Introduction to Bioinorganic Chemistry Flashcards

1
Q

What happens to atomic radius down the group + across the period?

A

Increases

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2
Q

What happens to ionisation energy down groups 1 + 2 and across period 1?

A

Increases

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3
Q

What is the equation for ionisation energy?

A

A(g) —-> A+(g) + e-(g)

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4
Q

What is the equation for e- affinity?

A

A+(g) + e-(g) —-> A-(g)

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5
Q

Where are elements that have highest e- affinity?

A

Top right

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6
Q

What is electronegativity?

A

Ability of an atom within a compound to attract e- towards itself

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7
Q

Where are atoms that are the most electronegative?

A

Top right

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8
Q

What are hardest atoms?

A

Highest ionisation energies
= small atoms, near fluorine

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9
Q

What are softest atoms?

A

Low ionisation energy

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10
Q

What are hard acid and bases?

A

Less polarisable
Form bonds with more ionic character

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11
Q

What are catalytic metals?

A

Many enzymes have metals attached to active site to act as catalyst

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12
Q

What factors influence the role of metal?

A

Valency
Ionic radius
Polarizability
Hydration energy
Radius of hydrated ion

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13
Q

What do hard acids prefer?
Works vice versa with soft acids

A

Hard bases

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14
Q

What is linear?

A

sp

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15
Q

What is equilateral triangle?

A

sp2

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16
Q

What is tetrahedron?

A

sp3

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17
Q

What is triagonal bi-pyramidal?

A

sp3d

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18
Q

What is octahedron?

A

sp3d2

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19
Q

What do different metals prefer?

A

Different coordination numbers

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20
Q

What are the most common coordination numbers found in biological systems?

A

4 = square planar tetrahedral
6 = octahedral

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21
Q

What can a ligand be?

A

Monodentate OR polydentate

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22
Q

What is monodentate?

A

Only one point of attachment to metal

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23
Q

What is polydentate?

A

More than one point of attachment too metal

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24
Q

What is ciprofloxacin?

A

Hard Lewis acid

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25
What is a macrocyclic molecule?
Cyclic molecule (at least 9 atoms), containing 3 donor atoms - typically N, O, S or P
26
What are macrocyclic complexes?
More thermodynamically + kinetically stable than non-cyclic ligands
27
Are polydentate ligands more stable than monodentate?
YES
28
What is the increasing stability of mono, poly + macrocyclic known as?
Chelate effect
29
What is clinical significance of chelation?
Chelation changes physical + chemical characteristics of both components
30
What are tetracyclines?
Broad-spectrum antibiotics Treat the clap
31
Describe tetracyclines mode of action
Bacteriostatic agents Target 30s subunit Block binding of aminoacyl tRNA in A-site
32
Which metal is involved in mode of action of tetracyclines?
Mg2+
33
What do tetracyclines form?
Chelates with Ca2+, Mg2+, Al3+, Fe2+ + Zn2+
34
What chelates do tetracyclines form with M3+?
3:1 drug-metal chelates
35
What chelates do tetracyclines form with M2+?
2:1 drug-metal chelates
36
What do Al or Mg hydroxide-based antacids do?
Reduce absorption of tetracyclines
37
What are tetracyclines not recommended for? Ca2+ chelates
Kids under 12 = teeth yellow Pregnant women = effect on skeletal growth
38
What can metal ions do and what does this mean?
Stabilise conjugate bases = pKa value of parent acid lowered
39
What does it mean if an acid has a lower pKa?
STRONGER
40
What does it mean if a base has a higher pKa?
STRONGER
41
pKa = pH
50% ionised
42
What do all carbonic anhydrase inhibitors contain?
All share sulphonamide = WAs
43
What is carbonic anhydrase involved in?
Regulation of acid/base balance Production of bicarbonate rich aq humor secretion
44
What does carbonic anhydrase do?
Catalyse reaction between H2O + CO2 to for carbonic acid
45
What is the equation for reaction between H2O + CO2?
CO2 (g) + H2O ⇌ carbonic acid ⇌ hydrogencarbonate (bicarbonate) + H+
46
Which metal does carbonic anhydrase contain?
Zn2+
47
Why is Zn2+ (metals) so important?
Metal drives it = remove Zn2+ = process doesn't work = catalyses process by modulating pKa of H2O = form OH- + giving correct geometry for cleft
48
Where does Zn2+ sit in carbonic anhydrase?
Bottom cleft, which has 2 faces
49
What is the hydrophobic face important for? Carbonic anhydrase
Binding the substrate
50
What is the hydrophilic face important for? Carbonic anhydrase
Shuttling proton
51
Does Ca2+ have a gradient?
YES = through different cellular compartments
52
What is the coordination number for Mg2+?
6
53
What is the coordination number for Ca2+?
7
54
What can Mg2+ + Ca2+ both be thought of as?
Lewis acids
55
What is Mg2+ main role?
Catalytic sites of DNA polymerase
56
What do protein kinases do?
Add phosphate group
57
What do phosphatases do?
Remove phosphate group
58
What is the phosphate supplied as?
Mg-ATP DOESN'T work without Mg2+
59
How is RNA different to DNA?
Perform catalytic functions
60
What does tRNA contain?
Half-crucifixes Mg2+ hold this shape
61
What do ribosomes require?
Mg2+ ions to catalyse their splicing reactions
62
Why is Mg2+ important in muscle cells?
Carries ATP/ADP so has to be present for it to be delivered
63
What does Ca2+ regularly do?
Exchange H2O with other ligands
64
What is calmodulin?
Protein involved in mediation of Ca2+ signal
65
Describe structure of calmodulin
Small, acidic protein Dumbbell shape Binds 4x Ca2+
66
What are the major donor groups for Ca2+?
Carbonyl + carboxylate groups