneously in the direction that lowers the system’s Gibb’s Free Energy: DG = Gb - Ga.

DG < 0 = spontaneous (exergonic - free energy of b is less than a, free energy is lost to surroundings, run is favoured and spontaneous)

DG > 0 = not spontaneous (endergonic - system takes in free energy from environment in order to occur)

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9
Q

What does Change in G equal?

A

DG = DH - TDS, where

H is enthalpy (internal energy/heat)
S is entropy (disorder)
T is temperature (measured in K)

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10
Q

If G is positive going from A to B..?

A

G will be negative going from B to A

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11
Q

Kelvin?

A

Degree size is same as Celsius, but 0 in Kelvin is absolute 0, meaning there is no kinetic energy (movement). very convenient because 0 is actually 0. They cannot be negative.

C to K is C +273.

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12
Q

Entropy?

A

Entropy (S) is proportional to the number of possible ways (W) a state can exist and the Boltzmann constant: S=Kb ln(W) which we don’t need to know.

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13
Q

Why does thermodynamics matter?

A

Things like thermodynamics make a huge difference in biochemistry because of all of our metabolic pathways that wouldn’t work well if they were processed backwards. Therefore, we need to keep an eye on the larger physical and chemical environment, processes, and principles as we look at biochemistry.

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14
Q

Thermodynamics…?

A

Thermodynamics predicts whether a reaction can proceed, yet whether it will proceed is dependent on kinetics.

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15
Q

General Example of G?

A

A: pool balls lined up (low S)
B: pool balls scattered (high S)

What is H? 0, no heat change
What is S? positive, disorder is higher in B
What is G? 0 - (pos) (pos) = negative

Therefore, the rxn is spontaneous from A-B and also exergonic. This is because delta G is negative in that context.

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16
Q

For a chemical reaction, if the change in enthalpy is negative and the change in entropy is positive, the reaction will be:

A) Never spontaneous
B) Always spontaneous
C) Sometimes spontaneous
D) Not enough info given

A

The answer is B - Always spontaneous. This is because delta g will always consist of a negative (enthalpy) subtracting a positive multiplied by a positive (temp times entropy), leading to an overall negative number every time.

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17
Q

What are the main classes of biomolecules?

A

Nucleic Acids: made of polymers of nucleotides (RNA/DNA)

Proteins: polymers of amino acids

Carbohydrates: polymers of monosaccharides (simple sugars like glucose)

Lipids: not made of discrete building blocks like the others - hydrophiobic molecules that tend to have long carbon chains (or rings).

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18
Q

Triglycerides?

A

Polar head and non-polar tails: HYDROPHOBIC

  • 3 fatty acids bonded to a glyceride through ester bonds
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19
Q

What do these molecules have in common?

A
  1. Three of the classes (NA, P, C) are polymers made up of monomers.
  2. They can all form large macromolecules. If you get a long polymer, large lipid, or big protein, or all the DNA in a genome, they make up quite sizeable molecules.
  3. Their structural backbones consist heavily of carbon. Carbon is the atom holding many things together!
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20
Q

The Elements of Biochemistry?

A

If we look at the elements that are a part of the molecules that for living systems, it is not the entire periodic table. It’s mostly small elements that mostly go across the entire PT.

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21
Q

CHNOPS?

A

The most abundant elements in living systems. CHNOPS are 92% of human dry weight (40% of total as we are 60% water) and form covalent bonds.

  • Carbon, Hydrogen, Nitrogen, Oxygen, Phosphorus, Sulphur.
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22
Q

Trace elements in biochemistry?

A

Found in smaller amounts. Important in systems and do have roles - just less abundant.

Ex. Iodine is in hormone thyroxine which is necessary for cells functioning properly.

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23
Q

Moderately abundant ions?

A

Common cations (K, Mg, Na, Ca) and anions (Cl) are moderately abundant in human systems.

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24
Q

Why are most abundant elements small?

A

These elements are abundant and stable and can form covalent bonds. They tend to be non-toxic.

  • Larger elements are typically unstable and are so large that they cannot be produced naturally (only in controlled environments or special conditions).
  • Many larger elements are also radioactive or toxic t living things such as mercury or lead.
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25
Electronegativities in biochemistry?
Another important factor that makes a difference in biochemistry. Thre important thing is that you want to look ate which atoms are most electronegative and which ones are the least, alongside what that tells you about the element's behaviours and relationships.
26
What is electronegativity?
Electronegativity is the abiity pof an element to attract a shared pair of electrons toward itself, resulting in partial changes and determining if bonding is ionic or covalent. - The tendency of an atom to hang onto its electrons. (typically a behaviour seen in the upper right side of the PT)
27
What does the formation and stability of molecules depend on?
The formation and stability of molecules depends on the fact that atoms like having 8 electrons in their outer valence shell.
28
Lewis Dot Symbols?
Lewis dot symbols represents valence electrons as dots. Ex. Carbon has 4 dots, therefore it will want to make 4 bonds sharing its electrons. - Some only need 2 in their valence shell, but most need 8.
29
Understanding Lewis Dot Structures
Thinking back to Lewis diagrams helps us understand why some molecules choose to bond with an element over a different one.
30
Bonds?
Atoms participate in either covalent bonds (sharing of electrons) or ionic bonds (transfer of electrons) to complete their valence shell (2 or 8)
31
What does geometry depend on?
Geometry depends on the number of bonded atoms and electron pairs.
32
What does geometry tell us?
The composition and geometry of a molecule determines if they are polar or non-polar.
33
Polar?
Distribution of positive negative and positive charges.
34
Non polar?
No partial negatives or positives
35
Which molecule would you expect to be non-polar? A) H2O B) CO2 C) NH3 D) CHCl3 E) They all have equal polarity
The answer is.... B! CO2 is the molecule that we anticipate will be non-polar, due to its linear geometry.
36
Biomolecules can be....?
Hydrophilic, hydrophobic, or amphipathic.
37
Amphipathic (amphiphilic)?
Amphipathic/amphiphilic molecules contain both polar and non-polar functional groups. Both the hydrophobic and hydrophilic portions are significant in order to be amphipathic.
38
Polar/hydrophilic molecules?
Poor molecules have an uneven distribution of charge (negative and positive ends). They can be charged but do not need to be ionized (like glucose). Highly electronegative molecules tend to be found in polar molecules/charged molecules (having many electronegative oxygens make it likely to be a polar molecule. DO NOT NEED NET CHARGE TO BE POLAR - just a charge distribution.
39
Nonpolar/hydrophobic molecules?
Fully nonpola molecules are hard to find inn biochemistry - so we mainly look at mostly hydrophobic molecules. Hard to be found due to the fact that we are mainly made up of water (polar) therefore most molecules will at least have a polar end.
40
Polar examples?
Glucose, Glycine, Aspartate, Lactate, Glycerol
41
Amphipathic examples?
Phenylalanine, Phosphatidylcholine
42
Nonpolar examples?
Typical waxes - long hydrocarbon chains with a tiny polar portion for the purpose of binding in cells (which are majorly polar!!)
43
What are some common functional groups in biomolecules?
Methyl, Ethyl, Hydroxyl, Anhydride, Amido, Amino, Disulfide, Phosphoryl - Huge variety in the polarity of these molecules! A huge factor in this is the electronegativities of these atoms.
44
Charge-charge interactions?
2 charged molecules interact.
45
Charge-dipole interaction?
Uneven charge distribution in a molecule.
46
Dipole-dipole interaction?
2 polar molecules: opposite poles will interact
47
Charge-induced dipole?
Charged molecule approaches molecule without charge distribution and induces a charge distribution where you get an uneven distribution of electrons, where the opposite charge is closest to what you get. Ex. positive molecule comes close = relative abundance of electrons come close to positive molecule because they're attracted to that.
48
Dipole-induced dipole?
A dipole induces another molecule
49
Dispersion?
Random charge distributions that can flicker in time will induce other random charge distributions that are opposite to them, that can flicker in time and cause interactions.
50
Hydrogen Bonds?
Occur between hydrogen and NOF! Bond length is specific (vary a little bit but stay defined).
51
Non-covalent interactions between molecules?
Charge-charge Charge-dipole Dipole-dipole Charge-induced dipole Dipole-induced dipole Dispersion Hydrogen Bond
52
Non-covalent interactions are...?
Non-covalent interactions are critically important to biochemistry and determine how molecules fold and associate with one another. Ex. Suppose you have a lot of amino acids that polymerize to form a protein that's a covalent polymer. How it folds into functional form is dependent on non-covalent interactions between different parts of the protein.
53
Non-covalent interactions over distance?
Non-covalent interactions weaken over distance (dependent also on the molecules involved).
54
Relative bond strengths in aqueous environments?
Covalent - strong in all environments Ionic interactions - very strong in vacuums but not as strong in polar environments like water. Water has high dielectric constant, meaning it shields the charges to some ions that would normally stay together. Hydrogen bonds - relatively weak Van der Waals interaction - very weak one their own.
55
Ionic bond strength?
Due to different dielectric constants (refers to how much a substance can shield electric charge) ionic bond strength varies depending on the solvent. Ex. It is 80 times stronger in a vacuum than in water
56
Biologically important hydrogen bonds?
- Between peptide groups in polypeptides (amino acids in a protein) - Between complementary bases of DNA
57
What are H-bonds?
H is shared between two electronegative atoms: strongest when the 3 atoms are in line. - They are non-covalent and reflect the sharing of a hydrogen proton (hydrogen's nucleus) between two electronegative atoms. Kind of like tug of war where 2 atoms share the hydrogen.
58
O---H-N example?
Oxygen is highly electronegative form because it is double bonded to carbon and likes to hold onto electrons. Hydrogen is basically a proton because its electron is with nitrogen and held close. The nitrogen is covalently bonded to the hydrogen, keeping the electron from H close to it. - The Oxygen will hydrogen bond with the hydrogen. - Oxygen is the acceptor in this case and Nitrogen is the donator.
59
Ionic interactions summary?
- Attractive or repulsive - Strength depends on Coulomb's law (don't need to know) - Weaker in polar environments
60
Van der Waals interactions summary?
- Very weak forces due to dipole or induced dipole interactions of closely spaced atoms - Significant in large numbers, where complementary binding surfaces contribute to biological specificity (can favour specificity) - Includes dipole-dipole, charge-induced dipole, dipole-induced dipole, and dispersion - Include charge, but not permanent charge (partial charge from electron clouding) doesn't mean they're polar, just means there is some polarity at the moment. - Weak on their own but powerful in numbers (breaking one won't do much but breaking all of them will make a difference).
61
Hydrogen bonds summary?
- H shared between two electronegative atoms with partial covalent character. - Strength (5-20kJ/mol) depends on being linear, atom electronegativity, and environment polarity - Very directional: contributes a lot to biological specificity.
62
Long and short range interactions?
Long range: Charge-charge and charge-dipole Short range: Dipole-dipole, charge-induced dipole, dipole-induced dipole, dispersion BONUS - Fixed length: Hydrogen bonds
63
Geckos and van der Waals?
They have many flat surfaces that maximize interactions with the surface they're on. Their surfaces will also form van der Waals interactions really nicely. - despite VDW being fairly weak, there is power in numbers. Each hairlike structure is host to many many VDW interactions, and there are many of those structures on their feet in general - leading to a strong gripping, therefore the gecko can walk up the wall.
64
Water forms hydrogen bonds?
The hydrogens in water are slightly positive while the oxygen is slightly negative due to bonding interactions. This allows the oxygen of one water molecule to accept a hydrogen donated by a separate water molecule (oxygen). - Water is the most important molecule in life as we are 60% water! - Water is also bent and very polar, with a high melting point and the temperature at which water is liquid is lower than other molecules.
65
Hydrogen bonds influence the structure of water?
Liquid water: fast changes to hydrogen bond pattern (flickering). At any given moment, there's lots of H-bonds but they change quickly and frequently. Ice: fixed hydrogen bonds (stable) where ice has an open lattice structure hence ice is less dense than water. Amorphous/vitreous ice: cool water below glass transition temperature in milliseconds! It is very squashed together and chips into small pieces easily.
66
Can ammonia form an ice-like network just like water?
No, ammonia cannot form as many hydrogen bonds as water because there are not enough H-bond acceptors. Therefore, it cannot form an ice-like network. NH3 has 3 donors and only 1 acceptor.
67
Hydrogen bonding influencing the properties of water?
H2O forms hydrogen bonds, which impart high melting and boiling points, dielectric constant, surface tension and more. Heat of vaporization is also higher compared to other similarly sized molecules. - H2O gas much more stable forms, which is a huge advantage for life.
68
Why doesn't everything (in cells) amalgamate into one?
Because of cell membranes having the hydrophobic effect!
69
What is water a good solvent for?
Water is a good solvent for ionic and polar molcules. Ex. for salt (NaCl) the Cl and H with the Na and O help pull apart the salt crystal and it becomes difficult to get the crystal back together afterwards.
70
Salt and water?
Hydrogen is attracted to the Cl and Na is attracted to the O, which effectively pulls apart the salt crystal, dissolving it in water. - Favourable enthalpathic interactions and gain in entropy of salt overcomes the loss of entropy of solvent water.
71
Non polar molceules in water?
The formation of the non polar molecule is fairly disordered and high entropy. The H2O is highly ordered and has low entropy. They will not mix.Hy
72
Hydrophobic effect?
The tendency of non polar substances tp aggregate in aqueous solutions.
73
Hydrophobic effect: thermodynamic explanation?
Any reversible process (A<->B) is or isn't spontaneous according to DG = DH - TDS. - The decreased entropy of water at the non-polar solute interface is not compensated by favourable (lower enthalpy) solute-solvent interactions. - The total area of contact is less in B than A, so b is favoured.
74
Consequences of hydrophobic effect?
The compartmentalization of cells. - Detergent micelles (polar outside and non-polar inside) - Lipid bilayer (selectively permeable) - Lipid vesicles and cells (aqueous cavity) - Protein folding - Surface tension.