Biomedical subjects
Kelly S Chichak
Publications and source records attributed to Kelly S Chichak.
Bioinspired detection of light using a porphyrin-sensitized single-wall nanotube field effect transistor.
Single-wall carbon nanotube (SWNT) field effect transistors (FETs), functionalized noncovalently with a zinc porphyrin derivative, were used to directly detect a photoinduced electron transfer (PET) within a donor/acceptor (D/A) system. We report here that the SWNTs act as the electron donor and the porphyrin molecules as the electron acceptor. The magnitude of the PET was measured to be a function of both the wavelength and intensity of applied light, with a maximum value of 0.37 electrons per porphyrin for light at 420 nm and 100 W/m2. A complete understanding of the photophysics of this D/A system is necessary, as it may form the basis for applications in artificial photosynthesis and alternative energy sources such as solar cells.
Nanoscale borromeates.
[Structure: See text] In addition to a parent zinc(II) Borromean ring (BR) complex, the preparation and characterization of two hexasubstituted BR complexes with either 4-acetoxymethylphenyl or 4-methylthiophenyl substituents associated in turn with all six pyridyl rings has been achieved convergently in good yields by appealing to the dynamic features of the reactions between primary amino groups in a preformed acyclic ligand and 2,6-diformylpyridine. Two molecules of the acyclic ligands react with two molecules of 2,6-diformylpyridine to form a cyclic [2 + 2] tetraimine in the presence of Zn(II) ions as templates in 2-propanol at 70 degrees C. The successful preparation of the two derivatives by convergent template-directed syntheses opens up opportunities to self-assemble, under equilibrium control, numerous nanoscale metallo-organic particles with potentially useful properties.
Dynamic nanoscale Borromean links.
Employing halogen atom labels on one of the ligand precursors, the lability of at least some of the 30 dative and 12 imine bonds stabilizing and constituting the three rings of a metallo-Borromean linked compound are scrambled in acidic methanolic solution.
Nanoscale Borromean links for real.
Borohydride reduction of a Borromean Ring (BR) complex containing six zinc(II) ions and 12 imine bonds has resulted in its demetallation, producing a neutral BR compound and also its free macrocycle, following cleavage of at least one of the imine bonds in the ethanolic reaction mixture.
Single-walled carbon nanotubes under the influence of dynamic coordination and supramolecular chemistry.
A dynamic coordinative-directed solubilization of single-walled carbon nanotubes (SWNTs) in aqueous solutions has been achieved through a combination of a Zn(II) metalloporphyrin complex and a cis-protected Pd(II) complex, which are believed to form charged acyclic and/or cyclic adducts on or around the side walls of SWNTs. The solubilization of SWNTs in aqueous solution only occurs when these acyclic and/or cyclic complexes are allowed to enter simultaneously into a self-assembly process with SWNTs under mild conditions. The aqueous solubility properties that these dynamic complexes confer upon SWNTs are believed to involve noncovalent bonding interactions between the two entities. They have been probed in solution using ultraviolet and visible absorption spectroscopy and in thin films using high-resolution transmission electron microscopy. The supramolecular electronic effects that the individual components of their acyclic and/or cyclic complexes impart upon a single semiconducting SWNT have been probed within a nanotube field-effect transistor device.
Nanoscale borromean rings.
The molecular expression of topologically interesting structures represents a formidable challenge for synthetic chemists. The nontrivial link known as the Borromean rings has long been regarded as one of the most ambitious targets in this field. Of ancient provenance, this symbol comprises three interlocked rings in an inseparable union, but cut any one of the rings and the whole assembly unravels into three separate pieces. This Account delineates different strategies that can be applied to the formation of molecules possessing this distinctive topology, culminating with two successful syntheses of such compounds, thus cutting the Gordian knot of topological chemistry.
Molecular borromean rings.
The realization of the Borromean link in a wholly synthetic molecular form is reported. The self-assembly of this link, which is topologically achiral, from 18 components by the template-directed formation of 12 imine and 30 dative bonds, associated with the coordination of three interlocked macrocycles, each tetranucleating and decadentate overall, to a total of six zinc(II) ions, is near quantitative. Three macrocycles present diagonally in pairs, six exo-bidentate bipyridyl and six endo-diiminopyridyl ligands to the six zinc(II) ions. The use, in concert, of coordination, supramolecular, and dynamic covalent chemistry allowed the highly efficient construction, by multiple cooperative self-assembly processes, of a nanoscale dodecacation with an approximate diameter of 2.5 nanometers and an inner chamber of volume 250 A(3), lined with 12 oxygen atoms.