Identification and evaluation of cycling yeast metabolites in two-dimensional comprehensive gas chromatography-time-of-flight-mass spectrometry data

A yeast metabolome exhibiting oscillatory behavior was analyzed using comprehensive two-dimensional gas chromatography-time-of-flight-mass spectrometry (GC x GC-TOF-MS) and in-house developed data analysis software methodology, referred to as a signal ratio method (S(ratio) method). In this study, 44 identified unique metabolites were found to exhibit cycling, with a depth-of-modulation amplitude greater than three. After the initial locations are found using the S(ratio) software, and identified preliminarily using ChromaTOF software, the refined mass spectra and peak volumes were subsequently obtained using parallel factor analysis (PARAFAC). The peak volumes provided by PARAFAC deconvolution provide a measurement of the cycling depth-of-modulation amplitude that is more accurate than the initial S(ratio) information (which serves as a rapid screening procedure to find the cycling metabolites while excluding peaks that do not cycle). The S(ratio) reported is a rapid method to determine the depth-of-modulation while not constraining the search to specific cycling frequencies. The phase delay of the cycling metabolites ranged widely in relation to the oxygen consumption cycling pattern.     

Photoinduced ultrafast electron transfer from CdSe quantum dots to Re-bipyridyl complexes

Ultrafast dissociation of excitons in CdSe quantum dots via electron transfer to adsorbed Re-bipyridyl complexes was demonstrated. The dissociation pathway was determined by the observation of reduced adsorbate using femtosecond IR spectroscopy. The rate of electron transfer was shown to increase at smaller QD sizes. Electron transfer time as fast as 2.3 ps was observed, faster than the exciton annihilation time in CdSe. The ultrafast charge separation in this quantum dot-adsorbate donor-acceptor complex provides a potential approach for separating multiple excitons in quantum dots.     

Bilinear Control and Application to Flexible a.c. Transmission Systems

The purpose of this paper is an integrated overview of bilinear systems (BLS) research which has evolved over the past few decades, and a new result on control of flexible a.c. transmission systems (FACTS) is presented. BLS may be derived in many cases from principles of physics, chemistry, biology, socioeconomics, and engineering. In other cases, BLS are more accurate approximations to nonlinear systems than are traditional linear systems, as shown for example by the added bilinear terms (in state and control) for the Taylor series.While an appropriately designed linear control system may be optimum relative to some quadratic performance index without added constraints, bilinear or parametric control can be designed to improve more global performance and indeed to increase the region of attainable states. Such controllability and stabilization of BLS and of a series line-capacitor controlled FACTS is presented.     

Die Bukettstoffe des Kirschwassers

Ohne Zusammenfassung     

Relative efficiencies of CpM(CO)(n)CH(3) and CpM(CO)(n)Ph (M = Cr,Mo, W,and Fe) complexes in photoinduced DNA cleavage

The relative efficiencies of photoinduced DNA cleavage by complexes of the type CpM(CO)(n)()R (M = Cr, Mo, or W, n = 3, R = CH(3) or Ph; M = Fe, n = 2, R = CH(3) or C(6)H(5)) have been investigated using a plasmid relaxation assay. Only the tungsten and iron complexes reproducibly caused single strand scission, in addition to which the iron systems efficiently gave double strand cleavage. The iron complexes gave strand scission at lower concentrations than the corresponding tungsten systems, with the phenyl complexes producing more damage than the methyl systems.     

pH-dependent electron transfer from re-bipyridyl complexes to metal oxide nanocrystalline thin films

Photoinduced interfacial electron transfer (ET) from molecular adsorbates to semiconductor nanoparticles has been a subject of intense recent interest. Unlike intramolecular ET, the existence of a quasicontinuum of electronic states in the solid leads to a dependence of ET rate on the density of accepting states in the semiconductor, which varies with the position of the adsorbate excited-state oxidation potential relative to the conduction band edge. For metal oxide semiconductors, their conduction band edge position varies with the pH of the solution, leading to pH-dependent interfacial ET rates in these materials. In this work we examine this dependence in Re(L(P))(CO)3Cl (or ReC1P) [L(P) = 2,2'-bipyridine-4,4'-bis-CH2PO(OH)2] and Re(L(A))(CO)3Cl (or ReC1A) [L(A) = 2,2'-bipyridine-4,4'-bis-CH2COOH] sensitized TiO2 and ReC1P sensitized SnO2 nanocrystalline thin films using femtosecond transient IR spectroscopy. ET rates are measured as a function of pH by monitoring the CO stretching modes of the adsorbates and mid-IR absorption of the injected electrons. The injection rate to TiO2 was found to decrease by 1000-fold from pH 0-9, while it reduced by only a factor of a few to SnO2 over a similar pH range. Comparison with the theoretical predictions based on Marcus' theory of nonadiabatic interfacial ET suggests that the observed pH-dependent ET rate can be qualitatively accounted for by considering the change of density of electron-accepting states caused by the pH-dependent conduction band edge position.     

Recent advancements in comprehensive two-dimensional separations with chemometrics

Comprehensive two-dimensional (2D) separations provide the analyst with a tremendous amount of complex data. In order to glean useful information from this complex data, advancements in commercially available software that implement chemometrics are currently available and continue to evolve. Future advancements will no doubt involve commercializing (or adapting) specialized, in-house chemometric techniques that are currently found only in the hands of technical experts and researchers in industry, government, and academia. In order to make timely advancements, future commercialization of novel chemometric techniques should involve collaborations among instrument software manufacturers, professional programmers, technical experts, and researchers. During the last decade, this field has seen a steady advancement from single analyte target analysis to comprehensive non-target analysis of entire multidimensional sample profiles (involving sample classification and/or data mining for discovery-based sample comparisons). The advancements in instrumentation and chemometric software tools have a tremendous impact in various applications: fuels, food, environmental, pharmaceuticals, metabolomics, etc. Most of the development has been for software to apply with gas chromatography-based instrumentation, such as comprehensive two-dimensional gas chromatography (GC x GC) and comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry (GC x GC-TOF-MS). More recently there have been notable advancements in liquid-phase instrumentation as well.