Reasons for different activities of various type catalysts in reactions of oxidation of inorganic substances

The dual role of catalysts in the interaction between an inorganic molecule AB and adsorbed oxygen ZO, as an electron donor (in the oxidative addition of AB) and as an electron acceptor (in subsequent ZO reduction), permits to interpret the orders of activities of various optimal catalysts and their dependence on the AB structure.

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AB ZO — ( AB) ( ZO). AB.

     

An Improved Measurement of Isotopic Ratios by High Resolution Mass Spectrometry

The study of protein kinetics requires an accurate measurement of isotopic ratios of peptides. Although Fourier transform-ion cyclotron resonance (FT-ICR) mass spectrometers yield accurate mass measurements of analytes, the isotopologue ratios are consistently lower than predicted. Recently, we demonstrated that the magnitude of the spectral error in the FT-ICR mass spectrometer is proportional to the scan duration of ions. Here, we present a novel isotopic ratio extrapolation (IRE) method for obtaining accurate isotopic ratio measurements. Accuracy is achieved by performing scans with different duration and extrapolation of the data to the initial moment of the ion rotation; IRE minimizes the absolute isotopic ratio error to ≤1 %. We demonstrate the application of IRE in protein turnover studies using ²H₂O-metabolic labeling. Overall, this technique allows accurate measurements of the isotopic ratios of proteolytic peptides, a critical step for enabling routine studies of proteome dynamics.      

A Versatile Long‐Wavelength‐Absorbing Scaffold for Eu‐Based Responsive Probes

Coumarin‐sensitized, long‐wavelength‐absorbing luminescent Eu^III‐complexes have been synthesized and characterized. The lanthanide binding site consists of a cyclen‐based chelating framework that is attached through a short linker to a 7‐hydroxycoumarin, a 7‐B(OH)₂‐coumarin, a 7‐O‐(4‐pinacolatoboronbenzyl)‐coumarin or a 7‐O‐(4‐methoxybenzyl)‐coumarin. The syntheses are straightforward, use readily available building blocks, and proceed through a small number of high‐yielding steps. The sensitivity of coumarin photophysics to the 7‐substituent enables modulation of the antenna‐absorption properties, and thus the lanthanide excitation spectrum. Reactions of the boronate‐based functionalities (cages) with H₂O₂ yielded the corresponding 7‐hydroxycoumarin species. The same species was produced with peroxynitrite in a ×10⁶–10⁷‐fold faster reaction. Both reactions resulted in the emergence of a strong ≈407 nm excitation band, with concomitant decrease of the 366 nm band of the caged probe. In aqueous solution the methoxybenzyl caged Eu‐complex was quenched by ONOO^?. We have shown that preliminary screening of simple coumarin‐based antennae through UV/Vis absorption spectroscopy is possible as the changes in absorption profile translate with good fidelity to changes in Eu^III‐excitation profile in the fully elaborated complex. Taken together, our results show that the 7‐hydroxycoumarin antenna is a viable scaffold for the construction of turn‐on and ratiometric luminescent probes.     

Ultraviolet-assisted frequency trimming of optical microsphere resonators

We have demonstrated the engineering of a precise shift in the resonance frequency of high-Q (10(8))whispering-gallery modes in microspheres of germanium-doped silica with UV irradiation. With 600 mW of 351-nm radiation from an Ar-ion laser, 18-GHz permanent frequency shifts were obtained for modes of 1550-nm wavelength, enough to tune a resonance over a full free spectral range.     

Microtorus: a high-finesse microcavity with whispering-gallery modes

We demonstrate a 165-mu;m oblate spheroidal microcavity with a free spectral range of 383.7 GHz (3.06 nm), a resonance bandwidth of 23 MHz (quality factor Q approximately 10(7)) at 1550 nm, and finesse F>/=10(4) . The highly oblate spheroidal dielectric microcavity combines a very high Q factor, typical of microspheres, with a vastly reduced number of excited whispering-gallery modes (by 2 orders of magnitude). The very large free spectral range in this novel microcavity-a few hundred gigahertz instead of a few gigahertz as in typical microspheres-is desirable for applications in spectral analysis, narrow-linewidth optical and rf oscillators, and cavity QED.     

Frequency tuning of the whispering-gallery modes of silica microspheres for cavity quantum electrodynamics and spectroscopy

We have tuned the whispering-gallery modes of a fused-silica microresonator over nearly 1 nm at 800 nm, i.e., over half a free spectral range, or 10(6) linewidths of the resonator. This result has been achieved by use of a new method based on the stretching of a two-stem microsphere. We describe devices that will permit new cavity QED experiments with this high- Q optical resonator when it is desirable to optimize its coupling to emitters with given transition frequencies. The demonstrated tuning capability is compatible with both UHV and low-temperature operation, which should be useful for future experiments with laser-cooled atoms or single quantum dots.     

Generation of near-infrared frequency combs from a MgF₂ whispering gallery mode resonator

We report on generation of a 20 nm wide, 35 GHz repetition rate optical frequency comb in a magnesium fluoride whispering gallery mode resonator pumped with 2 mW of 1543 nm light. The high efficiency of comb generation is associated with the small anomalous group velocity dispersion of the resonator. Growth dynamics of the comb is studied and compared with earlier theoretical predictions.     

Influence of external magnetic field on the etching of a steel ball in an aqueous solution of nitric acid

The effect of change of shape of a steel ball was revealed as a result of its etching in an aqueous solution of nitric acid under influence of an external magnetic field. The elongation of a ferromagnetic ball was observed along the direction of an external magnetic field while etching took place uniformly in all the directions without magnetic field application. The steel ball etching in a magnetic field is characterized by formation of three cylindrically symmetric regions with different etching rates and surface structures, divided from each other by clear borders (namely, the pole, equator and transition regions are formed). The non-monotone dependences of etching rate, surface structure of a sample and sample shape after etching on an external magnetic field are observed.     

Tunable optical frequency comb with a crystalline whispering gallery mode resonator

We report on the experimental demonstration of a tunable monolithic optical frequency comb generator. The device is based on four-wave mixing in a crystalline calcium fluoride whispering gallery mode resonator. The frequency spacing of the comb is given by an integer number of the free spectral range of the resonator. We select the desired number by tuning the frequency of the pumping laser with respect to the corresponding resonator mode. We also observe a rich variety of optical combs and high-frequency hyperparametric oscillation, depending on the experimental conditions. A potential application of the comb for generating tunable narrow band frequency microwave signals is demonstrated.