Combinatorics,graph theory,and computing

Journal of Algebraic Combinatorics -     

Acid/Base‐Triggered Switching of Circularly Polarized Luminescence and Electronic Circular Dichroism in Organic and Organometallic Helicenes

Electronic circular dichroism and circularly polarized luminescence acid/base switching activity has been demonstrated in helicene‐bipyridine proligand 1 a and in its “rollover” cycloplatinated derivative 2 a . Whereas proligand 1 a displays a strong bathochromic shift (>160 nm) of the nonpolarized and circularly polarized luminescence upon protonation, complex 2 a displays slightly stronger emission. This strikingly different behavior between singlet emission in the organic helicene and triplet emission in the organometallic derivative has been rationalized by using quantum‐chemical calculations. The very large bathochromic shift of the emission observed upon protonation of azahelicene‐bipyridine 1 a has been attributed to the decrease in aromaticity (promoting a charge‐transfer‐type transition rather than a π–π* transition) as well as an increase in the HOMO–LUMO character of the transition and stabilization of the LUMO level upon protonation.     

Bimetallic Gold(I) Complexes with Ethynyl‐Helicene and Bis‐Phosphole Ligands: Understanding the Role of Aurophilic Interactions in their Chiroptical Properties

Monometallic gold(I)‐alkynyl‐helicene complexes ( 1 a , b ) and bimetallic gold(I)‐alkynyl‐helicene architectures featuring the presence ( 2 a , b ) or absence ( 3 a , b ) of aurophilic intramolecular interactions were prepared by using different types of phosphole ligands (mono‐phosphole L1 or bis‐phospholes L2 , 3 ). The influence of the Au^I d¹⁰ metal center(s) on the electronic, photophysical, and chiroptical properties of these unprecedented phosphole‐gold(I)‐alkynyl‐helicene complexes was examined. Experimental and theoretical results highlight the importance of ligand‐to‐ligand‐type charge transfers and the strong effect of the presence or absence of Au^I–Au^I interactions in 2 a , b .     

High‐Energy Long‐Lived Mixed Frenkel–Charge‐Transfer Excitons: From Double Stranded (AT)n to Natural DNA

The electronic excited states populated upon absorption of UV photons by DNA are extensively studied in relation to the UV‐induced damage to the genetic code. Here, we report a new unexpected relaxation pathway in adenine–thymine double‐stranded structures (AT)_n. Fluorescence measurements on (AT)_n hairpins (six and ten base pairs) and duplexes (20 and 2000 base pairs) reveal the existence of an emission band peaking at approximately 320 nm and decaying on the nanosecond time scale. Time‐dependent (TD)‐DFT calculations, performed for two base pairs and exploring various relaxation pathways, allow the assignment of this emission band to excited states resulting from mixing between Frenkel excitons and adenine‐to‐thymine charge‐transfer states. Emission from such high‐energy long‐lived mixed (HELM) states is in agreement with their fluorescence anisotropy (0.03), which is lower than that expected for π–π* states (≥0.1). An increase in the size of the system quenches π–π* fluorescence while enhancing HELM fluorescence. The latter process varies linearly with the hypochromism of the absorption spectra, both depending on the coupling between π–π* and charge‐transfer states. Subsequently, we identify the common features between the HELM states of (AT)_n structures with those reported previously for alternating (GC)_n: high emission energy, low fluorescence anisotropy, nanosecond lifetimes, and sensitivity to conformational disorder. These features are also detected for calf thymus DNA in which HELM states could evolve toward reactive π–π* states, giving rise to delayed fluorescence.     

m-Chloroperbenzoic acid-oxchromium (VI)-mediated cleavage of 2,4,5-trisubstituted oxazoles

An array of 2-substituted-4,5-diphenyloxazoles were found to be cleaved to triacylamines and diacylamines (imides) using a reagent system composed of m-chloroperbenzoic acid (MCPBA) and 2,2′-bipyridinium chlorochromate (BPCC). The 2-alkyl-4,5-diphenyloxazoles give imides (38–60%) as the predominant cleavage product while the 2-aryl-4,5-diphenyloxazoles give triacylamines (44–71%). Two mechanisms involving intermediates such as cyclic endoperoxides or oxachromacycles were proposed. An application of the oxidative cleavage to the multi-step synthesis of (±)-phoracantholide I seco acid is detailed.     

Microgravity flow regime data and analysis

To utilize the advantageous properties of two-phase flow in microgravity applications, the knowledge base of two-phase flow phenomena must be extended to include the effects of gravity. In the experiment described, data regarding the behavior of two-phase flow in a conduit under microgravity conditions (essentially zero gravity) are explored. Of particular interest, knowledge of the void fraction of the gas and liquid in a conduit is necessary to develop models for heat and mass transfer, pressure drop, and wall shear. An experiment was conducted under reduced gravity conditions to collect data by means of a capacitance void fraction sensor and high speed visual imagery. Independent parameters were varied to map the flow regime regions. These independent parameters include gas and liquid volumetric flow rates and saturation pressures. Void fraction measurements were taken at a rate of 100 Hz with six sensors at two locations along the conduit. Further, statistical parameters were developed from the void fraction measurements. Statistical parameters such as variance, signal-to-noise ratio, half height value, and linear area difference were calculated and found to have characteristics allowing flow regime identification.     

TheL 2 squeezing property for nonlinear bipolar viscous fluids

A squeezing property inL ²() is established for orbits of the semigroup associated with the equations of motion of a nonlinear incompressible bipolar viscous fluid; it is assumed that=[0,L] ⁿ ,n=2 or 3,L>0, and that the velocity vector satisfies a spatial periodicity condition. The proof depends, in an essential manner, on key estimates for both the nonlinear operator generated by the nonlinear viscosity term in the model and the time integral of theH ³() norm of the velocity.     

Model analysis of box culverts subjected to highway loading

The strain distribution and the deflections of reinforced-concrete box culverts associated with highway loading are determined by testing scale models. Two types of scale models were constructured: 1/6-size concrete models and a 1/24-size photoelastic model. The concrete models were instrumented with electric-resistance strain gages, and the deflections were measured with dial indicators. Strain and deflection data due to live loading are compared with values from testing of prototypes. The results of testing indicate that box-culvert sections conforming to ASTM C 850 are overdesigned structurally. Testing of models of a redesigned box culvert indicates that they perform satisfactorily. Paper was presented in the Proceedings of the 1988 SEM Conference on Experimental Mechanics held in Portland, OR on June 5–10.