2011 BIOC221 Problem Set (2) Due date: Feb 1 (Tue, 11:30 am)

1. Pellagra, na!n ("tamn B3) de#!en!$, al!o%ol&m (Lehninger p. 519;

other sources including but not limited to
http://lpi.oregonstate.edu/infocenter/vitamins/niacin/)
Niacin (shon above) is a ater!soluble vitamin" hich is also #non as nicotinic acid or
vitamin $%. Nicotinamide is the derivative of niacin and used b& the bod& to form the coen'&mes
N() and N()*. Niacin deficienc&" hich affects all the N()(*)+!dependent deh&drogenases"
causes the serious human disease pellagra and a related disease in dogs" blac#tongue.
,ill the blan#s a-f.
(a) *ellagra and blac#tongue are classicall& described b& the .four )/s: ( a )" ( b )" ( c ) and
death.
(b) $ecause dietar& amino acid ( d ) can be metaboli'ed to niacin" foods rich in ( d ) (eg" dair&
products) can compensate for inade0uate dietar& niacin.
(!) *rimar& deficienc& usuall& occurs in areas here ( e ) constitutes a substantial part of the
diet. $ound niacin" found in ( e )" is not assimilated in the gastrointestinal tract unless it has been
previousl& treated ith al#ali" as hen tortillas are prepared. 1nterestingl&" pellagra as not
#non in 2e3ico" here ( e ) as also an important dietar& staple and much of the population
as also poor. 4he traditional preparation of tortillas in 2e3ico involves soa#ing the grain in a
lime (calcium o3ide) solution" prior to coo#ing. 4his process" #non as ( f )" has been practiced
b& native tribes in 2esoamerica" and the earliest evidence of ( f ) is found in 5uatemala6s
southern coast" ith e0uipment dating from 178891588 $:;.
2. Dal$ 'TP (tl)aton b$ *uman 'dult&
(a) ( total of %8.5 #</mol of free energ& is needed to s&nthesi'e (4* from ()* and *i
hen the reactants and products are at 1 2 concentrations and the temperature is 75
o
:
(standard state). $ecause the actual ph&siological concentrations of (4*" ()*" and *i are
not 1 2" and the temperature is %=
o
:" the free energ& re0uired to s&nthesi'e (4* under
ph&siological conditions is different from G'>. :alculate the free energ& re0uired to
s&nthesi'e (4* in the human hepatoc&te hen the ph&siological concentrations of (4*"
()*" and *i are %.5" 1.58" and 5.8 m2" respectivel&.
(b) ( ?@ #g (158 lb) adult re0uires a caloric inta#e of 7"888 #cal (@"%?8 #<) of food per da&
(7A hours). 4he food is metaboli'ed and the free energ& is used to s&nthesi'e (4*" hich
then provides energ& for the bod&/s dail& chemical and mechanical or#. (ssuming that the
efficienc& of converting food energ& into (4* is 58B" calculate (i) the amount of (4* and
(ii) the eight of (4* s&nthesi'ed for use b& a human adult in 7A hours. Chat percentage of
the bod& eight does this representD 4he molecular eight of (4* is 58%.
(!) 4he human bod& on average contains 8.1 mol of (4*. 4he maEorit& of (4F us not
usuall& s&nthesi'ed de novo" but is generated from ()* b& (4*!&ielding catabolism
including gl&col&sis and o3idative phosphor&lation. 4hus" at an& given time" the total
amount of (4* plus ()* remains fairl& constant. 4his is an e3ample of %omeo&ta&&" a
condition in hich the bod& s&nthesi'es and brea#s don (4* as needed. (4* cannot be
stored" hence its consumption closel& follos its s&nthesis. 4his means that each (4*
molecule is rec&cled man& times during a single da&. Fn average ho man& times is each
(4* molecule rec&cled during a da&D
3. *$drol$&& o# ,+,%o&,%oan%$drde brdge n 'TP
)ifferent values for G'> for the h&drol&sis of (4* to (2* and **i are used in different sources.
4able 1%!? of our te3tboo# lists a value of -A5.? #</mol" hile the value is said to be -%8.5 #</mol
in the same te3tboo# (G71 in p.575). ,re& and (rabshahi calculated the G'> to be -A5.? #</mol
(-18.9 #cal/mol) based on the folloing half reactions:
(4* H 7+7F (2* H 7*i G'> I -15.5 #cal/mol
7*i **i H +7F G'> I HA.? #cal/mol
JK2: (4* H +7F (2* H **i G'> I -18.9 #cal/mol
,or more details" see http://pubs.acs.org/doi/pdf/18.1871/bi888%?a881
4he chemical logic behind h& G'> for the h&drol&sis of "!phosphoanh&dride bridge ((4* to
(2*) is more negative than that for the h&drol&sis of "!phosphoanh&dride bridge ((4* to ()*)
is not clear. Nonetheless" the more negative value offers a rationale for certain bios&nthetic
reactions being driven b& cleavage of the "!phosphoanh&dride bridge in (4*.
J&nthesis of the activated form of acetate (acet&l!:o() is carried out in an (4*!dependent process:
(cetate H :o( H (4* acet&l!:o( H (2* H **i (1)
4his reaction is catal&'ed b& an en'&me acet&l!:o( s&nthetase. 4he G'> for the h&drol&sis of
acet&l!:o( to acetate and :o( is -%7.7 #</mol and that for h&drol&sis of (4* to ()* and *i is
-%8.5 #</mol.
(a) :alculate G'> values for the above reaction (1) using G'> of -A5.? #</mol for the
h&drol&sis of (4* to (2*.
(b) :alculate G'> values for the imaginar& reaction here acet&l!:o( formation is driven b&
the h&drol&sis of (4* to ()*:
(cetate H :o( H (4* acet&l!:o( H ()* H *i (7)
(!) Chich reaction is favored" reaction (1) or the imaginar& reaction (7)D Note that hen G'>
value of -A5.? #</mol is used" one does not need to attribute the practical irreversibilit& of the
reaction (1) to the presence of inorganic phosphatases to catal&'e the h&drol&sis of **i.
-. Bolog!al o.daton+redu!ton rea!ton&
,or each pair of ions or compounds belo" indicate hich is the more highl& reduced species.
(a) :o
7H
/:o
H
(b) 5lucose/:F7
(c) ,e
%H
/,e
7H
(d) (cetate/:F7
(e) ;thanol/acetic acid
(f) (cetic acid/acetaldeh&de
/. Standard 0edu!ton Potental& 4he standard reduction potential" E'>" of an& redo3 pair
is defined for the half!cell reaction:
F3idi'ing agent H n electrons reducing agent
4he E'> values for the N()
H
/N()+ and p&ruvate/lactate conEugate redo3 pairs are -8.%7 L
and -8.19 L" respectivel&.
(a) Chich redo3 pair has the greater tendenc& to lose electronsD ;3plain.
(b) Chich pair is the stronger o3idi'ing agentD ;3plain.
(!) $eginning ith 1 2 concentrations of each reactant and product at p+ = and 75
o
:" in
hich direction ill the folloing reaction proceedD
*&ruvate H N()+ H +
H
lactate H N()
H
(d) Chat is the standard free!energ& change (G'>) and the e0uilibrium constant (K/e0) for the
conversion of p&ruvate to lactateD
1. 2nerg$ S,an o# t%e 0e&,rator$ C%an ;lectron transfer in the mitochondrial
respirator& chain ma& be represented b& the net reaction e0uation
N()+ H +
H
H M F7 +7F H N()
H
(a) :alculate E'> for the net reaction of mitochondrial electron transfer. Kse E'> values
from 4able 1%9=.
(b) :alculate G'> for this reaction.
(!) +o man& (4* molecules can theoretically be generated b& this reaction if the free
energ& of (4* s&nthesis under cellular conditions is 57 #</molD
3. 'l!o%ol de%$drogena&e catal&'es the folloing reversible reaction:
(cetaldeh&de H N()+ H +
H
;thanol H N()
H
Kse the folloing information to anser the 0uestions belo:
(cetaldeh&de H 7+
H
H 7e
9
ethanol E'> I 98.78 L
N()
H
H +
H
H 7e
9
N()+ E'> I 98.%7 L
4he ,arada& constant" " is 9?.A@ #</LNmol.
(a) :alculateO G'> for the reaction as ritten. Jho &our or#.
(b) 5iven &our anser to (a)" hat is theO G'> for the reaction occurring in the reverse
directionD
(!) Chich reaction (forard or reverse) ill tend to occur spontaneousl& under standard
conditionsD
(d) 1n the cell" the reaction actuall& proceeds in the direction that has a positiveO G'>.
;3plain ho this could be possible.