研究领域
Organic Chemistry/Inorganic Chemistry
Our research program centers on the synthesis of new constructs capable of molecular recognition and the use of these systems for applications in catalysis and materials science.
SELF-ASSEMBLED CAGES WITH INTERNAL FUNCTIONALITY BIOMIMETIC
OXIDATION CATALYSIS SYNTHETIC RECEPTORS AS BIOSENSORS
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SELF-ASSEMBLED CAGES WITH INTERNAL FUNCTIONALITY
The central theme of catalysis by biomolecules is the presence of a selective active site which both binds substrate and activates it for reaction. To increase selectivity and reaction rate, biomolecules often position a reactive functional group towards the center of this active site. Our research is targeted towards the synthesis of self-assembled metal-ligand clusters that bind neutral species in their cavities and orient a functional group toward the bound substrate. Positioning Lewis acidic metals or reactive organic functionalities such as amines or acids in the vicinity of substrate should allow promotion of a variety of different reactions. These species can therefore act as enzyme mimics, but also have uses for novel material applications such as frameworks with defined pores.
BIOMIMETIC OXIDATION CATALYSIS
Enzymes provide a hydrophobic pocket for the binding and reaction of organic substrates, enclosing the reactants in a cavity. Performing chemical reactions in water is extremely desirable for both biomimetic and environmental reasons. By using properly functionalized molecules that provide a hydrophobic cavity for substrates, chemical reactions can be performed in water with both selectivity and turnover. The recognition component is provided by water-soluble cavitands, synthetic receptors that display both a hydrophobic binding pocket and upper rim functionality to perform selective CH oxidation processes. These hosts show controlled non-covalent recognition of hydrocarbons determined by size, shape and the hydrophobic effect. The ultimate goal is to discriminate between chemically identical CH bonds in a proximity-directed oxidation reaction. By pre-organizing these molecules inside the binding pocket, site-selective CH oxidation can be achieved, i.e. the ability to differentiate unactivated C-H bonds in the presence of other identical C-H bonds.
SYNTHETIC RECEPTORS AS BIOSENSORS (Collaboration with Prof. Quan Cheng, UC Riverside)
Synthetic host molecules non-covalently bind substrates with the correct size and shape complementarity. We study deep cavitands that can be incorporated in supported bilayer membranes, while retaining their host properties, allowing reversible binding and real-time sensing of a variety of biologically important analytes. Real-time analysis of the process is performed via surface plasmon resonance spectroscopy. This system provides a simple, flexible architecture for reactions and molecular recognition at a bilayer interface, controlled solely by cavitand:guest interactions in a truly biomimetic environment. This can be exploited for the in situ creation of polymer films atop the lipid bilayer, a process only possible when mediated by the membrane-bound cavitand. Our system is unique: the growth occurs at the bilayer itself, under mild conditions and the process can be reversed, as the polymer is connected to the bilayer by non-covalent molecular recognition with the cavitand hosts. The ultimate goal is to use the recognition system for a study of cell adhesion and sorting via the membrane-bound synthetic receptors or functionalized polymer domains on a supported lipid membrane interface.
近期论文
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Mettry, M.; Moehlig, M. P..; Hooley, R. J.
"Synthesis, Guest Binding, and Metal Coordination of Functionalized Self-Folding Deep Cavitands"
Org. lett. 2015, DOI: 10.1021/acs.orglett.5b00383
Ghang, Y-J.; Perez, L.; Morgan, M.; Si, F.; Hamdy, O.; Beecher, C.; Larive, C.; Julian, R.; Zhong, W.; Chenga, Q.; Hooley, R. J.
"Anionic deep cavitands enable the adhesion of unmodified proteins at a membrane bilayer"
Soft Matter. 2014,10, 9651-9656 DOI: 10.1039/c4sm02347a
Young, M. C.; Holloway, R. L.; Johnson, A. M.; Hooley, R. J.
"A Supramolecular Sorting Hat: Stereocontrol in Metal–Ligand Self-Assembly by Complementary Hydrogen Bonding"
Angew. Chem. Int. Ed. 2014, 53,9832 DOI: 10.1002/anie.20140524
Ghang, Y-J.; Lloyd, J.; Moehlig, M.; Arguelles, J.; Mettry, M.; Zhang, X.; Julian, R.; Cheng, Q.; Hooley, R. J.
"Labeled Protein Recognition at a Membrane Bilayer Interface by Embedded Synthetic Receptors" Langmuir, 2014, 30, 10161. DOI: 10.1021/la502629d
Hooley, R. J.; Gavette, J.; Mettry, M.; Ajami, D.; Rebek, J., Jr.
"Unusual Orientation and Reactivity of Alkyl Halides in Water-Soluble Cavitands" Chem. Sci., 2014, 5, 4382. DOI: 10.1039/C4SC01316F
Young, M. C.; Liew, E.; Hooley, R. J.
"Colorimetric Barbiturate Sensing with Hybrid Spin Crossover Assemblies" Chem. Commun., 2014, 50, 5043. DOI: 10.1039/C4CC01805B
Young, M. C.; Johnson, A. M.; Hooley, R. J.
"Self-Promoted Post-Synthetic Modification of Metal-Ligand M2L3 Mesocates" Chem. Commun., 2014, 50, 1378. DOI: 10.1039/C3CC48444K
Li, V.; Ghang, Y.-J.; Hooley, R. J.; Williams, T.
"Non-Covalent Self Assembly Controls the Relaxivity of Magnetically Active Guests" Chem. Commun., 2014, 50, 1375. DOI: 10.1039/C3CC48389D
Johnson, A. M.; Young, M. C.; Zhang, X.; Julian, R. R.; Hooley, R. J.
"Cooperative Thermodynamic Control of Selectivity in the Self-Assembly of Rare Earth Metal-Ligand Helices"
J. Am. Chem. Soc., 2013, 135, 17723. DOI: 10.1021/ja409882k
Hong, J.; Djernes, K. E.; Lee, I.; Hooley, R. J.; Zaera, F.
"Heterogeneous Catalyst for the Selective Oxidation of Unactivated Hydrocarbons Based on a Tethered Metal-Coordinated
Cavitand" ACS Catal., 2013, 3, 2154. DOI: 10.1021/cs400471b
Young, M. C.; Liew, E.; Ashby, J.; McCoy, K. E.; Hooley, R. J.
"Spin State Modulation of Iron Spin Crossover Complexes Via Hydrogen-Bonding Self-Assembly" Chem. Commun., 2013, 49, 6331. DOI: 10.1039/C3CC42851F
Ghang, Y-J.; Schramm, M. P.; Zhang, F.; Acey, R. A.; David, C. N.; Wilson, E. H.; Wang, Y.; Cheng, Q.; Hooley, R. J.
"Selective Cavitand-Mediated Endocytosis of Targeted Imaging Agents into Live Cells" J. Am. Chem. Soc., 2013, 135, 7090. DOI: 10.1021/ja401273g
Johnson, A. M.; Young, M. C.; Hooley, R. J.
"Reversible Multicomponent Self-Assembly Mediated By Bismuth Ions" Dalton Trans., 2013, 42, 8394. DOI: 10.1039/C3DT50578B
Young, M. C.; Johnson, A. M.; Gamboa, A. S.; Hooley, R. J.
"Achiral Endohedral Functionality Provides Stereochemical Control in Fe(II)-Based Self-Assemblies" Chem. Commun., 2013, 49, 1627. DOI: 10.1039/C3CC37912D
Djernes, K. E.; Padilla, M.; Mettry, M.; Young, M. C.; Hooley, R. J.
"Hydrocarbon Oxidation Catalyzed by Self-folded Metal-coordinated Cavitands" Chem. Commun., 2012, 48, 11576. DOI: 10.1039/C2CC36236H
Liu, Y.; Young, M. C.; Moshe, O.; Cheng, Q.; Hooley, R. J.
"A Membrane-Bound Synthetic Receptor Promotes Growth of a Polymeric Coating at the Bilayer–Water Interface" Angew. Chem. Int. Ed., 2012, 30, 7748; Angew. Chem., 2012, 124, 7868-7871. (Listed as a Very Important Publication) DOI: 10.1002/anie.201202635
Moehlig, A. R., Djernes, K. E., Krishnan, V. M., Hooley, R. J.
"Cytosine Derivatives Form Hemiprotonated Dimers in Solution and the Gas Phase" Org. Lett., 2012, 14, 2560. DOI: 10.1021/ol300861r
Djernes, K. E.; Moshe, O.; Mettry, M.; Richards, D. D.; Hooley, R. J.
"Metal-coordinated Water Soluble Cavitands act as C-H Oxidation Catalysts" Org. Lett., 2012, 14, 788. DOI: 10.1021/ol203243j
Liu, Y.; Taira, T.; Young, M. C.; Ajami, D.; Rebek, J., Jr.; Cheng, Q.; Hooley, R. J.
"Protein Recognition by a Self-Assembled Deep Cavitand Monolayer on a Gold Substrate" Langmuir, 2012, 28, 1391. DOI: 10.1021/la2039398
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