Biomedical subjects

Todd L Kurth

Publications and source records attributed to Todd L Kurth.

7 recordsLinked to original sources

PubMed2005

Electronic interactions in tertiary oligophenylureas.

The syntheses, structures, and spectroscopy of a series of oligomeric tertiary oligophenylureas possessing one to five phenyl rings are reported. A convergent synthetic method employing tertiary monoamine and diamine building blocks is employed. NMR and molecular modeling are indicative of folded structures for all of the oligophenylureas in which adjacent phenyl rings have a splayed face-to-face geometry. NMR chemical shifts, absorption and emission maxima, and electrochemical oxidation potentials are all dependent upon the number of phenyl rings. The addition of a first inner phenyl has a pronounced effect on the chemical shifts, while a second and third inner phenyl have diminished effects. The oxidation potentials of the oligophenylureas display an abrupt decrease upon the addition of the second inner phenyl. The absorption and emission spectra are relatively insensitive to the addition of one to three inner phenyl rings. The electronic structures of the oligophenylureas possessing one to eight rings have been analyzed using ZINDO calculations. The frontier orbitals of the ureas with one to three phenyl rings are localized on a single phenyl ring (the inner ring for the three-ring urea), whereas the frontier orbitals of the higher oligomers are delocalized over two phenyl rings. In all cases, urea-localized n,pi* transitions are lower in energy than the phenyl-localized pi,pi* transitions. The changes in properties with added phenyl rings parallel those previously observed for multilayered cyclophanes; however, they are less pronounced because of weaker coupling between the phenyl rings of the oligophenylureas.

Magnetic Resonance Spectroscopy↗

PubMed2004

Polyaryl anion radicals via alkali metal reduction of arylurea oligomers.

A series of N-methylated polyarylurea oligomers have been reduced with potassium metal in HMPA. These reductions result in the transient formation of arylurea anion radicals, which undergo reductive elimination of the urea linkages. The aryl moieties appear in the products as the anion radicals of oligoaryl systems. The reaction is intramolecular, and the sequencing in the polyaryl anion radical remains the same as in the polyarylureas due to the urea-enforced pi-pi stacking interactions.

Journal Article↗

PubMed2004

Dynamics and equilibrium for the formation of fluorescent Lewis acid-base exciplexes and triplexes between 9-aminophenanthrene and aliphatic amines.

The excited singlet states of 9-aminophenanthrene and its N-aminoalkyl derivatives are strongly fluorescent in cyclohexane. Addition of low concentrations of Et(3)N, Pr(2)NH, or PrNH(2) results in a red shift of the emission maximum and moderately decreased fluorescence intensity. Analysis of the fluorescence behavior using a combination of singular value decomposition with self-modeling and kinetic analysis provides evidence for the sequential formation of 1 : 1 (exciplex) and 1 : 2 (triplex) complexes between the excited 9-aminophenanthrene and ground-state alkylamine, both of which are strongly fluorescent. Both the formation and decay of the exciplex and triplex are dependent upon the extent of amine N-alkylation. Rate constants and equilibrium constants for complex formation follow the order 1 degree approximately 2 degree > 3 degree, analogous to that for the formation of ground-state complexes between amines and the soft Lewis base HgBr(2). Similarly, N-aminoalkyl derivatives of 9-aminophenanthrene form intramolecular exciplexes. Excited-state complex formation is attributed to a Lewis acid-base interaction between the excited aminophenanthrene (lone-pair acceptor) and ground-state amine (lone-pair donor). The factors which determine the stability of excited-state Lewis acid-base complexes are characteristic of the specific excited-state acceptor. No universal scale of lone-pair donor strength can be expected to describe the formation of such complexes.

Journal Article↗

PubMed2003

Ground-state conformational equilibrium and photochemical behavior of syn and anti N,N'-dimethyl-N,N'-di-1-naphthylurea protophanes.

The structure, spectroscopy, and photochemistry of N,N'-dimethyl-N,N'-di-1-naphthylurea have been investigated and compared to the properties of the corresponding secondary diarylurea N,N'-di-1-naphthylurea and the tertiary mono arylurea N,N,N'-trimethyl-N'-1-naphthylurea. The crystal structures and solution NMR spectra of the tertiary and secondary dinaphthylureas establish that they adopt folded (E,E) and extended (Z,Z) structures, respectively, both in the solid state and in solution. In solution, the tertiary E,E-dinaphthylurea exists as a mixture of syn and anti conformations separated by a barrier of ca. 14 kcal/mol, as determined by variable-temperature (1)H NMR spectroscopy. Computational exploration of the ground-state potential energy surface suggests that the lowest energy pathway for interconversion of the syn and anti conformers requires concurrent rotation about both the nitrogen-naphthalene and the nitrogen-carbonyl single bonds. The tertiary dinaphthylurea exhibits blue-shifted absorption and red-shifted emission attributed to excitonic interactions between the naphthalene rings. The secondary dinaphthylureas and mono naphthylurea have typical naphthalene-like monomer absorption and fluorescence spectra. Dual exponential fluorescence decay is assigned to the two conformers of the tertiary dinaphthylurea. Nonlinear fitting of the fluorescence decay times provides activation parameters for singlet decay of the two conformers. The decay process is attributed to nonsynchronous naphthalene-naphthalene bonding which, in the case of the syn conformer, results in the formation of a [2+2] intramolecular adduct. The preferred E,E conformation and moderate barrier to conformational isomerization make the tertiary dinaphthylurea an attractive building block for larger self-organizing pi-stacked aromatic arrays.

Journal Article↗

PubMed2003

N,N'-dimethyl-N,N'-diarylurea anion radicals: an intramolecular reductive elimination.

The one-electron reduction of tertiary N,N'-dimethyl-N,N'-diarylureas (aryl = phenyl, beta-naphthyl, alpha-naphthyl), in HMPA, results in anion radicals that undergo novel intramolecular reductive elimination reactions leading to the formation of the anion radicals of the corresponding biaryls. These results are due to face to face pi-pi stacking interactions involving the two aromatic rings in the urea systems. The overlapping p(pi)() orbitals on the ipso carbons of opposing aryl groups evolve into a sigma bond leading to the formation of the biaryl anion radical. In the case of the N,N'-dimethyl-N,N'-di-2-pyrenylurea system, there is a node in the LUMO of the number 2 carbon, and the parent anion radical remains intact.

Journal Article↗

PubMed2003

The complex between 9-(n-decanyl)acridone and bovine serum albumin. Part 2. What do fluorescence probes probe?

Factor analysis indicates that the fluorescence spectrum of 9-(n-decanyl)acridone (NDA), when bound to Bovine Serum Albumin (BSA), can be described quite adequately as the sum of two spectra, attributed to a "free" and a "bound" species. Kinetic evidence indicates that upon electronic excitation the system undergoes a net increase in free NDA, relative to the equilibrium distribution in the ground state, which would be consistent with Lewis acid sites on BSA being responsible for the binding. The system does not attain a position of equilibrium during the duration of the excited singlet state. This permits the determination of excited state rate constants for binding and unbinding of NDA on BSA, as well as the decay constants for the two forms of the probe.

Fluorescent Dyes↗

PubMed2002

Luminescence of extended and folded N,N'-diarylureas.

The relationship between molecular structure and luminescence of a series of secondary and tertiary N,N'-diarylureas (aryl = phenyl, 2-naphthyl, 2-anthryl, and pyren-1-yl) has been investigated at 77 K and at room temperature in the glass-forming solvent methyltetrahydrofuran. The secondary diarylureas possess planar extended structures, whereas the tertiary diarylureas possess folded structures in which the aryl groups are face-to-face. The secondary and tertiary diphenylureas display broad, weak fluorescence attributed to an n,pi* singlet state at low temperature and are non-fluorescent at room temperature. The other secondary diarylureas are strongly fluorescent both at 77 K and at room temperature. Their fluorescence resembles that of the parent arene and is assigned to a lowest pi,pi* singlet state. The fluorescence of the other tertiary diarylureas is similar to that of the secondary diarylureas at 77 K, but is broad and red-shifted in fluid solution, as a consequence of intramolecular excimer formation. The properties of these novel intramolecular excimers are compared with those of 1,3-diarylalkanes and paracyclophanes.

Journal Article↗