Winthrop University Zayed Almadidy PRESENTER TODAY TOPIC IS Inorganic Biochemistry WE ARE CURRENTLY ON SLIDE 1 of 27 In Vitro Generation of Cu I Through Redox Chemistry And Its Stabilization By Means of Organic Stabilizing Ligands

Winthrop University Small INTRO Background on the preparation of Cu I Common three oxidation states: Cu 0 Cu I Cu II Cu 0 is most abundant Cu I is difficult to work with under anaerobic and aerobic conditions. Comproportionation Cu II + Cu 0  2Cu I PLACE IMAGE HERE NOT STABLE Zayed Almadidy PRESENTER CURRENTLY WE ARE CURRENTLY HERE 2 of 27 In The Research labs of Winthrop University

YOU ARE LOOKING AT Presenter Name PRESENTER CURRENTLY WE ARE CURRENTLY HERE 3 of 27 Instability of Cu 1+ Equilibrium constants and reduction potential Cu II + e -  Cu I ∑ o = V Cu 0  Cu I + e - ∑ o =.153 V Cu 0 + Cu II  2Cu I ∑ o = V Zayed Almadidy PRESENTER CURRENTLY WE ARE CURRENTLY HERE 3 of 27 In The Research labs of Winthrop University

YOU ARE LOOKING AT Presenter Name PRESENTER CURRENTLY WE ARE CURRENTLY HERE 3 of 27 Gibbs Free ENERGY Nernst Equation and Equilibrium Theory Zayed Almadidy PRESENTER CURRENTLY WE ARE CURRENTLY HERE 4 of 27 In The Research labs of Winthrop University

YOU ARE LOOKING AT Presenter Name PRESENTER CURRENTLY WE ARE CURRENTLY HERE 3 of 27 Stabilizing Cu 1+ Utilizing BCA, BCS and MeCN Cu 0 + Cu II  2Cu I 2Cu I + X  2(Cu I X 2 ) LeChatlier’s Principle: Reaction will favor products Zayed Almadidy PRESENTER CURRENTLY WE ARE CURRENTLY HERE 5 of 27 In The Research labs of Winthrop University

Ligand BCS Structures of Organic Agents Zayed Almadidy PRESENTER CURRENTLY WE ARE CURRENTLY HERE 6 of 27 In The Research labs of Winthrop University

Ligand BCA Structures of Organic Agents Zayed Almadidy PRESENTER CURRENTLY WE ARE CURRENTLY HERE 7 of 27 In The Research labs of Winthrop University

Ligand MeCN Structures of Organic Agents Zayed Almadidy PRESENTER CURRENTLY WE ARE CURRENTLY HERE 8 of 27 In The Research labs of Winthrop University

Goals of the PROJECT What is the destination of the experiment? Understand kinetics of comproportionation reaction. Acquire a stability constant for the Cu II —Ligand complex. To optimize the reaction. PLACE IMAGE HERE Zayed Almadidy PRESENTER CURRENTLY WE ARE CURRENTLY HERE 9 of 27 In The Research labs of Winthrop University

Experimental PROCEDURE Used spectrophotometer 10 uL injections of X ligand Data recorded as a function of time PLACE IMAGE HERE Zayed Almadidy PRESENTER CURRENTLY WE ARE CURRENTLY HERE 10 of 27 In The Research labs of Winthrop University How it was accomplished 1.5 mL Buffer 1.5 mL H 2 O X mL Cu II

Accidental FINDING Zayed Almadidy PRESENTER CURRENTLY WE ARE CURRENTLY HERE 11 of 27 In The Research labs of Winthrop University

YOU ARE LOOKING AT Presenter Name PRESENTER CURRENTLY WE ARE CURRENTLY HERE 3 of 27 Data ANALYSIS What does it mean? Cu II + X  2Cu I Cu I + 2BCS  Cu I BCS nm peak indicative of Cu I /BCS Complex Zayed Almadidy PRESENTER CURRENTLY WE ARE CURRENTLY HERE 12 of 27 In The Research labs of Winthrop University

YOU ARE LOOKING AT Presenter Name PRESENTER CURRENTLY WE ARE CURRENTLY HERE 3 of 27 Electron SOURCE What is the reducing agent? 1. Water 2. Buffer One of these must have been the reducing agent Zayed Almadidy PRESENTER CURRENTLY WE ARE CURRENTLY HERE 13 of 27 In The Research labs of Winthrop University

YOU ARE LOOKING AT Presenter Name PRESENTER CURRENTLY WE ARE CURRENTLY HERE 3 of 27 Water HYPOTHESIS How is water yielding electrons? 4 OH -  2 H 2 O + O e - ∑ o = V 4(CuX 2 ) e -  4(CuX 2 ) 1+ ∑ o =.64 V 4(CuX 2 ) OH -  2 H 2 O + O 2 + 4(CuX 2 ) 1+ ∑ o =.239 V Zayed Almadidy PRESENTER CURRENTLY WE ARE CURRENTLY HERE 14 of 27 In The Research labs of Winthrop University

YOU ARE LOOKING AT Presenter Name PRESENTER CURRENTLY WE ARE CURRENTLY HERE 3 of 27 Testing HYPOTHESIS Altering the pH 4(CuX 2 ) OH -  2 H 2 O + O 2 + 4(CuX 2 ) 1+ LeChatlier’s Principle: Increased hydroxide  Increased products Zayed Almadidy PRESENTER CURRENTLY WE ARE CURRENTLY HERE 15 of 27 In The Research labs of Winthrop University

pH 8.3 HEPES Zayed Almadidy PRESENTER CURRENTLY WE ARE CURRENTLY HERE 16 of 27 In The Research labs of Winthrop University

pH COMPARISONS BCA Concentration T = Minutes MES At pH 6.5 HEPES At pH 7.5 HEPES At pH 8.3 ∆ = pH 8.3 – pH uM AU AU AU0.003 AU uM AU AU AU AU uM AU AU AU0.035 AU 500 uM AU AU AU0.088 AU uM AU AU AU0.122 AU uM AU AU AU0.151 AU Zayed Almadidy PRESENTER CURRENTLY WE ARE CURRENTLY HERE 17 of 27 In The Research labs of Winthrop University

Cu 0 to Cu 1+ PLACE IMAGE HERE Zayed Almadidy PRESENTER CURRENTLY WE ARE CURRENTLY HERE 18 of 27 In The Research labs of Winthrop University How it was accomplished Cu 0 wire.056 mL Cu II mL BCA 0.5 mL MOPS mL H 2 O Vial A Cu 0 wire mL BCA 0.5 mL MOPS 0.44 mL H 2 O Vial B

Winthrop University O 2 HYPOTHESIS Effect of oxygen on the reaction progression 2Cu 0  2Cu I + 2e - ∑ o = V 2H + + 2e - + ½O 2  H 2 O ∑ o = V 2Cu 0 + 2H + + ½ O 2  2Cu I + H 2 O ∑ o = V Zayed Almadidy PRESENTER CURRENTLY WE ARE CURRENTLY HERE 19 of 27 In The Research labs of Winthrop University Cu 0 wire 1000uM BCA pH 6.5 MOPS H 2 O Anaerobic Conditions

Winthrop University Observed RESULTS PLACE IMAGE HERE Zayed Almadidy PRESENTER CURRENTLY WE ARE CURRENTLY HERE 20 of 27 In The Research labs of Winthrop University What did we see? Cu 0 wire 1000uM BCA pH 6.5 MOPS H 2 O AnaerobicAerobic

Winthrop University Reaction KINETICS Quantifying stabilization reaction Cu II + Cu 0 + MeCN  (Cu I MeCN) Zayed Almadidy PRESENTER CURRENTLY WE ARE CURRENTLY HERE 21 of 27 In The Research labs of Winthrop University 50 mM Cu II Cu 0 Various MeCN pH 6.5 MES H 2 O Anaerobic Conditions

Rate DEPENDENCE [MeCN]V0V M M M M M M b = ± Zayed Almadidy PRESENTER CURRENTLY WE ARE CURRENTLY HERE 22 of 27 In The Research labs of Winthrop University

Cu 2+ DEPENDENCE Zayed Almadidy PRESENTER CURRENTLY WE ARE CURRENTLY HERE 23 of 27 In The Research labs of Winthrop University

YOU ARE LOOKING AT Presenter Name PRESENTER CURRENTLY WE ARE CURRENTLY HERE 3 of 27 Future WORK What’s next? Further optimize the reaction Zayed Almadidy PRESENTER CURRENTLY WE ARE CURRENTLY HERE 24 of 27 In The Research labs of Winthrop University Determine what effect the concentration of Cu I has on the kinetics

The CREW Mentor: Dr. Nicholas Grossoehme Sharon Jenkins Destinee Johnson Becca Toor Paisley Trantham Zayed Almadidy PRESENTER CURRENTLY WE ARE CURRENTLY HERE 25 of 27 In The Research labs of Winthrop University

YOU ARE LOOKING AT Presenter Name PRESENTER TODAY TOPIS IS HERE GOES THE TITLE OF THE TOPIC CURRENTLY WE ARE CURRENTLY HERE 7 of 27 Show is over Thank you! Zayed Almadidy PRESENTER CURRENTLY WE ARE CURRENTLY HERE 26 of 27 In The Research labs of Winthrop University