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.     

Extended hydrodynamic approach to quantum-classical nonequilibrium evolution. I. Theory

A mixed quantum-classical formulation is developed for a quantum subsystem in strong interaction with an N-particle environment, to be treated as classical in the framework of a hydrodynamic representation. Starting from the quantum Liouville equation for the N-particle distribution and the corresponding reduced single-particle distribution, exact quantum hydrodynamic equations are obtained for the momentum moments of the single-particle distribution coupled to a discretized quantum subsystem. The quantum-classical limit is subsequently taken and the resulting hierarchy of equations is further approximated by various closure schemes. These include, in particular, (i) a Grad-Hermite-type closure, (ii) a Gaussian closure at the level of a quantum-classical local Maxwellian distribution, and (iii) a dynamical density functional theory approximation by which the hydrodynamic pressure term is replaced by a free energy functional derivative. The latter limit yields a mixed quantum-classical formulation which has previously been introduced by I. Burghardt and B. Bagchi, Chem. Phys. 134, 343 (2006).     

SYNTHESIS OF CHIRAL THIOCARBAMOYLPHOSPHINES DERIVED FROM AMINO ACIDS1

Abstract

The methylester hydrochlorides of the (S)-amino acids L-alanine (la), L-phenylalanine (1b), L-valine (1c) and L-lysine (1d) were converted to the corresponding isothiocyanates 2a-d by thiophosgenation. 2a-d react with secondary phosphines and phosphine oxides to give the thiocarbamoylphosphines 3a-d and P-oxides 4a, b.     

Polydomain model predictions of liquid crystalline polymer orientation in mixed shear/extensional channel flows

 The Larson-Doi (LD) polydomain model is used to simulate orientation development along the centerline of slit-expansion and slit-contraction flows of liquid crystalline polymers (LCPs). Orientation is computed using the LD structural evolution equations, subject to an imposed velocity field that accounts for the spatial variation of both shear and extension rates characteristic of this class of flows. Computed axial distributions of orientation averaged through the sample thickness are qualitatively similar to birefringence and X-ray scattering measurements of molecular orientation in similar flows of lyotropic and thermotropic LCPs. In slit-expansion flows, the simulations predict a 90^∘ flip in orientation direction near the midplane due to transverse stretching in the expansion region. Far away from the midplane where shear gradients dominate, orientation remains primarily along the flow direction. Within the LD model, tumbling and flow aligning materials respond in a qualitatively similar manner to mixed shear and extension, although tumbling materials are systematically more susceptible to the effects of extension. Received: 22 October 1999/Accepted: 13 January 2000     

The Effects of a Mathematics Infusion Curriculum on Middle School Student Mathematics Achievement

Increasing mathematical competencies of American students has been a focus for educators, researchers, and policy makers alike. One purported approach to increase student learning is through connecting mathematics and science curricula. Yet there is a lack of research examining the impact of making these connections. The Mathematics Infusion into Science Project, funded by the National Science Foundation, developed a middle school mathematics‐infused science curriculum. Twenty teachers utilized this curriculum with over 1,200 students. The current research evaluated the effects of this curriculum on students' mathematics learning and compared effects to students who did not receive the curriculum. Students who were taught the infusion curriculum showed a significant increase in mathematical content scores when compared with the control students.     

Ultrasonic fatigue tests with stabilized amplitude and controlled temperature

An attachment for fatigue testing was developed, complementary to a commercially available ultrasonic generator with a power of 200 W. The fundamental improvements are: a control system which stabilizes the fatigue amplitude, and a programming attachment which supplies ultrasonic fatigue pulses in order to prevent undesirable temperature rises caused by internal friction. Similar attachments were developed for generators with powers of 400, 1 000 and 2 500 W. These improved fatigue testing machines permit investigations concerning the fatigue behaviour of metals with a remarkably high degree of damping.     

Mass spectral determination of skeletal/cardiac actin isoform ratios in cardiac muscle

Skeletal and cardiac muscle contains actin isoforms that vary by two juxtaposed amino acids and two amino acid substitutions (Met299Leu and Ser358Thr). This close sequence homology does not allow cardiac and skeletal actin isoforms to be resolved in traditional SDS-PAGE analysis as the molecular weights (Deltamass = 32 Da) are not significantly different and the pIs are identical (5.2). Although cardiac actin is the predominant form in cardiac muscle, there appears to be a specific skeletal/cardiac actin ratio in a normal heart that may vary in a compromised or diseased heart. In an effort to ascertain the validity of this hypothesis we developed a mass spectrometric technique to measure the ratio of skeletal to cardiac actin. The technique involves purification of muscle actin and subsequent liquid chromatography coupled with electrospray ionization Fourier transform ion cylcotron resonance (LC/FTICR-MS) mass spectrometry. A 7 Tesla FTICR mass spectrometer was utilized to compare skeletal/cardiac actin isoform ratios. Additionally, a new dual electrospray ionization source was employed to determine accurate masses of the alpha-skeletal and alpha-cardiac actins.