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Inorganic Biochemistry
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In Vitro Generation of CuI Through Redox Chemistry
And Its Stabilization By Means of Organic Stabilizing Ligands
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Small INTROBackground on the preparation of CuI
Common three oxidation states:Cu0
CuI
CuII
Cu0 is most abundant
CuI is difficult to work with under anaerobic and aerobic conditions.
Comproportionation
CuII + Cu0D2CuI
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NOT STABLE
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Instability of Cu1+Equilibrium constants and reduction potential
CuII + e- D CuI ∑o = -.521 VCu0 D CuI + e- ∑o = .153 V
Cu0 + CuII D 2CuI ∑o = -.368 V
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Gibbs Free ENERGYNernst Equation and Equilibrium Theory
Using Equilibrium Theory:There will be 832.31 times more CuII than CuIZayed AlmadidyZayed Almadidy
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Stabilizing Cu1+Utilizing BCA, BCS and MeCN
Cu0 + CuII D 2CuI 2CuI + X D 2(CuIX2)
LeChatlier’s Principle:Reaction will favor products
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Ligand BCSStructures of Organic Agents
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Ligand BCAStructures of Organic Agents
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Ligand MeCNStructures of Organic Agents
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Goals of the PROJECTWhat is the destination of the experiment?
Understand kinetics of comproportionation reaction.
Acquire a stability constant for the CuII—Ligand complex.
To optimize the reaction.
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Experimental PROCEDURE
Used spectrophotometer
10 uL injections of X ligand
Data recorded as a function of time
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How it was accomplished
1.5 mL Buffer
1.5 mL H2O
X mL CuII
400420
440460
480500
0
0.01
0.02
0.03
0.04
0.05
0.0600000000000001
0.0700000000000001
50uM Cu(II) + 10mM BCS in pH 7.5 MOPS Buffer
0 uM 33.22 uM66.23 uM 99.01 uM131.58 uM 163.93 uM196.08 uM 228.01 uM259.74 uM 291.26 uM322.58 uM 353.69 uM384.62 uM 415.34 uM445.86 uM 476.19 uM506.33 uM 536.28 uM566.038 uM 595.61 uM625 uM 654.21 uM683.23 uM 712.08 uM740.74 uM 769.23 uM
Wavelength (nm)
Abs
orba
nce
(AU
) 483 nm
Accidental FINDING
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Data ANALYSISWhat does it mean?
CuII + X D 2CuI CuI + 2BCS D CuIBCS2
483 nm peak indicative ofCuI/BCS Complex
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Electron SOURCEWhat is the reducing agent?
1. Water2. Buffer
One of these must have been the reducing agent
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Water HYPOTHESISHow is water yielding electrons?
4 OH- D 2 H2O + O2 + 4 e- ∑o = -.401 V4(CuX2)2+ + 4e- D 4(CuX2)1+ ∑o = .64 V
4(CuX2)2+ + 4 OH- D2 H2O + O2 + 4(CuX2)1+
∑o = .239 V
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Testing HYPOTHESISAltering the pH
4(CuX2)2+ + 4 OH- D2 H2O + O2 + 4(CuX2)1+
LeChatlier’s Principle:Increased hydroxide Increased products
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pH 8.3 HEPES
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0 25 50 75 100 125 150 175 200 225 2500
0.05
0.1
0.15
0.2
0.25
0.3
0.35
Various BCA Concentrations in pH 8.3 HEPES Buffer
Series1
0.00 uM
166 uM
333 uM
500 uM
666 uM
833 uM
Time (Minutes)
Ab
sorb
ance
(A
U)
pH COMPARISONSBCA ConcentrationT = 239.98 Minutes
MESAt pH 6.5
HEPES At pH 7.5
HEPES At pH 8.3 ∆ = pH 8.3 – pH 7.5
0 uM -0.0003 AU -0.0029 AU -0.0002 AU 0.003 AU
166.67 uM 0.152 AU 0.1312 AU 0.0997 AU -0.032 AU
333.33 uM 0.1448 AU 0.1685 AU 0.2037 AU 0.035 AU
500 uM 0.0891 AU 0.1693 AU 0.2571 AU 0.088 AU
666.67 uM 0.0951 AU 0.1702 AU 0.2924 AU 0.122 AU
833.33 uM 0.1497 AU 0.166 AU 0.3166 AU 0.151 AU
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Cu0 to Cu1+
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How it was accomplished
Cu0 wire.056 mL CuII
0.060 mL BCA0.5 mL MOPS0.439 mL H2O
Vial A
Cu0 wire0.060 mL BCA0.5 mL MOPS0.44 mL H2O
Vial B
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O2 HYPOTHESISEffect of oxygen on the reaction progression
2Cu0 D2CuI + 2e-
∑o = - 0.521 V2H+ + 2e- + ½O2 D H2O
∑o = 2.421 V
2Cu0 + 2H+ + ½ O2 D 2CuI + H2O
∑o = 1.900 V
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Cu0 wire1000uM BCApH 6.5 MOPS H2O
Anaerobic Conditions
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Observed RESULTS
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What did we see?
Cu0 wire1000uM BCApH 6.5 MOPS H2O
Anaerobic Aerobic
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Reaction KINETICSQuantifying stabilization reaction
CuII + Cu0 + MeCN D(CuIMeCN)
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50 mM CuII
Cu0
Various MeCNpH 6.5 MES H2O
Anaerobic Conditions
Rate DEPENDENCE
= k[CuII]a[MeCN]b[CuI]c
[MeCN] V0
0.25 M 0.0007360.50 M 0.003430.75 M 0.00711.00 M 0.008972.00 M 0.014094.00 M 0.0254
b = 0.754227 ± 0.072543
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Cu2+ DEPENDENCE
0 12 24 36 48 60-0.0499999999999998
0.0500000000000002
0.15
0.25
0.35
0.45
0.55
0.65
0.75
Absorbance @ 562 nm of Various Concentrations of Cu(II) in 1000 mM MeCN
2.5 mM12.5 mM25 mM
Time (Minutes)
Ab
sorb
an
ce (
AU
)
𝑉0= k[CuII]a[MeCN]b[CuI]c
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Future WORKWhat’s next?
Further optimize the reaction
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Determine what effect the concentration of CuI has on the kinetics
The CREW Mentor:
Dr. Nicholas GrossoehmeSharon JenkinsDestinee JohnsonBecca ToorPaisley Trantham
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