Chemical Stability 2 Flashcards

1
Q

What is oxidation defined as?

A

Addition of O
Removal of H
Loss of e-

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2
Q

What is reduction refined as?

A

Removal of O
Addition of H
Addition of e-

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3
Q

What is autooxidation?

A

Molecular oxygen (O2) is the ultimate source
Formation of reactive oxygen species (ROS)

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4
Q

What does activation of ground state molecular O produce?

A

Range of ROS

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5
Q

What is a free radical?

A

Has unpaired e-

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6
Q

What are the 2 key reactions of radicals?

A

Fenton
Udenfriend

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7
Q

What is a Fenton reaction?

A

Generated .HO radicals

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8
Q

What is a Udenfriend reaction?

A

Complex multistep process

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9
Q

What can hydrogen peroxide undertake oxidation reactions on?

A

Povidone
PEG

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10
Q

What is the original component in Udenfriend reaction?

A

Fe2+
EDTA (metal chelator)
Ascorbic acid (reducing agent)

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11
Q

What is phenol/catechol oxidised to?

A

Quinone

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12
Q

What is phenol oxidised to?

A

Dimeric products

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13
Q

What is amines oxidised to?

A

N-oxides

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14
Q

What is thioether oxidised to?

A

S-oxide

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15
Q

What is thiol oxidised to?

A

Disulphide

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16
Q

What does a “fish hook” arrow show?

A

1 e- going to A + other goes with B

17
Q

Describe 7 valence electrons
(radical)

A

Same as carbocation = sp2

18
Q

Describe the stability of radicals from methyl to tertiary

A

Increase

19
Q

What are the steps in radical formation?

A

Initiation
Propagation
Termination

20
Q

What is a good oxidation initiation?

A

Light, UV light

21
Q

What are susceptible to C-H oxidation?

A

Ethers
Aliphatic amines
Aldehydes

22
Q

What are susceptible to O-H + N-H oxidation?

A

Phenols
Aromatic amines

23
Q

How can you minimise oxidation by preventing inititation?

A

Protect from light
Limit peroxides
Use optimum pH
Add chelating agent to remove metal ions

24
Q

How can you minimise oxidation by stopping oxidation?

A

Pack under inert gas - eg. nitrogen
Add antioxidant

25
Q

What is oxidation via atmospheric oxygen a significant issue for?

A

Proteins
Proteins in solution
Freeze-dried samples
Amino acids

26
Q

Describe no-radical reactions of peroxides

A

H2O2 can act as a precursor
To hydroxyl radical
BUT can also directly oxidise amines + sulphides
SN2 reaction

27
Q

When is oxidation observed with aromatic amines?

A

X = H = oxidation
X = EDG = oxidation
X = EWG = NO oxidation

28
Q

What do COOH produce under hydrogen peroxide?

A

Carboxyl peracids

29
Q

What do bicarbonate produce under hydrogen peroxide?

A

Peroxymonocarbonate

30
Q

What do nitriles produce under hydrogen peroxide?

A

Peroxycarbimidic

31
Q

Describe the oxidation of thioethers by hydrogen peroxide

A

Nu- attack by sulphur on peroxide
Yields sulfoxide