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Time-resolved femtosecond x-ray diffraction patterns from laser-excited molecular iodine are used to create a movie of intramolecular motion with a temporal and spatial resolution of 30 fs and 0.3 Å. This high fidelity is due to interference between the nonstationary excitation and the stationary initial charge distribution. The initial state is used as the local oscillator for heterodyne amplification of the excited charge distribution to retrieve real-space movies of atomic motion on ångstrom and femtosecond scales. This x-ray interference has not been employed to image internal motion in molecules before. Coherent vibrational motion and dispersion, dissociation, and rotational dephasing are all clearly visible in the data, thereby demonstrating the stunning sensitivity of heterodyne methods.
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Superionic conductors, or solid-state ion-conductors surpassing 0.01 S/cm in conductivity, can enable more energy dense batteries, robust artificial ion pumps, and optimized fuel cells. However, tailoring superionic conductors requires precise knowledge of ion migration mechanisms that are still not well understood due to limitations set by available spectroscopic tools. Most spectroscopic techniques do not probe ion hopping at its inherent picosecond timescale nor the many-body correlations between the migrating ions, lattice vibrational modes, and charge screening clouds-all of which are posited to greatly enhance ionic conduction. Here, we develop an ultrafast technique that measures the time-resolved change in impedance upon light excitation, which triggers selective ion-coupled correlations. We also develop a cost-effective, non-time-resolved laser-driven impedance method that is more accessible for lab-scale adoption. We use both techniques to compare the relative changes in impedance of a solid-state Li+ conductor Li0.5La0.5TiO3 (LLTO) before and after UV to THz frequency excitations to elucidate the corresponding ion-many-body-interaction correlations. From our techniques, we determine that electronic screening and phonon-mode interactions dominate the ion migration pathway of LLTO. Although we only present one case study, our technique can extend to O2-, H+, or other charge carrier transport phenomena where ultrafast correlations control transport. Furthermore, the temporal relaxation of the measured impedance can distinguish ion transport effects caused by many-body correlations, optical heating, correlation, and memory behavior.
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BACKGROUND AND PURPOSE: Quantitative metrics of the dural sac such as the cross-sectional area are commonly used to evaluate central canal stenosis. The aim of this study was to analyze 2 new metrics to measure spinal stenosis on the basis of the ratio between the dural sac and disc cross-sectional areas (DDRCA) and the dural sac and disc anterior-posterior diameters (DDRDIA) and compare them with established quantitative metrics of the dural sac. MATERIALS AND METHODS: T2-weighted axial MR images (n = 260 patients) were retrospectively evaluated, graded for central canal stenosis as normal (no stenosis), mild, moderate, or severe from L1/L2 through L5/S1 with 1 grade per spinal level and annotated to measure the DDRCA and DDRDIA. Thresholds were obtained using a decision tree classifier on a subset of patients (n = 130) and evaluated on the remaining patients (n = 130) for accuracy and consistency across demographics, anatomic variation, and clinical outcomes. RESULTS: DDRCA and DDRDIA had areas under the receiver operating characteristic curve of 98.6 (97.4-99.3) and 98.0 (96.7-98.9) compared with dural sac cross-sectional area at 96.5 (95.0-97.7) for binary classification. DDRDIA and DDRCA had κ scores of 0.75 (0.71-0.79) and 0.80 (0.75-0.83) compared with dural sac cross-sectional area at 0.62 (0.57-0.66) for multigrade classification. No significant differences (P > .1) in the area under the receiver operating characteristic curve were observed for the DDRDIA across variations in the body mass index. The DDRDIA also had the highest area under the receiver operating characteristic curve among symptomatic patients (visual analog scale ≥ 7) or patients who underwent surgery. CONCLUSIONS: Ratio-based metrics (DDRDIA and DDRCA) are accurate and robust to anatomic and demographic variability compared with quantitative metrics of the dural sac and better correlated with symptomatology and surgical outcomes.
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Estenose Espinal , Humanos , Estenose Espinal/diagnóstico por imagem , Estudos Retrospectivos , Imageamento por Ressonância Magnética/métodos , Vértebras Lombares/diagnóstico por imagem , Constrição PatológicaRESUMO
Ultrafast strong-field physics provides insight into quantum phenomena that evolve on an attosecond time scale, the most fundamental of which is quantum tunneling. The tunneling process initiates a range of strong field phenomena such as high harmonic generation (HHG), laser-induced electron diffraction, double ionization and photoelectron holography-all evolving during a fraction of the optical cycle. Here we apply attosecond photoelectron holography as a method to resolve the temporal properties of the tunneling process. Adding a weak second harmonic (SH) field to a strong fundamental laser field enables us to reconstruct the ionization times of photoelectrons that play a role in the formation of a photoelectron hologram with attosecond precision. We decouple the contributions of the two arms of the hologram and resolve the subtle differences in their ionization times, separated by only a few tens of attoseconds.
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Many photoinduced processes including photosynthesis and human vision happen in organic molecules and involve coupled femtosecond dynamics of nuclei and electrons. Organic molecules with heteroatoms often possess an important excited-state relaxation channel from an optically allowed ππ* to a dark nπ* state. The ππ*/nπ* internal conversion is difficult to investigate, as most spectroscopic methods are not exclusively sensitive to changes in the excited-state electronic structure. Here, we report achieving the required sensitivity by exploiting the element and site specificity of near-edge soft X-ray absorption spectroscopy. As a hole forms in the n orbital during ππ*/nπ* internal conversion, the absorption spectrum at the heteroatom K-edge exhibits an additional resonance. We demonstrate the concept using the nucleobase thymine at the oxygen K-edge, and unambiguously show that ππ*/nπ* internal conversion takes place within (60 ± 30) fs. High-level-coupled cluster calculations confirm the method's impressive electronic structure sensitivity for excited-state investigations.Many photo-induced processes such as photosynthesis occur in organic molecules, but their femtosecond excited-state dynamics are difficult to track. Here, the authors exploit the element and site selectivity of soft X-ray absorption to sensitively follow the ultrafast ππ*/nπ* electronic relaxation of hetero-organic molecules.
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With the help of previously introduced enumeration procedure (M.Yu. Shchelkanov, A.N. Yudin, A.V Antonov, N.S. Starikov, A.A. Vedenov, E.V. Karamov, J. Biomol. Struct. Dyn. 15, 217-229 (1997)) and probability distribution function for the enumeration after some substitution steps (M.Yu. Shchelkanov, L.A. Soinov, V.V. Zalunin, D.A. Gumennyi, A.N. Yudin, A.A. Natan, V.B. Kireev, E.V. Karamov, J. Biomol. Struct. Dyn. 15, N 4, (1998)) we have demonstrated that dependencies of replication acts number on Hamming distance are identical for one-parameter discrete models of both direct and parallel genetic diversity.
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Variação Genética , Proteína gp120 do Envelope de HIV/genética , Modelos Moleculares , Modelos Estatísticos , Fragmentos de Peptídeos/genética , Evolução Molecular , HumanosRESUMO
One-parameter discrete model estimating genetic distance between precursor and descendant nucleotide sequences after several steps of substitution acts is developed. This model based on the previously introduced symbol sequences enumeration procedure (M.Y. Shchelkanov, A.N. Yudin, A.V. Antonov, N.S. Starikov, A.A. Vedenov, E.V. Karamov, J. Biomol. Struct. Dyn. 15, 231-241 (1997)) differs from Jukes-Cantor and Kimura models by the absence of the assumptions usual for continuous Markov's processes. Formula obtained with the help of our model are more preferable since they take into account multiple repetition substitution ability and they are correct in the entire admissible range of parameters.
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Globinas/genética , Computação Matemática , Modelos Genéticos , Animais , Galinhas , CoelhosRESUMO
Molecules can efficiently and selectively convert light energy into other degrees of freedom. Disentangling the underlying ultrafast motion of electrons and nuclei of the photoexcited molecule presents a challenge to current spectroscopic approaches. Here we explore the photoexcited dynamics of molecules by an interaction with an ultrafast X-ray pulse creating a highly localized core hole that decays via Auger emission. We discover that the Auger spectrum as a function of photoexcitation--X-ray-probe delay contains valuable information about the nuclear and electronic degrees of freedom from an element-specific point of view. For the nucleobase thymine, the oxygen Auger spectrum shifts towards high kinetic energies, resulting from a particular C-O bond stretch in the ππ* photoexcited state. A subsequent shift of the Auger spectrum towards lower kinetic energies displays the electronic relaxation of the initial photoexcited state within 200 fs. Ab-initio simulations reinforce our interpretation and indicate an electronic decay to the nπ* state.