Improving precision in resonance ionization mass spectrometry: influence of laser bandwidth in uranium isotope ratio measurements.

The use of broad bandwidth lasers with automated feedback control of wavelength was applied to the measurement of (235)U/(238)U ratios by resonance ionization mass spectrometry (RIMS) to decrease laser-induced isotopic fractionation. By broadening the bandwidth of the first laser in a three-color, three-photon ionization process from a bandwidth of 1.8 GHz to about 10 GHz, the variation in sequential relative isotope abundance measurements decreased from 10% to less than 0.5%. This procedure was demonstrated for the direct interrogation of uranium oxide targets with essentially no sample preparation.

Increased silver activity for direct propylene epoxidation via subnanometer size effects.

Production of the industrial chemical propylene oxide is energy-intensive and environmentally unfriendly. Catalysts based on bulk silver surfaces with direct propylene epoxidation by molecular oxygen have not resolved these problems because of substantial formation of carbon dioxide. We found that unpromoted, size-selected Ag3 clusters and approximately 3.5-nanometer Ag nanoparticles on alumina supports can catalyze this reaction with only a negligible amount of carbon dioxide formation and with high activity at low temperatures. Density functional calculations show that, relative to extended silver surfaces, oxidized silver trimers are more active and selective for epoxidation because of the open-shell nature of their electronic structure. The results suggest that new architectures based on ultrasmall silver particles may provide highly efficient catalysts for propylene epoxidation.

GaPO4 sensors for gravimetric monitoring during atomic layer deposition at high temperatures.

The quartz crystal microbalance is extremely useful for in situ monitoring of thin-film growth by atomic layer deposition (ALD) in a viscous flow environment. Unfortunately, conventional AT-quartz sensors are limited to growth temperatures below approximately 300 degrees C. Gallium orthophosphate (GaPO4) is an alternative piezoelectric material offering much greater high-temperature frequency stability than AT-quartz (SiO2). Our measurements reveal that the temperature coefficient for Y-11 degrees GaPO4 decreases linearly with temperature reaching 3 Hz/ degrees C at 450 degrees C. In contrast, the temperature coefficient for the SiO2 sensor increases as the cube of the sensor temperature to 650 Hz/ degrees C at 390 degrees C. To examine the effect of temperature fluctuations on the sensor frequency, we exposed the SiO2 and GaPO4 sensors to helium pulses at 400 degrees C. The resulting frequency change measured for the SiO2 sensor was approximately 40 times greater than that of the GaPO4 sensor. Next, we performed Al2O3 ALD using alternating tri-methylaluminum/water exposures at 400 degrees C and monitored the growth using the SiO2 and GaPO4 sensors. The GaPO4 sensor yielded well-defined pulse shapes in agreement with predictions, while the SiO2 pulses were severely distorted. Measurements during TiO2 ALD using alternating titanium tetrachloride/water exposures at 450 degrees C with the GaPO4 sensor also showed well-defined ALD mass steps.

Modulation of the primary electron transfer rate in photosynthetic reaction centers by reduction of a secondary acceptor.

Photosynthetic application of picosecond spectroscopic techniques to bacterial reaction centers has led to a much greater understanding of the chemical nature of the initial steps of photosynthesis. Within 10 ps after excitation, a charge transfer complex is formed between the primary donor, a "special pair" of bacteriochlorophyll molecules, and a transient acceptor involving bacteriopheophytin. This complex subsequently decays in about 120 ps by donating the electron to a metastable acceptor, a tightly bound quinone.Recent experiments with conventional optical and ESR techniques have shown that when reaction centers are illuminated by a series of single turnover flashes in the presence of excess electron donors and acceptors, a stable, anionic ubisemiquinone is formed on odd flashes and destroyed on even flashes, suggesting that the acceptor region contains a second quinone that acts as a two-electron gate between the reaction center and subsequent electron transport events involving the quinone pool.Utilizing standard picosecond techniques, we have examined the decay of the charge transfer complex in reaction centers in the presence of the stable semiquinone, formed by flash illumination with a dye laser 10 s before excitation by a picosecond pulse. In this state the decay rate for the charge transfer complex is considerably slower than when no electron is present in the quinone acceptor region. This indicates fairly strong coupling between constituents of the reaction center-quinone acceptor complex and may provide a probe into the relative positions of the various components.

Molecular analysis by ionization of laser-desorbed neutral species.

A powerful molecular surface analysis technique for the analysis of complex materials, such as polymer/additive systems, consists of laser desorption of surface molecules and subsequent ionization of these gas-phase molecules with resonant or nonresonant laser ionization. These molecular ions are subsequently detected by Fourier-transform mass spectrometry or time-of-flight mass spectrometry. We show that different wavelengths for the postionization step permit selectivity that provides important additional information on the chemical makeup of these complex materials. Near-UV wavelengthsselectively ionize aromatic polymer additives, far-UV wavelengths photoionize other nonaromatic species; and vacuum-UV wavelengths provide access to all the desorbed species. In addition to these applied results, we study many fundamental issues of laser desorption, such as desorption thresholds, velocity distributions, postionization wavelength selectivity, etc. The Fourier-transform mass spectrometer and time-of-flight mass spectrometer are discussed in detail.

Surface mass spectrometry of biotinylated self-assembled monolayers.

Biotin and biotinylated self-assembled monolayers (SAMs) on gold have been investigated using time-of-flight secondary ion mass spectrometry, direct laser desorption, laser desorption with 193 nm photoionization of ion- and laser-desorbed species, and laser desorption with vacuum ultraviolet (VUV, 118 nm) photoionization. Our results indicate that direct laser desorption and laser desorption combined with 193 nm multiphoton ionization can detect a chromophoric molecule like biotin that is covalently bound to a SAM. However, secondary ion mass spectra were dominated by fragmentation, and ion desorption/193 nm photoionization detected no species related to biotin. The dominant features of the laser desorption/VUV mass spectra were neat and Au-complexed dimers of intact and fragmented biotinylated SAM molecules. Multiphoton and single-photon ionization of laser-desorbed neutrals from biotinylated SAMs both led to the production of ions useful for chemical analysis of the monolayer. Multiphoton ionization with ultraviolet radiation was experimentally less challenging but required a chromophore for ionization and resulted in significant fragmentation of the adsorbate. Single-photon ionization with VUV radiation was experimentally more challenging but did not require a chromophore and led to less fragmentation. X-ray photoelectron spectra indicated that the biotinylated SAM formed a disordered, 40-60 Å thick monolayer on Au. Additionally, projection photolithography with a Schwarzschild microscope was used to pattern the biotinylated SAM surface and laser desorption/photoionization was used to detect biotinylated adsorbates from the ∼10 µm sized pattern.