2b Flashcards

1
Q

aa are normally in what form

A

dipolar ions

aka zwitterions

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2
Q

do aa like to have their amine and carboxylyc groups neutral or charged

A

they prefer them to be charged

but for the overal charge to be 0.

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3
Q

how do diff phs change aa

A

the amine and cooh groups have diff charges at diff phs

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4
Q

aa physical properties are influenced by the ionic states of what groups

A
  • ionic alpha coo-
  • ionic alpha nh3+
  • ionic groups in the R side chain
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5
Q

why does the ph and therefore the ionic states of the FG important and what do they influence

A

ph is important bc the fg have diff ionic states at diff phs

diff ionic states can influence the 3d protein structure and the function of the protein aka if its an enzyme u can change the acrive site and change its function etc.

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6
Q

HA + H2O equation

A

HA + H2O <–> H3O+. + A-

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7
Q

ka equation

A

ka = (H3O+)(A-) / (HA)

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8
Q

the larger the ka the what

A

the larger the ka = the more acidic the thing ,, bc u get more of the A- and H3O+ stuff bc those are the numerators which HA aka the non dissociated state is the denominator.

more dissociation = more acidic

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9
Q

pka in terms of ka

A

pka = -log (ka)

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10
Q

pka and ph ,, what does what mean

A

low pka = more acidic !!!

bc more ka = more aicdic

and pka = -log(ka)

so the larger the ka for being more acidic ,, the lower the pka value.

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11
Q

what does pX mean

A

the -log of X

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12
Q

2H2O equation

A

2H2O <–> H3O+ + OH-

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13
Q

kw = what

A

(H3O+)(OH-) = 10^-14

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14
Q

pkw = what

A

pka + pkb = 14

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15
Q

ph in terms of H3O+

A

ph = -log(H3O+)

so (H3O+) = 10^-ph

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16
Q

when does (A-) = (HA)

A

when half of it is dissociated

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17
Q

if (A-) = (HA) how does this effect ph = pka + log( (A-)/(HA))

A

it makes the fraction = 1,, and the log of 1 =0

so u can avoid that part so the pH = Pka when the conc of A- and HA is the same!! aka when its half deionised

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18
Q

when is pH > PKA

A

when (A-) > (HA)

aka at high PH’s

bc at high phs,, the NH3 becomes NH2 meaning u just have the coo- giving it a - sign

the conc of the conjugate base is larger

19
Q

when is pka > ph

A

more acidic ph
lower ph

when (HA) > (A-)
the conc of the acid is larger

20
Q

(A-) / (HA) = what

A

10^4

ph is 4 units greater than pka. the major component is the conc of A-

21
Q

normal cooh pka is

22
Q

amino acid alpha cooh is what pka

23
Q

alpha cooh pka range is what

24
Q

why is the pka of alpha cooh less than a normal cooh

A

in alpha cooh,, u have the NH3+ near it,, aka attached to the same carbon,, meaning it attracts some of the e- via inductive effect,, stabilising the negative charge and therefore making it more acidic.

whereas in a normal cooh,, theres no inductive stabilisation from NH3+

and the NH3+ is the way it is bc its in an acidic env,, so obvs its gonna be the NH3+ form

25
what happens when theres an extra COOH in the R side chain,, whats the pka of these
it depends on how far away it is from the NH3+ and therefore the chiral carbon. the further away it is,, the closer th epka to a normal COOH at 4.76. the closer it is,, the smaller pka and more acidic it is,, bc its getting more inductive effect stabilisation
26
pka of an alpha, beta and gamma cooh
alpha = 2.35 beta = 3.86 gamma = 4.07
27
whats the acidicity of an alpha NH3+ in aa
9.47pka
28
whats the acidity of a normal ammonium cation
10.76
29
range of pka for an alpha nh3+
9-9.5
30
whats cool about zwitterions
they can act as bases and as acids
31
when things can act as an acid and a base,, what kind of behaviour do they have
they have amphoteric behaviour
32
is nh3+ a strong or weak acid
its A WEAK ACID it gives a h to water its nh3+ form is preferred tho
33
is coo- a strong or weak base
its a weak base it takes a h from water its coo- form is preferred tho
34
describe an amino acid whenu have a neutral ph
u have the zwitterion form the nh3+ and the coo- form.
35
describe an amino acid at acidic ph
u have the nh3+ but u have the cooh positive cation
36
describe an amino acid in a basic environment
u have the NH2 but the coo- so u have the negative anion
37
does ph affect both the nh3 and coo-
nope the ph normally just changes one of them ,, so think strategically about which one its gona be
38
for non polar amino acids which a non ionisable side R chain,, the abundance of each form depends on what
depends o nthe pka and ph of the solution the pka depends on the pka of the ionisable nh3+ and coo-
39
if u have the zwitterion // neutral form when u have a neutral ph,, when do u have the cationic and anionic form
anionic = u have the nh2 and coo- so this must be when the the ph> pka cationic = u have the NH3 and the cooH ,, so this must be in an acidic ph < pka
40
at ph of 7 aka neutral ph,, how are the ionisable groups such as coohs or nh3s affected if theyre in the side R chain
they will be in their ionised form. if theres 2 nh type things in one r group,, the most basic one will change to the nh whilst the other one stays charged.
41
aa normally exist as what specie
they normally exist as their charged specie
42
write an equilirbium reaction for thr dissociation of leucine with a high aka basic ph.. what do we need to do
look at the diff pka values for the nh3 and coo-. obvs neutral: coo- and nh3+ giving a neutral species acidic ph where the ph < PKa u get cooh so u get a cationic specie when the ph> pka2,, u get NH2 and coo- meaning u have the anionic form!! u draw the diff forms with equilibrium arrows between the 3 species and then write low and high ph on the sides.
43
what do we do when we want to calculate the ratio f the conc of leucine ionised species with a net charge 0 and with a ne charge of -1 for an aqueous solution at ph 8.2. the pka values of leucine are pka1 = 2.36 and pka2 = 9.60 which pka do we need to consider which of the two species will be present in the higher conc
okay so the ph of solution is 8.2 which is most similar to the pka2 of 9.60 meaning ur more basic than neutral ,, but not more than 9.60 which of the 2 soeies will be present at a higher conc : the neutral one,, bc the ph is higher than neutral but its not higher than pka2 just yet!!! so u have a higher conc of the neutral form . aka what pka is the ph more similar to ,, and then does the ph overtake it or not.
44
calc the ratio of the conc of leucine ionised specie with a net charge of 0 and that with net charge = -1 for an aqueous solution at ph 7.4 pka 1 = 2.36 and pka2 = 9.60
ph = pka + log( [A-1]/[HA]) ph is most similar to pka2 ,, 9.60 so the equilirbium is between the neutral and anionic form . 7.4 = 9.60 + log( [AA-1]/[AA0]) -2.2 = log ([AA-1]/[AA0]) 2.2 = log ( [AA0]/[AA-1]) 10^2.2 = [AA0]/[AA-1]) so 158.5 = [AA0]/[AA-1]) so thats the ratio between the 2 species + the answer.