Open-shell singlet character of stable derivatives of nonacene, hexacene and teranthene

The electronic ground states of the recently synthesized stable nonacene derivatives (J. Am. Chem. Soc. 2010, 132, 1261) are open-shell singlets with a polyradical nature instead of closed-shell singlets as originally assumed, according to the unrestricted broken spin-symmetry density functional theory (UBS-DFT) computations (at B3LYP/6-31G*). It is the bulky protecting groups, not the transfer from the open-shell singlet to closed-shell singlet ground state, that stabilizes these longest characterized acenes. Similar analyses also confirmed the open-shell singlet character of the hexacene and teranthene derivatives.     

Catalytic asymmetric synthesis of (+)-anthecotulide using enyne and Meyer-Schuster rearrangements

The bioactive sesquiterpene lactone (+)-anthecotulide (1) is synthesized for the first time, in a six-step sequence devoid of protecting groups. The key transformations are a novel Rh(I)-catalyzed asymmetric enyne rearrangement of a terminal alkynyl ester (4), to form the α-methylene-γ-butyrolactone core, and a final-step mild Au(I)-catalyzed Meyer-Schuster rearrangement.     

c(2×2) water-hydroxyl layer on Cu(110): a wetting layer stabilized by Bjerrum defects

Understanding the composition and stability of mixed water-hydroxyl layers is a key step in describing wetting and how surfaces respond to redox processes. Here we show that, instead of forming a complete hydrogen bonding network, structures containing an excess of water over hydroxyl are stabilized on Cu(110) by forming a distorted hexagonal network of water-hydroxyl trimers containing Bjerrum defects. This arrangement maximizes the number of strong bonds formed by water donation to OH and provides uncoordinated OH groups able to hydrogen bond multilayer water and nucleate growth.     

Chemical approaches towards unravelling kinase-mediated signalling pathways

Protein kinases control the function of about one third of cellular proteins by catalysing the transfer of the γ-phosphate group of ATP onto their substrate proteins. Protein phosphatases counter this action and also control the activation status of many kinases. Cellular responses to environmental changes, or signalling events, temporarily tilt the balance of protein phosphorylation and dephosphorylation to one side or the other. The identification of protein-kinase-substrate pairs and substrate-phosphatase pairs is critical to understanding cell function and how cells respond to environmental changes. Identification of these substrate-enzyme pairs is non-trivial, because of the structural and mechanistic conservation of the catalytic cores of protein kinases. In this tutorial review we review recent progress towards identifying protein-kinase-substrate pairs by emphasising the use of chemical genetics and purpose-designed ATP analogues that target one particular protein kinase. In addition, we discuss activity-based chemical profiling approaches, based on ATP analogues, for the detection of active kinases.     

Simultaneous quantitative analysis of polyphenolic compounds in human plasma by liquid chromatography tandem mass spectrometry

A diet rich in polyphenolic compounds has recognized health benefits, and as such is routinely monitored as part of dietary intervention studies. A method for the simultaneous determination of 36 phenolic compounds, including phenolic acids and flavonoids, using liquid chromatography and tandem mass spectrometry is described here. The target analytes were quantified based on their specific mass spectral fragments using a selected reaction monitoring approach. A C18 column with embedded aromatic functionality ensured separation of all phenolic compounds studied which included several pairs of isomers. Sample preparation involved the use of β‐glucuronidase to release the phenolic compounds from their conjugated forms. The intra‐day and inter‐day precision and accuracy was less than 7% for all phenolic compounds studied. Recoveries, where plasma was spiked with three different concentrations of the analytes, ranged from 95–115%. The limits of detection and quantification were 0.23–3.89 and 1.15–7.79 nM, respectively. The method was successfully applied to real samples and the range reported for each phenolic compound, with the exception of hydroferulic acid, nordihydroguaiaretic acid, methylgallate, and m‐coumaric acid, was at least an order of magnitude higher than the limit of quantification for the method.     

Spectroscopic Characterization of an Eight‐Iron Nitrogenase Cofactor Precursor that Lacks the “9th Sulfur”

Nitrogenases catalyze the reduction of N₂ to NH₄⁺ at its cofactor site. Designated the M‐cluster, this [MoFe₇S₉C(R‐homocitrate)] cofactor is synthesized via the transformation of a [Fe₄S₄] cluster pair into an [Fe₈S₉C] precursor (designated the L‐cluster) prior to insertion of Mo and homocitrate. We report the characterization of an eight‐iron cofactor precursor (designated the L*‐cluster), which is proposed to have the composition [Fe₈S₈C] and lack the “9^th sulfur” in the belt region of the L‐cluster. Our X‐ray absorption and electron spin echo envelope modulation (ESEEM) analyses strongly suggest that the L*‐cluster represents a structural homologue to the l ‐cluster except for the missing belt sulfur. The absence of a belt sulfur from the L*‐cluster may prove beneficial for labeling the catalytically important belt region, which could in turn facilitate investigations into the reaction mechanism of nitrogenases.     

On the accuracy of models for predicting sound propagation in fitted rooms

The objective of this article is to make a contribution to the evaluation of the accuracy and applicability of models for predicting the sound propagation in fitted rooms such as factories, classrooms, and offices. The models studied are 1:50 scale models; the method-of-image models of Jovicic, Lindqvist, Hodgson, Kurze, and of Lemire and Nicolas; the emprical formula of Friberg; and Ondet and Barbry's ray-tracing model. Sound propagation predictions by the analytic models are compared with the results of sound propagation measurements in a 1:50 scale model and in a warehouse, both containing various densities of approximately isotropically distributed, rectangular-parallelepipedic fittings. The results indicate that the models of Friberg and of Lemire and Nicolas are fundamentally incorrect. While more generally applicable versions exist, the versions of the models of Jovicic and Kurze studied here are found to be of limited applicability since they ignore vertical-wall reflections. The Hodgson and Lindqvist models appear to be accurate in certain limited cases. This preliminary study found the ray-tracing model of Ondet and Barbry to be the most accurate of all the cases studied. Furthermore, it has the necessary flexibility with respect to room geometry, surface-absorption distribution, and fitting distribution. It appears to be the model with the greatest applicability to fitted-room sound propagation prediction.     

Theory of white lines in the x-ray absorption spectra of lanthanide complexes

Self-consistent multiple scattered wave formation was used to calculate the theoretical L-absorption edges of hydrated and unhydrated erbium trichloride in both bound state and continuum regions, in order to investigate the white line behavior. The white line was found to correspond to a transition to a d-like bound state lying just below the continuum threshold.     

The location of public facilities intermediate to the journey to work

Location—allocation models typically locate facilities with respect to points to be served, for example to the homes of potential patrons. Certain types of facility, however, are employed by persons who travel to the facility from their homes and continue their journey to another location. Child care facilities are an example of this pattern of patronage, with parents dropping children off at a centre en route to work. The paper presents a discrete-space location—allocation model minimizing the diversion of patrons' journeys to work. The problem reduces to the structure and combinatorial dimensions of the simple P-median problem. The model is applied to the transit worktrip patterns of single parents in Edmonton, Canada. The facilities generated by the model tend to central locations in the city where workplaces are concentrated and transit connections are efficient. The model provides a compromise between ones minimizing home-facility travel times and facility-workplace travel times.     

Effect of noise and occupancy on optimal reverberation times for speech intelligibility in classrooms

The question of what is the optimal reverberation time for speech intelligibility in an occupied classroom has been studied recently in two different ways, with contradictory results. Experiments have been performed under various conditions of speech-signal to background-noise level difference and reverberation time, finding an optimal reverberation time of zero. Theoretical predictions of appropriate speech-intelligibility metrics, based on diffuse-field theory, found nonzero optimal reverberation times. These two contradictory results are explained by the different ways in which the two methods account for background noise, both of which are unrealistic. To obtain more realistic and accurate predictions, noise sources inside the classroom are considered. A more realistic treatment of noise is incorporated into diffuse-field theory by considering both speech and noise sources and the effects of reverberation on their steady-state levels. The model shows that the optimal reverberation time is zero when the speech source is closer to the listener than the noise source, and nonzero when the noise source is closer than the speech source. Diffuse-field theory is used to determine optimal reverberation times in unoccupied classrooms given optimal values for the occupied classroom. Resulting times can be as high as several seconds in large classrooms; in some cases, optimal values are unachievable, because the occupants contribute too much absorption.