Quantum decoherence can be viewed as the mechanism responsible for the quantum-to-classical transition as the initially prepared quantum state interacts with its environment in an irreversible manner. One of the most common mechanisms responsible for the macroscopically observed decoherence involves collisions of an atom or molecule, initially prepared in a coherent superposition of states, with gas particles. In this work, a coherent superposition of quantum internal states of NO molecules is prepared by the interaction between the molecule with both a static and a radiofrequency electric field. Subsequently, NO + Ar collision decoherence experiments are investigated by measuring the loss of coherence as a function of the number of collisions. Data analysis using a model based on the interaction potential of the collisional partners allowed to unravel the molecular mechanism responsible for the loss of coherence in the prepared NO quantum superposition of internal states. The relevance of the present work relies on several aspects. On the one hand, the use of radio-waves introduces a new way for the production of coherent beams. On the other hand, the employed methodology could be useful in investigating the Stereodynamics of chemical reactions with coherent reagents. © 2013 American Chemical Society.

A number of isomer structures can be formed in hydrogen-bonded clusters, reflecting the essential variety of structural motifs of hydrogen bond networks. Control of isomer distribution of a cluster is important not only in practical use for isomer-specific spectroscopy but also in understanding of isomerization processes of hydrogen bond networks. Protonated methanol clusters have relatively simple networks and they are model systems suitable to investigate isomer distribution changes. In this paper, isomer distribution of H+(CH3OH)7 is studied by size-selective infrared spectroscopy in the OH and CH stretching vibrational region and density functional theory calculations. While the clusters produced by a supersonic jet expansion combined with electron ionization were predominantly isomers having open hydrogen bond networks such as a linear chain, the Ar or Ne attachment (so-called rare gas tagging) entirely switches the isomer structures to compactly folded ones, which are composed only of closed multiple rings. The origin of the isomer switching is discussed in terms of thermal effects and specific isomer preference.

We utilize single molecule spectroscopy combined with time-correlated single-photon counting to probe electron transfer (ET) kinetics from CdSe/ZnS (core/shell) quantum dots (QDs) to TiO2 through various lengths of linker molecules. The QD-linker-TiO2 complexes with varied linker length, linker structure, and QD size are fabricated by a surface-based stepwise method to show control of the rate and of the magnitude of fluctuations of photo-induced ET at the single molecule level. The ET rate constants are determined to be 2.8×107, 1.9×107, and 3.5×106s-1 for the chain length of 1.5, 6.2 and 13.8Å, respectively. The electronic coupling strengths between QDs and TiO2 are further calculated to be 3.68, 3.60, and 1.59cm-1 for the three different chain lengths by using the Marcus ET model. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

This Note aims to clarify the source of CO in photodissociation of acetyl cyanide (CH3COCN) at 308 nm. From the theoretical aspects, a new pathway via isomerization transition state (TS) at 391 ± 8 kJ/mol is found leading to the CO + CH3NC products. An amount of 60% reactant molecules at 300 K is estimated to successfully surpass the average TS barrier lying above the excitation energy by 3.5 kJ/mol. Further, a prior distribution method is conducted to characterize the vibrational energy distribution of CO on a statistical basis. The pathway to CH3NC + CO yields a vibrational branching ratio (v = 0:v = 1:v = 2:v = 3∼0.63:0.25:0.093:0.032) in excellent agreement with the observation (0.62:0.25:0.09:0.05). © 2013 AIP Publishing LLC.

Upon one-photon excitation at 248 nm, gaseous CH3C(O)SH is dissociated following three pathways with the products of (1) OCS + CH 4, (2) CH3SH + CO, and (3) CH2CO + H 2S that are detected using time-resolved Fourier-transform infrared emission spectroscopy. The excited state 1(nO, π *CO) has a radiative lifetime of 249 ± 11 ns long enough to allow for Ar collisions that induce internal conversion and enhance the fragment yields. The rate constant of collision-induced internal conversion is estimated to be 1.1 × 10-10 cm3 molecule -1 s-1. Among the primary dissociation products, a fraction of the CH2CO moiety may undergo further decomposition to CH2 + CO, of which CH2 is confirmed by reaction with O2 producing CO2, CO, OH, and H2CO. Such a secondary decomposition was not observed previously in the Ar matrix-isolated experiments. The high-resolution spectra of CO are analyzed to determine the ro-vibrational energy deposition of 8.7 ± 0.7 kcal/mol, while the remaining primary products with smaller rotational constants are recognized but cannot be spectrally resolved. The CO fragment detected is mainly ascribed to the primary production. A prior distribution method is applied to predict the vibrational distribution of CO that is consistent with the experimental findings. © 2013 American Institute of Physics.

BACKGROUND AND PURPOSE: Telomerase is the enzyme responsible for extending G-strand telomeric DNA and represents a promising target for treatment of neoplasia. Inhibition of telomerase can be achieved by stabilization of G-quadruplex DNA structures. Here, we characterize the cellular effects of a novel G-quadruplex stabilizing compound, 3,6-bis(4-methyl-2-vinylpyrazinium iodine) carbazole (BMVC4). EXPERIMENTAL APPROACH: The cellular effects of BMVC4 were characterized in both telomerase-positive and alternative lengthening of telomeres (ALT) cancer cells. The molecular mechanism of how BMVC4 induced senescence is also addressed. KEY RESULTS: BMVC4-treated cancer cells showed typical senescence phenotypes. BMVC4 induced senescence in both ALT and telomerase-overexpressing cells, suggesting that telomere shortening through telomerase inhibition might not be the cause for senescence. A large fraction of DNA damage foci was not localized to telomeres in BMVC4-treated cells and BMVC4 suppressed c-myc expression through stabilizing the G-quadruplex structure located at its promoter. These results indicated that the cellular targets of BMVC4 were not limited to telomeres. Further analyses showed that BMVC4 induced DNA breaks and activation of ataxia telangiectasia-mutated mediated DNA damage response pathway. CONCLUSIONS AND IMPLICATIONS: BMVC4, a G-quadruplex stabilizer, induced senescence by activation of pathways of response to DNA damage that was independent of its telomerase inhibitory activity. Thus, BMVC4 has the potential to be developed as a chemotherapeutic agent against both telomerase positive and ALT cancer cells.

We demonstrate that the long-lived bound states (supermolecules) can exist in the dilute limit when we tune the shape of the effective potential between polar molecules by an external microwave field. Binding energies, average sizes, and phase diagrams for both s-orbital (bosons) and p-orbital (fermions) dimers are studied, together with bosonic trimer states. We explicitly show that the nonadiabatic transition rate can be easily tuned small for such ground-state supermolecules, so that the system can be stable from collapse even near the associated potential resonance. Our results, therefore, suggest a feasible cold molecule system to investigate novel few-body and many-body physics (for example, the p-wave BCS-Bose-Einstein-condensate crossover for fermions and the paired condensate for bosons) that cannot be easily accessed in single species atomic gases.

A p-T phase diagram of graphene nanoribbons (GNRs) terminated by hydrogen atoms is established based on first-principles calculations, where the stable phase at standard conditions (25 degrees C and 1 bar) is found to be a zigzag GNR (zzGNR). The stability of this new GNR is understood based on an electron-counting model, which predicts semiconducting nonmagnetic zzGNRs. Quantum confinement of Dirac fermions in the stable zzGNRs is found to be qualitatively different from that in ordinary semiconductors. Bifurcation of the band gap is predicted to take place, leading to the formation of polymorphs with distinct band gaps but equal thermodynamic stability. A tight-binding model analysis reveals the role of edge symmetry on the band-gap bifurcation.

The Hofstadter butterfly spectrum for Landau levels in a two-dimensional periodic lattice is a rare example exhibiting fractal properties in a truly quantum system. However, the observation of this physical phenomenon in a conventional material will require a magnetic field strength several orders of magnitude larger than what can be produced in a modern laboratory. It turns out that for a specific range of rotational angles twisted bilayer graphene serves as a special system with a fractal energy spectrum under laboratory accessible magnetic field strengths. This unique feature arises from an intriguing electronic structure induced by the interlayer coupling. Using a recursive tight-binding method, we systematically map out the spectra of these Landau levels as a function of the rotational angle. Our results give a complete description of LLs in twisted bilayer graphene for both commensurate and incommensurate rotational angles and provide quantitative predictions of magnetic field strengths for observing the fractal spectra in these graphene systems.

Three binary molecule conjugates were designed and synthesized by conjugating a chromophore (3, 6-bis-(1-methyl-4-vinylpyridinium)-carbazole diiodide, BMVC) to mono-, bis- and trishydroxyl photosensitizers, respectively. BMVC plays the role of cancer cells recognizer; AIEE (aggregation-induced emission enhancement) generator and FRET (Fluorescence Resonance Energy Transfer) donor. The self assembling properties of these binary conjugates result in different degrees of AIEE and then achieve the formations of FONs (fluorescent organic nanoparticles), which present efficient FRET and singlet oxygen generations. Biologically, FONs-photosensitizers from these compounds were much more phototoxicities to cancer cell than to normal cell without significant dark toxicity. In addition, their intracellular fluorescent colors switching upon photo-excitation are expected to be used for further cell death biomarker applications. This improved photodynamic activity might be due to the aggregation of compounds in the cell that form FONs which can promote PDT (photodynamic therapy) and are observed in cancer cell but not normal cell.

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