1/29/2020 1 Comenzamos en breve, a las 1 CST / 2 EST El Trigésimo primero Webinar en Español auspiciado por ACS y SQM 1 https:// www.acs.org/content/acs/en/acs-webinars/spanish/fulerenos.html Serendipia en Química: Historia del Descubrimiento de los Fulerenos y sus Aplicaciones Biomédicas y Fotovoltaicas Ponente y Moderadora Escriba y someta sus preguntas durante la presentación 2 “¿Por qué he sido “silenciado”? No se preocupe. Todo el mundo ha sido silenciado, excepto el ponente y la moderadora. Gracias, y disfruten de la presentación. ¿Tiene preguntas para el ponente?
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1/29/2020
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Comenzamos en breve, a las 1 CST / 2 EST
El Trigésimo primero Webinar en Español auspiciado por ACS y SQM
Khakina, E. A.; Kraevaya, O. g. A.; Popova, M. L.; Peregudov, A. S.; Troyanov, S. I.; Chernyak, A. V.; Martynenko, V. M.; Kulikov, A. V.; Schols, D.; Troshin, P. A. Org. Biomol. Chem. 2016. doi: 10.1039/c6ob02251k
Fullerene derivatives as HIV agents
1993
2016
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C60 Derivatives as Anti-HIV Agents
Marchesan, S.; Da Ros, T.; Spalluto, G.; Balzarini, J.; Prato, M. Bioorg. Med. Chem. Lett. 2005, 15, 3615
Windsor,; Raines,.Sci. Rep. 2015, 5, 11286. Freed, E. O. Nat. Rev. Micro. 2015, 13, 484.
FRET pair (EDANS and DABCYL)
Quencher
DABCYL = 4-(4-dimethylamino
phenylazo)benzoic acid
Fluorophore
EDANS = 5-((2-aminoethyl)
amino)naphthalene-1-sulfonic acid
P17 P24
Quencher
Fluorophore
P17 P24
P24P17
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Regioisomeric mixture
2Trans-3
1
Indinavir
Martinez, Z. S.; Castro, E.; Seong, C. S.; Ceron, M. R.; Echegoyen, L.; Llano, M. Antimicrob. Agents Chemother. 2016, 60 (10), 5731-5741
Indinavir tested at 0.1 μM.
3 μM
In Vitro Protease Assay at Different Concentrations
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Late Stage HIV Inhibition and In Vitro Protease Assay
0
10000
20000
30000
40000
50000
0 30 60 90
RF
I
Time (min)
Full.6
Indinavir
DMSO
In vitro protease assay at 3 µM concentration
* Indinavir tested at 0.1 μM.
0
20
40
60
80
100
DMSO Indinavir 6 a-C70 b-C70
100
3.43 0.026 0.047 0.003
% I
nfe
ctiv
ity
Fullerenes Tested at 3 µM
* Indinavir tested at 0.1 μM.
a-C70 b-C70
Castro, E.; Martinez, Z. S.; Seong, C. S.; Cabrera-Espinoza, A.; Ruiz, M.; Hernandez, G., A; Valdez, F.; Llano, M.; Echegoyen, L. A. J. Med. Chem. 2016, 59, 10963-10973
6 7 8Indinavir
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Regioisomeric mixture
6Indinavir
Trans-3
1
Effectiveness Against Drug-Resistant Single Round Infectious Viruses
020406080
100100
3.43
62.9 62.4350.44
67.04 67.3586.1
Indinavir
Infe
cti
vit
y %
* Indinavir tested at 0.1 μM. * Fullerenes tested at 3 μM.
Castro, E.; Martinez, Z. S.; Seong, C. S.; Cabrera-Espinoza, A.; Ruiz, M.; Hernandez, G., A; Valdez, F.; Llano, M.; Echegoyen, L. A. J. Med. Chem. 2016, 59, 10963-10973 35
Pull Down Experiments
Castro, E.; Martinez, Z. S.; Seong, C. S.; Cabrera-Espinoza, A.; Ruiz, M.; Hernandez, G., A; Valdez, F.; Llano, M.; Echegoyen, L. A. J. Med. Chem. 2016, 59, 10963-10973 36
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Click Reaction
Before reaction After 6 h reaction After 1 minute
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Pull Down Experiments
Castro, E.; Martinez, Z. S.; Seong, C. S.; Cabrera-Espinoza, A.; Ruiz, M.; Hernandez, G., A; Valdez, F.; Llano, M.; Echegoyen, L. A. J. Med. Chem. 2016, 59, 10963-10973 38
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Pull Down Experiments
Castro, E.; Martinez, Z. S.; Seong, C. S.; Cabrera-Espinoza, A.; Ruiz, M.; Hernandez, G., A; Valdez, F.; Llano, M.; Echegoyen, L. A. J. Med. Chem. 2016, 59, 10963-10973
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Thin Layer Photovoltaics
Image retrieved from: http://www.oled-display.net/files/u1/heliatek-solarcell.jpg October 11, 2010
Flexible, Potential to be Mass Produced, Light (25-50 g/m2), Better
Global Energy Balance, Color Flexibility
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Fullerenes as Acceptors
• Low-lying LUMO energy levels
• Low internal and solution re-organization energies that accelerate the charge separation process and decrease the charge recombination
• 3D charge transport properties
Allemand, Wudl, F. J. Am. Chem. Soc. 1991, 113, 1050 – 1051.
Singh et al, Org. Electron. 2005, 6, 105
Imahori et al J. Phys. Chem. A, 2001, 105, 1750-1756
Marcus, R. A. J. Chem. Phys. 1956, 24, 966-978.
Reaction Path Reaction Path
41 41
Solar Cell Efficiencies Perovskite Cell = 25.2%!
3.8% in 2009 to 25.2% in 2019
NREL, Best Research-Cell Efficiencies, https://www.nrel.gov/pv/assets/images/efficiency-chart.png, (accessed November, 2019) 42
New J. Chem., 42, 2896-2902, 2018J. Mater. Chem. A, 5, 7326-7332, 2017
J-V curves
Efficiencies
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Conclusions
PC61BM
PC61BEH
PC61BM PC61BEH
Solubility
C. Tian, K. Kochiss, E. Castro, G. Betancourt-Solis, H. Han, L. Echegoyen, J. Mater. Chem. A. 2017, 5, 7326.
Packing
E. Castro, G. Zavala, S. Seetharaman, F. D'Souza, L. Echegoyen, J. Mater. Chem. A. 2017, 5, 19485.ACS Applied Materials & Interfaces 2019, 11, 34408-34415, ACS. App.
Mater. Interfaces. 2016, 8, 31426.
PC61BM
PC71BM
DMEC60
DMEC70
DMEC60 DMEC70
Specific Interfacial InteractionsIsomeric Purity
C. Tian, E. Castro, G. Betancourt-Solis, Z. Nan, O. Fernandez-Delgado, S. Jankuru, L. Echegoyen, New J. Chem., 42, 2896-2902, 2018.
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Progress in Fullerene-based Hybrid Perovskite Solar Cells
E. Castro, J. Murillo, O. Fernandez-Delgado, L. Echegoyen, J. Mat. Chem.- C 2018, 6, 2635.
Review
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Summary
• The importance of Serendipity
• Fullerenes exhibit a range of interesting properties that make them useful in many different applications.
• Some derivatives are active against diseases such as cancer, viral infections, etc.
• Mainly due to their unique electronic properties, especially good electron accepting abilities, they
are excellent N-doped materials in photovoltaic devices.
• Controlling their structures and electronic properties allows the optimization of the open circuit
voltage as well as of the interfacial interactions with Perovskite layer materials.
• Anti-HIV activity involves interactions with a capsid or capsid-SP1 protein, not the HIV protease,
as previously believed.
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M3N@C2n
M2S@C2nM3NC@C2n
M2–4C2@C2n MxOy@C2n
M3CH@C2n
Fullerenes as Nanocontainers
Families of Cluster Metallofullerenes M = group-III (Sc, Y, and Lanthanides)