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81.
    
We are reporting the application of scanning electrochemical cell microscopy to probe and identify nanometric defects in a multilayered aryl film formed by aryldiazonium reduction. We have determined by numerical simulation that, due to pipette geometry restrictions, the best sensitivity towards pinhole size can be obtained when measuring small pinholes (≤10 nm) with moderately large pipette sizes (ca. 500 nm).  相似文献   
82.
We investigate a life time broadened and coherently prepared five-state system for multi-wave mixing processes. We show that very efficient wave mixing occurs, producing an unconventional mixing wave that has the characteristics of both conventional four-wave mixing (FWM) and stimulated hyper-Raman (SHR) emission. In addition, we show interesting multiple simultaneous multi-photon interference effects at large propagation distances and demonstrate more than 10 orders of magnitude suppression of populations of the probe wave terminal state and the near three-photon resonance mixing wave generating state. These new type of multi-photon interference based induced transparency effects, which are critically dependent on two distinctive relaxation processes involving both an external supplied and an internally generated fields, are fundamentally different from the conventional three-state electromagnetically induced transparency effect which does not depend on propagation. As a consequence, both the probe and the wave-mixing field to propagate nearly free of absorption and distortions in a highly dispersive medium.  相似文献   
83.
We report the first experimental observation of strong suppression of matter-wave superradiance using blue-detuned pump light and demonstrate a pump-laser detuning asymmetry in the collective atomic recoil motion. In contrast to all previous theoretical frameworks, which predict that the process should be symmetric with respect to the sign of the detuning of the pump laser from the one-photon resonance, we find that for condensates the symmetry is broken. With high condensate densities and red-detuned pump light the distinctive multiorder, matter-wave scattering pattern is clearly visible, whereas with blue-detuned pump light superradiance is strongly suppressed. However, in the limit of a dilute atomic gas symmetry is restored.  相似文献   
84.
Choline is a precursor of cellular phospholipid metabolism that provides Magnetic Resonance (MR) and Positron Emission Tomography (PET) biomarkers for cancer detection and response assessment. Employing Dynamic Nuclear Polarization we show that the MR signal of 15N in choline can be enhanced by at least 4 orders of magnitude with a relaxation time of ca. 4 min, providing a method to observe the action of choline kinase, an important target for novel cancer therapeutics.  相似文献   
85.
The reactivity of triplet 16-electron organometallic species has been studied in room-temperature solution using femtosecond UV pump IR probe spectroscopy. Specifically, the Si-H bond-activation reaction of photogenerated triplet Fe(CO)(4) and triplet CpCo(CO) with triethylsilane has been characterized and compared to the known singlet species CpRh(CO). The intermediates observed were studied using density functional theory (DFT) as well as ab initio quantum chemical calculations. The triplet organometallics have a greater overall reactivity than singlet species due to a change in the Si-H activation mechanism, which is due to the fact that triplet intermediates coordinate weakly at best with the ethyl groups of triethylsilane. Consequently, the triplet species do not become trapped in alkyl-solvated intermediate states. The experimental results are compared to the theoretical calculations, which qualitatively reproduce the trends in the data.  相似文献   
86.
The phosphorus based radical precursors N-ethylpiperidine hypophosphite (EPHP) and diethylphosphine oxide (DEPO) are efficient reagents for carrying out the formation of seven- and eight-membered rings. Esters and amides were successfully converted into the corresponding eight-membered lactones and seven- and eight-membered lactams in good to excellent yields.  相似文献   
87.
    
Despite the unique chemical properties of selenocysteine (Sec), ligation at Sec is an under‐utilized methodology for protein synthesis. We describe herein an unprecedented protocol for the conversion of Sec to serine (Ser) in a single, high‐yielding step. When coupled with ligation at Sec, this transformation provides a new approach to programmed ligations at Ser residues. This new reaction is compatible with a wide range of functionality, including the presence of unprotected amino acid side chains and appended glycans. The utility of the methodology is demonstrated in the rapid synthesis of complex glycopeptide fragments of the epithelial glycoproteins MUC5AC and MUC4 and through the total synthesis of the structured, cysteine (Cys)‐free protein eglin C.  相似文献   
88.
    
First principles electronic structure calculations are typically performed in terms of molecular orbitals (or bands), providing a straightforward theoretical avenue for approximations of increasing sophistication, but do not usually provide any qualitative chemical information about the system. We can derive such information via post‐processing using natural bond orbital (NBO) analysis, which produces a chemical picture of bonding in terms of localized Lewis‐type bond and lone pair orbitals that we can use to understand molecular structure and interactions. We present NBO analysis of large‐scale calculations with the ONETEP linear‐scaling density functional theory package, which we have interfaced with the NBO 5 analysis program. In ONETEP calculations involving thousands of atoms, one is typically interested in particular regions of a nanosystem whilst accounting for long‐range electronic effects from the entire system. We show that by transforming the Non‐orthogonal Generalized Wannier Functions of ONETEP to natural atomic orbitals, NBO analysis can be performed within a localized region in such a way that ensures the results are identical to an analysis on the full system. We demonstrate the capabilities of this approach by performing illustrative studies of large proteins—namely, investigating changes in charge transfer between the heme group of myoglobin and its ligands with increasing system size and between a protein and its explicit solvent, estimating the contribution of electronic delocalization to the stabilization of hydrogen bonds in the binding pocket of a drug‐receptor complex, and observing, in situ, the n → π* hyperconjugative interactions between carbonyl groups that stabilize protein backbones. © 2012 Wiley Periodicals, Inc.  相似文献   
89.
    
Quantitative chemical state X‐ray photoelectron spectroscopic analysis of mixed nickel metal, oxide, hydroxide and oxyhydroxide systems is challenging due to the complexity of the Ni 2p peak shapes resulting from multiplet splitting, shake‐up and plasmon loss structures. Quantification of mixed nickel chemical states and the qualitative determination of low concentrations of Ni(III) species are demonstrated via an approach based on standard spectra from quality reference samples (Ni, NiO, Ni(OH)2, NiOOH), subtraction of these spectra, and data analysis that integrates information from the Ni 2p spectrum and the O 1s spectra. Quantification of a commercial nickel powder and a thin nickel oxide film grown at 1‐Torr O2 and 300 °C for 20 min is demonstrated. The effect of uncertain relative sensitivity factors (e.g. Ni 2.67 ± 0.54) is discussed, as is the depth of measurement for thin film analysis based on calculated inelastic mean free paths. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   
90.
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