On the iron oxide neutral cluster distribution in the gas phase. I. Detection through 193 nm multiphoton ionization

Iron oxide (FemOn) neutral clusters are generated in the gas phase through laser ablation of the metal and reaction with various concentrations of O2 in He. The mixture of expansion gas and neutral FemOn cluster species is expanded through a supersonic nozzle into a vacuum system, in which the clusters are ionized by an ArF excimer laser at 193 nm, and the ions are detected and identified in a time-of-flight mass spectrometer. In this report, the experimental parameters that influence the observed cluster distributions, such as ablation laser power, expansion pressure, vacuum system pressure, and 193 nm ArF ionization laser power, are explored. In the second paper in this series, the effect of the ionization laser wavelength (355 nm, 193 nm, 118 nm) on the observed cluster ion distribution is explored. The cluster ion distribution observed employing 193 nm laser ionization, is sensitive to the neutral cluster distribution as evidenced by the change in the observed time-of-flight mass spectra with changes in laser power, growth conditions, and expansion conditions. The thermodynamically stable neutral clusters for saturated O2 growth conditions are suggested to be of the forms FemOm, FemO(m+1), and FemO(m+2); which one of these series of neutral clusters is most stable depends on the size of the cluster. For m < 10, FemOm is the most stable neutral cluster series, for 10 < or = m < or = 20, FemO(m+1) is the most stable neutral cluster series, and for 21 < or = m < = 30, FemO(m+2) is the most stable neutral cluster series. Some neutral cluster fragmentation is clearly present for 193 nm ionization due to multiphoton absorption in both the neutral and ionic cluster species.     

Rpd3p relocation mediates a transcriptional response to rapamycin in yeast

Treating yeast cells with rapamycin, a small molecule that inhibits the TOR proteins, leads to the repression of many genes. Consistent with prior studies, we find that RPD3, which encodes a histone deacetylase (HDAC), is required for repression upon rapamycin treatment. To elucidate the mechanism underlying RPD3-mediated repression, we screened all promoters in yeast for occupancy by Rpd3p before and after treatment with rapamycin. We find that Rpd3p binds to the promoters of rapamycin-repressible genes only following treatment. These data conflict with a previously proposed model suggesting that Rpd3p is constitutively bound to rapamycin-repressible genes and becomes active only after a stimulus such as treatment with rapamycin. Rather, the comprehensive analysis presented here strongly supports a model in which recruitment of Rpd3p to gene promoters is a regulated step in the control of gene repression.     

Preparation of a diketopiperazine analog of leukotriene D4 (LTD4)

A LTD₄ analog has been synthesized in which the peptidyl fragment has been replaced by a nonionic diketopiperazine. Biological evaluation showed agonist activity, giving key information on LTD₄ geometry to the receptor.     

Sarcophine,a new epoxy cembranolide from marine origin

From the soft bodied coral Sarcophytum glaucum a crystalline compound-sarcophine (1), which is believed to be one of the repellents protecting the coral against predators, was isolated. The functional groups of 1 have been deduced from detailed NMR study and the whole molecular structure has been determined by a single-crystal 3-dimensional X-ray diffraction study proceeding from direct methods. The compound crystallizes in orthorhombic crystals, space group P2₁2₁2₁, and there are four molecules in each unit cell of dimensions a = 12·429(3), b = 13·766(3) and c = 10·750(1). The structure was found to be a new epoxy cembranolide. The mass spectrum and CD of 1 and several simple derivatives as well as the conformation of 1 in solution are discussed.     

Preparation of ethyl 5(s),6-epoxy-3(r)-(methoxymethoxy)hexanoate: a key chiral intermediate for mevinolin and compactin.

The synthesis of Ethyl 5(S),6-Epoxy-3(R)-(methoxymethoxy)hexanoate, a key chiral synthon for the β-hydroxy-δ-lactone portion of Mevinolin and Compactin, $\text{via}$ a regiospecific ring opening of a tetrahydrofuran derivative by dimethylboron bromide, is described.     

Patterns in Hydrogen Bonding: Functionality and Graph Set Analysis in Crystals

Whereas much of organic chemistry has classically dealt with the preparation and study of the properties of individual molecules, an increasingly significant portion of the activity in chemical research involves understanding and utilizing the nature of the interactions between molecules. Two representative areas of this evolution are supramolecular chemistry and molecular recognition. The interactions between molecules are governed by intermolecular forces whose energetic and geometric properties are much less well understood than those of classical chemical bonds between atoms. Among the strongest of these interactions, however, are hydrogen bonds, whose directional properties are better understood on the local level (that is, for a single hydrogen bond) than many other types of non-bonded interactions. Nevertheless, the means by which to characterize, understand, and predict the consequences of many hydrogen bonds among molecules, and the resulting formation of molecular aggregates (on the microscopic scale) or crystals (on the macroscopic scale) has remained largely enigmatic. One of the most promising systematic approaches to resolving this enigma was initially developed by the late M. C. Etter, who applied graph theory to recognize, and then utilize, patterns of hydrogen bonding for the understanding and design of molecular crystals. In working with Etter's original ideas the power and potential utility of this approach on one hand, and on the other, the need to develop and extend the initial Etter formalism was generally recognized. It with that latter purpose that we originally undertook the present review.     

Lateralization of sinusoidally amplitude-modulated tones: effects of spectral locus and temporal variation

It has long been recognized that listeners are sensitive to interaural temporal disparities (ITDs) of low-frequency (i.e., below 1600 Hz) stimuli. Within the last three decades, it has often been demonstrated that listeners are also sensitive to ITDs within the envelope of high-frequency, complex stimuli. Because these studies, for the most part, employed discrimination tasks, few data exist concerning the extent of laterality produced by ITDs as a function of the spectral locus of the stimulus. To this end, we employed an acoustic "pointing" task in which listeners varied the interaural intensity difference of a 500-Hz narrow-band noise (the pointer) so that it matched the intracranial position of a second, experimenter-controlled stimulus (the target). Targets were sinusoidally amplitude-modulated tones centered on 500 Hz, 1, 2, 3, or 4 kHz and modulated at rates ranging from 50 to 800 Hz. Targets were presented with either the entire waveform delayed or with only the envelope delayed. Our results suggest that: (1) for low-frequency targets, lateralization is influenced by ITDs in the envelope but is dominated by ITDs in the fine structure; (2) for high-frequency targets, envelope-based delays produce displacements of the acoustic images which are affected greatly by the rate of modulation; rather large extents of laterality could be produced with high rates of modulation; these data are consistent with those obtained previously in discrimination experiments; (3) for low rates of modulation (e.g., 100 Hz), delays of the entire waveform (both envelope and fine structure) produce much greater displacements of the acoustic image for low-frequency than for high-frequency targets (where fine-structure-based cues are not utilizable); (4) there appear to be no consistent relations among extent of laterality, rate of modulation, and the frequency of the carrier within and across listeners.     

Automatic assignment of 1H‐NMR spectra of small molecules

A novel data‐evaluation procedure for the automatic atom to peak or multiplet assignment of ¹H‐NMR spectra of small molecules has been developed using a fast and robust expert system. The applicability and reliability of the method are demonstrated by comparison of a manually assigned database of ¹H‐NMR spectra with the assignments produced by the automatic procedure. The results of this analysis show an excellent success ratio, indicating that this new algorithm can have a major impact as a time saving tool for the organic chemist. A new graphical feature used to illustrate both the stability and quality of the elementary assignments is also introduced. Copyright © 2013 John Wiley & Sons, Ltd.