Probing the adsorption structure of a multifunctional organic molecule: a NIXSW and NEXAFS study of 3-chlorothiophene on Cu(111)

The adsorption structure of 3-chlorothiophene on Cu(111) has been investigated using a combination of normal incidence X-ray standing wavefield absorption (NIXSW) and near edge X-ray absorption fine structure (NEXAFS) spectroscopy. For coverages up to saturation of the chemisorbed layer, the 3-chlorothiophene bonds through the S atom. The S atom adsorbs in an atop site with a Cu–S distance identical, within experimental error, to that observed for thiophene on the same substrate. From a combination of NEXAFS and NIXSW, thiophene was found to adsorb with the aromatic ring flat lying. From NIXSW measurements the S–Cl axis was found to be inclined by 12±2° from the surface. Whilst NEXAFS data suggested an orientation of 23±8° for the aromatic ring of 3-chlorothiophene. The Cl atom interacted only weakly with the substrate, with a Cl–surface distance longer than the Cu–Cl van der Waal separation.     

Bicyclobutanes: from curiosities to versatile reagents and covalent warheads

The unique chemistry of small, strained carbocyclic systems has long captivated organic chemists from a theoretical and fundamental standpoint. A resurgence of interest in strained carbocyclic species has been prompted by their potential as bioisosteres, high fraction of sp³ carbons, and limited appearance in the patent literature. Among strained ring systems, bicyclo[1.1.0]butane (BCB) stands apart as the smallest bicyclic carbocycle and is amongst the most strained carbocycles known. Despite the fact that BCBs have been synthesized and studied for well over 50 years, they have long been regarded as laboratory curiosities. However, new approaches for preparing, functionalizing, and using BCBs in “strain-release” transformations have positioned BCBs to be powerful synthetic workhorses. Further, the olefinic character of the bridgehead bond enables BCBs to be elaborated into various other ring systems and function as covalent warheads for bioconjugation. This review will discuss the recent developments in the synthesis and functionalization of BCBs as well as the applications of these strained rings in synthesis and drug discovery. An overview of the properties and the historical context of this interesting structure will be provided.

A flurry of reports for preparing, functionalizing, and using bicyclo[1.1.0]butanes (BCBs) have positioned them to be powerful synthons with numerous applications. This review discusses the recent developments regarding this strained carbocycle.     

Structure reactivity relationship in the reaction of DNA guanyl radicals with hydroxybenzoates

In DNA, guanine bases are the sites from which electrons are most easily removed. As a result of hole migration to this stable location on guanine, guanyl radicals are major intermediates in DNA damage produced by the direct effect of ionizing radiation (ionization of the DNA itself and not through the intermediacy of water radicals). We have modeled this process by employing gamma irradiation in the presence of thiocyanate ions, a method which also produces single electron oxidized guanyl radicals in plasmid DNA in aqueous solution. The stable products formed in DNA from these radicals are detected as strand breaks after incubation with the FPG protein. When a phenolic compound is present in the solution during gamma irradiation, the formation of guanyl radical species is decreased by electron donation from the phenol to the guanyl radical. We have quantified the rate of this reaction for four different phenolic compounds bearing carboxylate substituents as proton acceptors. A comparison of the rates of these reactions with the redox strengths of the phenolic compounds reveals that salicylate reacts ca. 10-fold faster than its structural analogs. This observation is consistent with a reaction mechanism involving a proton coupled electron transfer, because intra-molecular transfer of a proton from the phenolic hydroxyl group to the carboxylate group is possible only in salicylate, and is favored by the strong 6-membered ring intra-molecular hydrogen bond in this compound.     

Exact derivation of aperture errors in antenna measurements

Antenna-pattern measurements are generally undertaken by placing the antenna under test (usually the receiving antenna) sufficiently far from the transmitting antenna that the receiving antenna is illuminated with a plane wave. Gain measurements, whether by substitution, paired horns, or integration of the area under the beam pattern, depend upon the same criterion. A true plane wave is only achieved by separating the two antennas by an infinite distance, but it has been shown by Milne (1950) that small departures from a plane wave do not usually seriously degrade the measurement. The authors consider three aspects of the fields across a linear aperture. The finite spacing between the antennas produces a phase deviation and an amplitude taper. If we are only interested in the apparent gain loss, we need to combine both tapers into an illumination efficiency. It is surprising how little the illumination loss is when the phase deviation and amplitude taper are large. The formulation is given in terms of linear apertures, and can be easily extended to circular or rectangular apertures by adjusting the limits of the integrals     

The role of carbide morphology on low-cycle-fatigue behavior of iron-carbon alloys

A series of iron-carbon binary alloys having a pearlitic and spheroidized microstructure were reverse cycled in a uniaxial tension-compression mode. The carbon level varied from pure iron through four carbon levels up to 2 percent. The specimens had an hourglass-shaped configuration. The diometral strain was measured and controlled with a ring-type LVDT. The diametral strain was converted and reported as longitudinal strain based on constancy of volume considerations. Total longitudinal strain range varied from 1 percent to 4 percent, giving cyclic lives in the region from 300–5,000. Increasing the carbon content significantly influenced the cyclic life for the pearlitic structure but had only a slight influence on the spheroidized material.     

The gross hydrostatic-pressure effect as related to foil and wire strain gages

An analysis of gross pressure effect for strain gages is presented. This is defined as the difference between the predicted hydrostatic strain and the experimental strain. Values of the theoretical strain per unit pressure are based on the Voigt-Reuss-Hill approximation using published values of elastic moduli and compliances. These theoretical values are adjusted by the pressure effect calculated from an equation based on the assumption that the pressure effect is independent of the elastic properties of the substrate. The modified values of theoretical strain per unit pressure are then compared with the experimentally observed values. The differences are small except for the substrate materials of zinc, cadmium and lead. Experimental pressure-strain data are presented for constantan foil gages mounted on tungsten, copper, tin, molybdenum, titanium, cadmium, brass, zinc and lead as well as constantan wire gages mounted on steel, aluminum and magnesium for hydrostatic pressures up to 140 ksi. Data for foil and wire gages mounted with various adhesives are presented and show that the adhesive or backing materials appear to have a relatively minor effect on the over-all gage performance.     

The effects of high pressure on foil strain gages

The purpose of this investigation was to determine whether a linear pressure-strain response was possible for gages subjected to hydrostatic pressures to 140 ksi. This was motivated by the desire to use this information to measure the elastic-plastic behavior of material at the inside surface of thick-walled cylinders subjected to high internal pressure. This paper shows the effects of fluid pressure to 140 ksi on four different types of foil strain gage. Linear pressure-strain curves were obtained for these gages mounted on flat surfaces of tungsten, steel and aluminum specimens. The linear strains of several materials due to pressure are compared with the compressibility constant (1–2ν)/E as calculated from experimentally determined values ofE and ν, whereE is defined as the modulus of elasticity and ν is Poisson's ratio. Experimental results show the percent deviation between the constants to be a function of the material, being greatest for tungsten and least for aluminum. The fact that a linear pressure-strain response was obtained makes it possible to correct the readings for strain gages mounted on flat surfaces of materials subjected to direct hydrostatic pressure. Temperature effects as a function of pressurization rate were investigated. Various gage failures encountered along with photomicrographs showing probable causes are presented.     

Polarization loss in a link budget when using measuredcircular-polarization gains of antennas

What is the correct polarization loss, when calculating the transmission between two antennas whose gains are measured with respect to circular polarization, such as, from a ground station to a satellite? Previously published charts made assumptions, which do not quite fit this situation. We need to revisit this problem, and be made aware of the assumptions behind these charts, so that we obtain the right answer. In general, the previous charts over-estimate the loss. All these charts are correct when used in the proper situation. As a part of this discussion, the author also covers methods of measuring the gain of circularly polarized antennas. A new nomograph calculates the polarization efficiency to be used in a link budget, when the gain of the antennas have been measured with respect to a pure-polarization incident wave. A comparison is made to previous nomographs, and the assumptions made in deriving them     

Application of selected ion flow tube mass spectrometry to real‐time atmospheric monitoring

Data are presented for real‐time atmospheric monitoring of volatile organic chemicals (VOCs) in air using selected ion flow tube mass spectrometry (SIFT‐MS) technology. These measurements were made by one of the new generation of SIFT‐MS instruments. Results are shown for five VOCs that were continually monitored from a stationary sampling point over a 4‐day period: ethene, ethanol, 1,3‐butadiene, benzene and toluene. All analytes except ethene in the study have at least two simultaneous and independent measures of concentration. These results demonstrate the great advances in SIFT‐MS that have been made in recent years. 1,3‐Butadiene is measured at a concentration of 9 pptv with a precision of 44%. For a 1‐s integration time, a detection limit of 50 pptv is achieved. Instrument sensitivities are reported for all five analytes. Copyright © 2010 John Wiley & Sons, Ltd.     

Applications of fluorescence and bioluminescence resonance energy transfer to drug discovery at G protein coupled receptors

The role of G protein coupled receptors (GPCRs) in numerous physiological processes that may be disrupted or modified in disease makes them key targets for the development of new therapeutic medicines. A wide variety of resonance energy transfer (RET) techniques such as fluorescence RET and bioluminescence RET have been developed in recent years to detect protein–protein interactions in living cells. Furthermore, these techniques are now being exploited to screen for novel compounds that activate or block GPCRs and to search for new, previously undiscovered signaling pathways activated by well-known pharmacologically classified drugs. The high resolution that can be achieved with these RET methods means that they are well suited to study both intramolecular conformational changes in response to ligand binding at the receptor level and intermolecular interactions involving protein translocation in subcellular compartments resulting from external stimuli. In this review we highlight the latest advances in these technologies to illustrate general principles.