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排序方式: 共有473条查询结果,搜索用时 11 毫秒
1.
Cappa CD Drisdell WS Smith JD Saykally RJ Cohen RC 《The journal of physical chemistry. B》2005,109(51):24391-24400
The microscopic events engendering liquid water evaporation have received much attention over the last century, but remain incompletely understood. We present measurements of isotope fractionation occurring during free molecular evaporation from liquid microjets and show that the isotope ratios of evaporating molecules exhibit dramatic differences from equilibrium vapor values, strong variations with the solution deuterium mole fraction, and a clear temperature dependence. These results indicate the existence of an energetic barrier to evaporation and that the evaporation coefficient of water is less than unity. These new insights into water evaporation promise to advance our understanding of the processes that control the formation and lifetime of clouds in the atmosphere. 相似文献
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Crochet JJ Hoseinkhani S Lüer L Hertel T Doorn SK Lanzani G 《Physical review letters》2011,107(25):257402
We present evidence for the generation of free carriers in aggregated single-wall carbon nanotubes by photoexcitation in the energetic range of the π→π(*) transition associated with the M saddle point of the graphene lattice. The underlying broad absorption culminating at 4.3 eV can be fit well with a Fano line shape that describes strong coupling of a saddle-point exciton to an underlying free electron-hole pair continuum. Moreover, it is demonstrated that transitions in this energetic region autoionize into the continuum by detecting features unique to the presence of free charges in the transient transmission spectra of the continuum-embedded second sub-band exciton, S(2). 相似文献
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Thomas JK Lovstedt SP Blotter JD Sommerfeldt SD 《The Journal of the Acoustical Society of America》2008,123(6):4238-4249
The FXLMS algorithm, which is extensively used in active noise control, exhibits frequency dependent convergence behavior. This leads to degraded performance for time-varying and multiple frequency signals. A new algorithm called the eigenvalue equalization filtered-x least mean squares (EE-FXLMS) has been developed to overcome this limitation without increasing the computational burden of the controller. The algorithm is easily implemented for either single or multichannel control. The magnitude coefficients of the secondary path transfer function estimate are altered while preserving the phase. For a reference signal that has the same magnitude at all frequencies, the secondary path estimate is given a flat response over frequency. For a reference signal that contains tonal components of unequal magnitudes, the magnitude coefficients of the secondary path are adjusted to be the inverse magnitude of the reference tones. Both modifications reduce the variation in the eigenvalues of the filtered-x autocorrelation matrix and lead to increased performance. Experimental results show that the EE-FXLMS algorithm provides 3.5-4.4 dB additional attenuation at the error sensor compared to normal FXLMS control. The EE-FXLMS algorithm's convergence rate at individual frequencies is faster and more uniform than the normal FXLMS algorithm with several second improvement being seen in some cases. 相似文献
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Yasmine S. Zubi Bingqing Liu Yifan Gu Dipankar Sahoo Jared C. Lewis 《Chemical science》2022,13(5):1459
Visible light photocatalysis enables a broad range of organic transformations that proceed via single electron or energy transfer. Metal polypyridyl complexes are among the most commonly employed visible light photocatalysts. The photophysical properties of these complexes have been extensively studied and can be tuned by modifying the substituents on the pyridine ligands. On the other hand, ligand modifications that enable substrate binding to control reaction selectivity remain rare. Given the exquisite control that enzymes exert over electron and energy transfer processes in nature, we envisioned that artificial metalloenzymes (ArMs) created by incorporating Ru(ii) polypyridyl complexes into a suitable protein scaffold could provide a means to control photocatalyst properties. This study describes approaches to create covalent and non-covalent ArMs from a variety of Ru(ii) polypyridyl cofactors and a prolyl oligopeptidase scaffold. A panel of ArMs with enhanced photophysical properties were engineered, and the nature of the scaffold/cofactor interactions in these systems was investigated. These ArMs provided higher yields and rates than Ru(Bpy)32+ for the reductive cyclization of dienones and the [2 + 2] photocycloaddition between C-cinnamoyl imidazole and 4-methoxystyrene, suggesting that protein scaffolds could provide a means to improve the efficiency of visible light photocatalysts.Artificial metalloenzyme visible light photocatalysts possess enhanced optical properties and are competent towards single electron and energy transfer organic transformations. 相似文献
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Lea Kremer Elisabeth Hennes Alexandra Brause Andrei Ursu Lucas Robke Hideaki T. Matsubayashi Yuta Nihongaki Jana Flegel Ivana Mejdrov Jan Eickhoff Matthias Baumann Radim Nencka Petra Janning Susanne Kordes Hans R. Schler Jared Sterneckert Takanari Inoue Slava Ziegler Herbert Waldmann 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(46):16770-16781
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The synthesis of 1,3-diaminated stereotriads via the bis-aziridination of allenes is reported. The reactive 1,4-diazaspiro[2.2]pentane intermediates undergo a mild Br?nsted acid-promoted rearrangement to yield 1,3-diaminated ketones in good yields with excellent stereocontrol. Directed reduction of the ketone can be achieved to yield a C-N/C-O/C-N stereotriad in high dr. The ability to transfer the axial chirality of the substrates to the products allows for the facile preparation of enantioenriched stereotriads from allenes in two simple steps. 相似文献