- Therapeutic Nanosystem Consisting of Singlet-Oxygen-Responsive Prodrug and Photosensitizer Excited by Two-Photon Light
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Using light as the sole stimulus and employing the generated singlet oxygen as a therapeutic agent and the trigger to activate chemo-drug release could serve as an elegant way to bring into full play the advantageous features of light and enhance therapeu
- Lin, Yi,Jiang, Xiao-Fang,Duan, Xiangyan,Zeng, Fang,Wu, Bo,Wu, Shuizhu
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- Effect of Structure on the Spin-Spin Interactions of Tethered Dicyanomethyl Diradicals
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Stable organic radicals with switchable spin states have attracted attention for a variety of applications, but a fundamental understanding of how radical structure effects the weak bonding interactions between organic radicals is limited. To evaluate the effect of chemical structure on the strength and nature of such spin interactions, a series of 14 tethered aryl dicyanomethyl diradicals were synthesized, and the structure and thermodynamic properties of the diradicals were investigated. These studies indicate that the nature of the dimer and the equilibrium thermodynamic parameters of the diradical-dimer equilibria are highly sensitive to the attachment point of the linker, the length of the linker, and the substituents on the radical itself. Values of the intramolecular Ka vary from as small as 5 to as high as 105 depending on these variables. An X-ray crystal structure for a linked ortho-substituted diradical shows that the diradical forms an intramolecular sigma dimer in the crystalline state with an elongated C-C bond (1.637 ?). Subtle changes to the radical structure influences the nature of the spin interactions, as fixing the dimethylamino substituent on the radical into a ring to make a julolidine-derived diradical leads to the weakest bonding interaction observed (ΔGbonding = 1 kcal mol-1) and changes the spin-paired species from a sigma dimer to a diradical pimer. This work has implications for the design of stimuli-responsive materials that can reversibly switch between the dramatically different properties of closed-shell species and the unique properties of diradicals.
- Zhang, Rui,Peterson, Joshua P.,Fischer, Logan J.,Ellern, Arkady,Winter, Arthur H.
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supporting information
p. 14308 - 14313
(2018/10/24)
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- Design and synthesis of polymeric chiral bicyclo[3.3.0] diene as reusable ligand for rhodium-catalyzed asymmetric 1,4-addition
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A series of A-B type sterically regular bicyclio[3.3.0] diene-based polymers were designed and synthesized as immobilized chiral diene ligands for asymmetric catalysis. With polymeric diene 6b, good to excellent enantioselectivities can be achieved in Rh-catalyzed asymmetric 1,4-addition of arylboronic acids to α,β-unsaturated ketones. A series of A-B type sterically regular bicyclio[3.3.0] diene-based polymers were designed and synthesized as immobilized chiral diene ligands for asymmetric catalysis. By using polymeric diene, good to excellent enantioselectivities can be achieved in Rh-catalyzed asymmetric 1,4-addition of arylboronic acids to α,β-unsaturated ketones. Copyright
- Yang, Hongyu,Xu, Minghua
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supporting information
p. 119 - 122
(2013/08/24)
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- Photosensitizer drug delivery via an optical fiber
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An optical fiber has been developed with a maneuverable mini-probe tip that sparges O2 gas and photodetaches pheophorbide (sensitizer) molecules. Singlet oxygen is produced at the probe tip surface which reacts with an alkene spacer group relea
- Zamadar, Matibur,Ghosh, Goutam,Mahendran, Adaickapillai,Minnis, Mihaela,Kruft, Bonnie I.,Ghogare, Ashwini,Aebisher, David,Greer, Alexander
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supporting information; experimental part
p. 7882 - 7891
(2011/06/27)
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- Synthesis of Acetylene-Terminated α,ω-Bisphenoxyalkanes
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Nine, α,ω-bis(4-ethynylphenoxy)alkanes were synthesized from the corresponding α,ω-dibromoalkanes by (1) reaction with p-bromophenol/KOH, (2) palladium-catalyzed coupling with 2-methyl-3-butyn-2-ol, and (3) caustic hydrolysis of the hydroxy intermediates.The structures of the ethynyl compounds were confirmed by IR, (1)H NMR, and DSC.
- Babirad, Stephan A.,Feld, William A.
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p. 140 - 141
(2007/10/02)
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- NEW APPROACHES TO SYNTHETIC RECEPTORS. STUDIES ON THE SYNTHESIS AND PROPERTIES OF MACROCYCLIC C-GLYCOSYL COMPOUNDS AS CHIRAL, WATER-SOLUBLE CYCLOPHANES
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In an approach for the preparation of macrocyclic C-glycosyl compounds, the C-glycosyl residue is synthesized by acid assisted reduction of a cyclic hemiacetal with sodium cyanoborohydride.Macrocyclic formation is effected by the reaction of a symmetrical
- Wilcox, Craig S.,Cowart, Marlon D.
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p. 141 - 160
(2007/10/02)
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