Bio week 3

AReduction loxidation Reactions

•redox rns: transfer of e- biw 2 componds /atoms
Oxidation : losee
• reduction gaine
• reduction potential (Ed): the amount of energy
transferred in a redox xn Cotandard rxn) → VolBI millivak
- more negative clower on tower) = less likely to
accept e- Coxidized)
- more positive Chigher on tower) = more likely to
aceept e- Creauced)
- reduced compounds can donate e to oxidized
compands wh higher reduction potentials
- Oxidized companas can accept e from reduced
compands w/ lower reduction potentials
• positive Elo: if a test compound has a stronger altraction
to e
B) Predox Tower
• oxidized compand written ist.
reduced compand 2nd
• compound at bottome good oxidizing agenß
to reduced forms - weak reducing agent3
c) AGO! and DEO
AG'º = -n FAE'S n= # of e transferred
F=96,485 mol
E' = 26 oxidant to reductant
NADY/H & FADH / H2
• act as é carriers
• derived from vitamin b groups a nucleotides
• can be reauced or oxidized + depends on Eó of donor /accepton
•NADHI+ = derived from B3 Chichin)
oxidizing
oxidized
- NAD+ = oxidized form
RH+RADT NADH TR
reduced
- NADH=reduced form caceepts 2e { \ H7) reducing
agent
aerent
D) NADTH FADHI H2
• NADP+ = similar to NADT but w/ an extra phosphate group
& plays a role in anabolic rans leg photosynthesis)
• FAO= nucleoticte based , derived from Be Cribo avin)
_reduced forms FADHz
•more t bonds=more reduced
E) oxidation of Pynvare & the TCA Cycle
• Pynware is Oxidized Looses I carbon via decarboxylation
Be creates aceryl-COA
Laceryl-CoA enters the TCAI Krebs cycie
F) Fates of ATP & NADH & celular pynvate
I if external a acceptor isn't available, the é in NADH get
dumped on an internal metabolite
y turns back to NAD+
I. NADH CHSO donates e to the election transport chaun CETC)
ZNAD
App
III. ATP can be used to couple or as bel for cellular
functions
I. Pyrvate can be used as a terminal é acceptor
in fermentation rans
Zeynuate
V. Dyrvate can be forther oxidized to get more energy
II pynvate could be used as an intermediate linking some
core carbon processing pathways
G) Oxidation of Pynuate Cin respiring bactenar archae)
"in aerobiccally respiring eukaryotes, pynvate moteuses are
transported to the mitochondria
• O2 aets as terminal é aceeptor
• Pyruvate is decarboxylatea & covalently linked to verrymea
through a this ester linkage
bmakes aceryl-CoA enters Frebs cycle
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it) Conversion of Pynuate to Acetyl-CoA
oron catalyzed by pynware denydogenase
•pyruvate as oxidized by NAD+ , decarboxylated, then
covalently linked via an this ester linkage to coenzyme a
• 2 moteutes of pynuucite produced after glycolusis
in 2 of the og carbons- eliminated as con
-reactanto: 2 pyruvate, 2 NADt
- products :2002, 2Acetyl COA 2 NADH
Carboxyl group
is removed
COA-SH
SCOA
1
C=0
Ćso
c=0
90
CHB
NADT
CH3
NADH tcor
acetyl COA
pyruvat x2
oxidation ran
I) TCA Cycie Ctricarboxylic Acid)
•when there's a terminate aceeptor, aceryl COA delivers
(exchanges abond) iB cacetyl group to a 4 carbon moreaute
Coxaloacetated to make citrate
• bacterial archae rang = in cytosa
• eukaryotes= in matrix of mitochondra
• TCA = closed loop Cregenerates itself
•For L aceryl COA :
- produced: 2002
i GTP CATP equivalent)
x2
x2 for
3 NADH
acetyl COA
moreenies
IFADH
• series of redox, denyaration, hydration, & defor boxylation
runs
o most enzymes water sowore except succinate dehydwgenase
3
both
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I) TCA Cycle cont.
I. Steps of TCA cycle:
1.•conctensation ron
•consumed: 2 carbon acetyl group of acetylcom, I
.4 carbon molecure of oxabacetate
•produced: citrate, free coenzyme A
•very exergonic Cirreversible)
• rate of rxn controlled by ATP Cregative feedback)
-TF ATP increases, han decreases
2.cirate loses I H2o moreure B gains another
• citrate is converted to it isomer isocitrate
3.0 socitrate is oxialized by NAD & decarboxylated
• carbon reaves cell as waste
produced- 5 carbon mote cure Ca-ketoglutarave), CO2,
NADH
• also regulated by negative feedback from ATP & NADH
Cpositive feedback w/ ADP)
4. . catalyzed by guccinare denycugenase
•x-ketoglutarate is oxidized by NADT
Loreads to decarboxylanon loss of another c
• accinate dehydwgenase capies the energy from the
redox rant crearrooxylanón to form a thioester bond
bin coenzyme-A7 succinate
h regulated by feedback inhibinon og ATP, suceinyl cont, &
NADH
5. •substrate level phosphorylation
• Inorganic phosphate is cadded to GDP or ADP to make
Gre or ATP
to energy comes from the hydrolysis of Con from
succinyl-COA to make succinate
-GTP-like ate but its use is more restricted
ITCA cycle cont.
6.• redox rin
• succinate 08 oxcclized by FAQ
to makes FADH2 & fumarate
• FADH stays attached to the eneyme of transfers e-to
ETC directly
7. •H2O is added to fumarate
Lomalate is produced
8.oxawacetate is regenerated
via oxication of malate w/ NAP+
- makes oxalo acetate to NADH
j) Precursors from Guycousis 2 TCA cycle
I Glycowsis: 6 preursors
• glucose-6-p, fructose-6-8, trios-e, 3-phospho glycerate,
phosphoenolpyruvate, purvate
I. TCA Cycle: 4 precursors
• acetyl-CoA, alpha ketoglutarate, oxawacetate, sucking colt
11 Respiration
As Overview
• enzymes carry out linked series of redux rons that
transfer ane to a terminal acceptor
• linked rong=(ETClé transport chains
Caenbic eukaryotes) EXC = 4 multipustein complexes inside the
inner mitochondnal membrane + 2 é carriers
2é
•redox rans couple the exergonic redox transfers to
the endergonic transport of hydrogen cons aewss the
membrane
- creates an excetrochemical gradient
- DEó = 60 kcalmo) - NADH
~ 45 kaymo- FADH2
•oxidative phosphorylation process of iransferring a phosphate group
to ADP to make ate using the electrochemical gradient
generated by the redox reaction chains.
B) ETC Summary
1. NADH, FADH2, or other reduced compands clonare é to
the ist acceptor
2. é moves through é transporters (protein carriers) that
undergo redox rens
3. Free energy from I rens moves protons aeuss the membrane
polarizes the membrane → makes electrical potential
and chemical potential (pH difference) electo-chemical
gradient forms
4. é is transferred to terminal accepton CO2 in ppi)
-doesn't have to be 02
C) ETC complexes
oxidoreductases multipntein emzyme complexes Cquartermany Sumanne)
that perform both oxidation & reduction rens
• reductases: oth Oxidation B reduction complexes Except
the terminal comprex (mostly just recluction though)
6) ETC complexes cont.
Omdase : enzymes involved when 02 is an aceeptor of
Ht or e
• posthetic grapi.carry out redox rans inside the complexes
non protein
action
quinones: election comer Lipid) that can be directly
oxidbed (reduced by Oxidoreducares
-quinone rea & quinoneox = water soluble a can move
bin complexes
•2 goups of prosthetic groups
I cany e-
2. carry é BHT
D) Electron B Protein carriers
• avopuoteins (fp) : contain the Ravin prosthenc group whren
undergoes the oxidation/ reduction rxn
ex. PADH2
• Quinones: sowbre lipids
• NADH & NADPH: cany 24t B ke-
• Cytochromes: proteins that contain a herme prosthetic group
- can cany lé
Iron-Sulfur proteins: Fe-S prosthenic group
- carry le-
o Anaerobic vs Aerobic Respiration
Demo bic respiration using 02 as terminal accepton in an ETC
Oncerobic respiration Other terminal acceptor
ex. (NO3) NO2) Fest
cyta
inremembrane
ht
Space
Priest
Juwel well
mitochondrias
24:013
FAD
NAOH
ZH+ + 4202
tho
Ht
Mit le toy
inter
Tul
we
mitochondrial
memorame
ze-
NADT
fl
 amin mononucleoticle
-
I. Complex 1 EMN & Fe-S" INADH dehuschagenase
I.
2e are cared to 18t comprex by NADH
pumps 4 Ht across membrane
II. Comprex 2 a Q:
•comprex 2 recieves FADH2 but é don't pass through
• Uoquinone (@) connect comprexes 283
to reduced to QH2 & cames the e scary pair of e-)
recteres é from NADH & FADH2
"FADH2 makes fower ATP bc it bypasses the 1st complexa
makes less gradient
III. complex 3:
• Betype cytocnome, c-type cytochrome, & an iron-sulfur cluster
(called cytochrome bc, complex]
• cytochrome-cellular pigment
metal bound by here (carries é but not 02)
ioncs reduced (Fezt) Boxcclized CFe3+)
• pumps protons through membrane a passes é to cytochrome a
to only take le at a time
IV. Cytochrome C
aneme protein
• carries le from complex 3 to complex 4
•can undergo reduction & oxidation
V. Complex 4:
(copper)
•2 henre groups (a aas) 83 coions (2 CUA & CUB incytochrome as)
ocytochromes hold Oz tightly by the iron a copper irons until the hol is
reduced
• reduced to picks up 2 Ht to make H2o
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1.15 cont.
F) Chemiosmosis :
"ht long cant diffuse through the lipid bilayer & can
only pass through ATP anthase
blowers activation energy of the ADPtP; ATP reaction
& capres the energy from the movement of it down
in gradient to the encrergonic addition of a phosphate
grep to ADP
• 90% of ATP is mache during aerobic glucose catabolism
1.16 Photosynthesis
A) vont
X-wavelength:
c-speed
• higher frequency (shorter wavelength) = more energy
•blue Motet = high energy (short waverengths)
• orangelred= lower energy Clonger wavelengths)
• organie pigments: absorb a certain wavelength
is due to chemical makeup #stwatures
• 400nm toonm= what we can see
•plants can absorb 300-800mm
• green plants re ect green & absorb all else
Digment Types
1. Chiorophylus
pigmentzab,c,d, f
• chlorophyll a related to ancient moreasles in bacteria →
bacterio chlorophylus (3rd type of pigment)
• ring-like porphyrin group that has a metalion
brelated to here compounds
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3) Pigment types cont.
2. Carotenoids:
•rea, orange, yellow pigments Cabsorbs blue)
• used to attract seed dispersers
•in photosynthesis, they act as light harvesting or
protective Cenorgy clispersing) pigments
3. Bacteriochilorophyllis
te love
() Photon Absorbtion
"When an atom abstras a light photon, ané aquires the
energy and reaves is ground arbital for a higher energy
arbital unstable)
•Fates of an excited e-
1. The é relaxes to a lower avantum state of transfers
energy as heat or light
2. The energy can be transferred by resonance to a
neighboring molecure as the e-returns to a lower avanturm
state
-no energy lost calmost none)
3 the molawle changed its reduction potential becomes a
Strong é clonor. The high energy é can exergonically
be transferred to a good é acceptor
Lo can be involved in a reclox ran Cphotochemical ran)
D) Photophosphorylation Summary
o pristopnosphorylation transfeming energy from light to AFP
• evolved after etc & anaerobic resp
"photon is absorbed by pigment, é becomes excited, pigment
becomes reducing agent, é pass from carrier to carrier via
redox rans which couple a proton gradient, this makes ATP w/
atp synthase é return to oxidized chlorophyl ron center
D) Photo phosphorylation Cont.
•é might instead go through diff camers cnot make tt
gradient) & be deposited on NADP Creative of NAD+)
- this generates NADPH which is used to build sugar
from CO2
-é is NOI recycled
E Oxygenic phosphorylation
•function of light-dependent rang is to convert solar
energy into chemical energy in NADPH a ATP
to supports light-independent rang & assembly of sugar
oxygerie photosynthesis has 2 non centers wil diff reduction
potentials
bean cerive e from tho
opootosystem multipigment complex
opigments in beaded in thylakoid membrane or bacterial
inner membrane
• photosystem II: C carries 685) used 1st → PSIT
C
· photosy stem I : Ccames P700) used 2nd → PSI
-differ be of where they get és where they donate e to
power ATR B NAPPH pwanction
antenna proteins: surand reaction center, covered in chlorophyll
reaction center where photo Chemistry takes place
form a light-harvesting complex
photon excites a chlorophyll 3 causes a chain ran until
the energy is delivered to the ran center
NOTE A Cenergy has been transferred, NOT electrons)
-2chlorophyl a molecules are near an Oxidizing agent
3 when excited, undergo oxidation
- energy becomes more stable Chemical energy
- all following redox rans pomp protons or deliver é to
NADP becomes neelucea)
joins Calvin cycle we deposited on CO2 for Storage
• Calvin cycle= in stoma
9 The ETC
; PSI delivers high energy é to a primary é accepton
Pogo & they pass through the ato
-go through plastoquinones to cytochrome to plastocyanin
.éis passed to oxidized chlorophyll in PSI
- along the way, cytochrome complex postes tt
across the thy lakoid membrane cinto the lonen)
> makes a H+ gradient
•8680.ox's missing é is replaced by taking one from the
• splitting 1 420 makes zé 12ht, and 10
- must split 2 H2o to make os gas
"water splitting part of PSI has a manganese core that
gradually releases e to re ll the "hote" in PSI
- when the manganese gels depleted enough clooses ter)
it takes the 4e from 2H20 molecules
releases 4147 2
mas travel through protcins blw PSIL *PS1 they undergo
redox rano lexergonies
these rans power the transport of tit from the
stromal side of the membrane to the thylakoid lumen
- the tit create proton gradient which powers
ATP synthesis
• at end of ETC, é are deposited on PSI in their
ground state
--
- they are re-energized w/ light
• the re-energized é are reloaded on another ETC
and are donated to NADP+
• another é is delivered to PSI via the ETC that
started w/ PSI
- energy as transferred to reaction center of PSI (P700)
optoo is oxidized & senas é through redox rans to
reduce NADP+ to NADPH
fi
o The ETC cont.
* Poll captures light energy & couples its transfer
via recox vxns to the formation of a Ht gradient
• relaxation of gradient pawers ATP synthesis
G) light Independent Rxns/ Carbon Fixation
i. carbon xation overview:
o some cells can take coz and reduce it to a
usable cellular fom
- in photosyntheti bacteria & plants
• ATP + NADPH from photooynthesis/light bxns is coupled
to carbon xation
incorporates Co2 into organic molecules
-initially goes into Glyceraldehyere-3-phosphare CA3P)
- next into glucose
• autotrophs: dotain required caroon from coz
• heterotrophs: require organic sarce of carbon
• Calvin Cycle reductive pathway that reduces co2
to GBP
H) Calvin cycle
oin plants, occurs in stroma of chloroplasts
• bacteria - occurs in cytoplasm
i. Stepi carbon Fixation
- producto:3002, ributose-1,5-biphosphare carboxylasel
Oxygenase (RuBisCO) 3Riberose-4, 5-biphosphare CRUBP)
- RUBP = 5 carbon + 2 phosphates
- RuBisco- catalyzes ran bin c028 RUBP
for CO2 R I RUBP e-carbon molecures are made
6-c mareute immediately split to make 3-PGA
(note: must ron initial phase 34)
total of 3 e-carbon morecules for all 3 CO2
8 6 3-PGAS
fi
fi
HCalvin Cycle cont
2. Step 2: reduction
- ATP B NADPH are used to convert the le 3-PGA's into
le 63 P marcctes
6 ATP BONADPH used & returned to thylakad
3. Step 3: Begeneration
- 3 Rub is needed to "beed off" LGBP
omust use 5 GBP left to regenerate 3 Robp
- 3 more ATP used
I cyclic phosphorylation
•bacteriochicrophyllred at the reaction Center (1840)
absorbs a photon enegizes an é
-é is transferred to ETC
-redox rxn at one carrier pavers a proton pomp
-é reduces bacteric chicrophylox (makes loop)
•potons travel through ATP synthase to make ATP
js Non cydic Phosphorylation
té are removed from the photosystem toc they end up
on NADPH after the ETC (doesn't pump protons)
- NADPH IS used for crben Rxation
- need a source of e-
Lisarce must be a lover reduction potential chigher up)
than the bacterio chlorophyll
•green-sulfur bacteria use H2S as an é donor
• reaction produces NADPH (2e required) or ATP Cle")
i doesnt produce both