Structure, energetics and reactions of metal cation complexes of dipeptides in the gas phase

Structure, energetics and reactions of ions in the gas phase can be revealed by mass spectrometry techniques coupled to ions activation methods. Ions can gain enough energy for dissociation by absorbing IR light photons introduced by an IR laser to the mass spectrometer. Also collisions with a neutral molecule can increase the internal energy of ions and provide the dissociation threshold energy. Infrared multiple photon dissociation (IRMPD) or sustained off-resonance irradiation collision-induced dissociation (SORI-CID) methods are combined with Fourier Transform Ion Cyclotron Resonance (FT-ICR) mass spectrometers where ions can be held at low pressures for a long time. The outcome of ion activation techniques especially when it is compared to the computational methods results is of great importance since it provides useful information about the structure, thermochemistry and reactivity of ions of interest. In this work structure, energetics and reactivity of metal cation complexes with dipeptides are investigated. Effect of metal cation size and charge as well as microsolvation on the structure of these complexes has been studied. Structures of bare and hydrated Na and Ca complexes with isomeric dipeptides AlaGly and GlyAla are characterized by means of IRMPD spectroscopy and computational methods. At the second step unimolecular dissociation reactions of singly charged and doubly charged multimetallic complexes of alkaline earth metal cations with GlyGly are examined by CID method. Also structural features of these complexes are revealed by comparing their IRMPD spectra with calculated IR spectra of possible structures. At last the unimolecular dissociation reactions of Mn complexes are studied. IRMPD spectroscopy along with computational methods is also employed for structural elucidation of Mn complexes. In addition the ion-molecule reactions of Mn complexes with CO and water are explored in the low pressures obtained in the ICR cell.

Genesis and character of thin-bedded turbidites associated with submarine channels

Acknowledgements We acknowledge the support of the PRACSS Joint Industry Project at University of Aberdeen, funded by BG Group, BP, DONG, RWE Dea, Petrochina, Statoil and Tullow Oil. We also acknowledge the entire crew of the Urania Research vessel which was used to acquire the CHIRP lines, bathymetric data and gravity cores from the Tyrrhenian Sea, Italy. Our colleagues Michal Janocko and Mike Mayall are thanked for the discussions and comments. Our colleagues Pan Li, Amanda Santa Catharina, Guilherme Bozetti and Matheus Silveira Sobiesiak are thanked for their assistance during field work where some of the ideas in this paper were synthesized. Finally we thank one anonymous reviewer and Brian Romans for their invaluable feedback which made some of the ideas introduced in this review much more succinct.

Different cation-protonation patterns in mol-ecular salts of unsymmetrical dimethyhydrazine : C2H9N2·Br and C2H9N2·H2PO3

Peer reviewed

On the mobility, membrane location and functionality of mechanosensitive channels in Escherichia coli

We thank Frans Bianchi and Franz Ho for assistance with molecular cloning, Tim Rasmussen for providing the pTRC-MscK plasmid, Andrew Robinson for providing the pBAD-mEos3.2 plasmid, Matthias Heinemann for assistance with the flow cytometry measurements, Paul Schavemaker for performing Smoldyn simulations and Michiel Punter for programming ImageJ plugins for PALM reconstructions and single-particle tracking. We thank Ian Booth for critical reading of the manuscript, and Christoffer Åberg and Matteo Gabba for valuable discussions. The authors would like to thank David Dryden and Marcel Reuter for performing preliminary experiments from which this work has been built. The work was funded by the EU FP7 ITN-network program NICHE.

4 Tb/s transmission reach enhancement using 10 × 400 Gb/s super-channels and polarization insensitive dual band optical phase conjugation

In this paper, we experimentally demonstrate the benefit of polarization insensitive dual-band optical phase conjugation for up to ten 400 Gb/s optical super-channels using a Raman amplified transmission link with a realistic span length of 75 km. We demonstrate that the resultant increase in transmission distance may be predicted analytically if the detrimental impacts of power asymmetry and polarization mode dispersion are taken into account.

Impact of scatterer density on the performances of double-scattering MIMO channels

We investigate a MIMO double-scattering model with both local and remote scatterers, aiming to investigate the effect of scatterer density on channel performances, such as capacity, correlation, and the condition number of the channel matrix in flat and frequency-selective fading channels. The investigations are carried out in terms of scatterer density. It is shown that in flat fading channels the scatterer density has a marginal effect on channel performances when the area of the two scatterer zones is fixed, while a significant impact is observed when the area of the scatterer zones is allowed to change. In frequency-selective fading channels, no matter the area of the scatterer zones is fixed or not, scatterer density can affect the channel capacity to a certain degree that depends on the length of the coding block of the transmitted signals. © 2010 IEEE.

A facile spin-cast route for cation exchange of multilayer perpendicularly-aligned nanorod assemblies

A facile spin cast route was developed to convert perpendicularly aligned nanorod assemblies of cadmium chalcogenides into their silver and copper analogues. The assemblies are rapidly cation exchanged without affecting either the individual rod dimensions or collective superlattice order extending over several multilayers.

Synergy between Piezo1 and Piezo2 channels confers high-strain mechanosensitivity to articular cartilage.

Diarthrodial joints are essential for load bearing and locomotion. Physiologically, articular cartilage sustains millions of cycles of mechanical loading. Chondrocytes, the cells in cartilage, regulate their metabolic activities in response to mechanical loading. Pathological mechanical stress can lead to maladaptive cellular responses and subsequent cartilage degeneration. We sought to deconstruct chondrocyte mechanotransduction by identifying mechanosensitive ion channels functioning at injurious levels of strain. We detected robust expression of the recently identified mechanosensitive channels, PIEZO1 and PIEZO2. Combined directed expression of Piezo1 and -2 sustained potentiated mechanically induced Ca(2+) signals and electrical currents compared with single-Piezo expression. In primary articular chondrocytes, mechanically evoked Ca(2+) transients produced by atomic force microscopy were inhibited by GsMTx4, a PIEZO-blocking peptide, and by Piezo1- or Piezo2-specific siRNA. We complemented the cellular approach with an explant-cartilage injury model. GsMTx4 reduced chondrocyte death after mechanical injury, suggesting a possible therapy for reducing cartilage injury and posttraumatic osteoarthritis by attenuating Piezo-mediated cartilage mechanotransduction of injurious strains.

Low valence cation doping of bulk Cr2O3: Charge compensation and oxygen vacancy formation

The different oxidation states of chromium allow its bulk oxide form to be reducible, facilitating the oxygen vacancy formation process, which is a key property in applications such as catalysis. Similar to other useful oxides such as TiO2, and CeO2, the effect of substitutional metal dopants in bulk Cr2O3 and its effect on the electronic structure and oxygen vacancy formation are of interest, particularly in enhancing the latter. In this paper, density functional theory (DFT) calculations with a Hubbard + U correction (DFT+U) applied to the Cr 3d and O 2p states, are carried out on pure and metal-doped bulk Cr2O3 to examine the effect of doping on the electronic and geometric structure. The role of dopants in enhancing the reducibility of Cr2O3 is examined to promote oxygen vacancy formation. The dopants are Mg, Cu, Ni, and Zn, which have a formal +2 oxidation state in their bulk oxides. Given this difference in host and, dopant oxidation states, we show that to predict the correct ground state two metal dopants charge compensated with an oxygen vacancy are required. The second oxygen atom removed is termed "the active" oxygen vacancy and it is the energy required to remove this atom that is related to the reduction process. In all cases, we find that substitutional doping improves the oxygen vacancy formation of bulk Cr2O3 by lowering the energy cost.

‘Never Let Me Down Again’1: Loyal customer attitudes towards ticket distribution channels for live music events: a netnographic exploration of the US leg of the Depeche Mode 2005–2006 World Tour

Ticket distribution channels for live music events have been revolutionised through the increased take-up of internet technologies, and the music supply-chain has evolved into a multi-channel value network. The assumption that this creates increased consumer autonomy and improved service quality is explored here through a case-study of the ticket pre-sale for the US leg of the Depeche Mode 2005–06 World Tour, which utilises an innovative virtual channel strategy, promoted as a service to loyal fans. A multi-method analysis, adopting Kozinets' (2002) Kozinets, R. V. 2002. The field behind the screen: using netnography for marketing research in online communities. Journal of Marketing Research, 39: 61–72. [CrossRef], [Web of Science ®] netnography methodology, is employed to map responses of the band's serious fan base on an internet message board (IMB) throughout the tour pre-sale. The analysis focuses on concerns of pricing, ethics, scope of the offer, use of technology, service quality and perceived brand performance fit of channel partners. Findings indicate that fans behaviour is unpredictable in response to channel partners' performance, and that such offers need careful management to avoid alienation of loyal consumers.

Modeling, Analysis and Performance Comparison of Two Direct Sampling DCSK Receivers under Frequency Nonselective Fading Channels

Two direct sampling correlator-type receivers for differential chaos shift keying (DCSK) communication systems under frequency non-selective fading channels are proposed. These receivers operate based on the same hardware platform with different architectures. In the first scheme, namely sum-delay-sum (SDS) receiver, the sum of all samples in a chip period is correlated with its delayed version. The correlation value obtained in each bit period is then compared with a fixed threshold to decide the binary value of recovered bit at the output. On the other hand, the second scheme, namely delay-sum-sum (DSS) receiver, calculates the correlation value of all samples with its delayed version in a chip period. The sum of correlation values in each bit period is then compared with the threshold to recover the data. The conventional DCSK transmitter, frequency non-selective Rayleigh fading channel, and two proposed receivers are mathematically modelled in discrete-time domain. The authors evaluated the bit error rate performance of the receivers by means of both theoretical analysis and numerical simulation. The performance comparison shows that the two proposed receivers can perform well under the studied channel, where the performances get better when the number of paths increases and the DSS receiver outperforms the SDS one.

Outage performance of cognitive cooperative networks with relay selection over double-Rayleigh fading channels

This study considers a dual-hop cognitive inter-vehicular relay-assisted communication system where all
communication links are non-line of sight ones and their fading is modelled by the double Rayleigh fading distribution.
Road-side relays (or access points) implementing the decode-and-forward relaying protocol are employed and one of
them is selected according to a predetermined policy to enable communication between vehicles. The performance of
the considered cognitive cooperative system is investigated for Kth best partial and full relay selection (RS) as well as
for two distinct fading scenarios. In the first scenario, all channels are double Rayleigh distributed. In the second
scenario, only the secondary source to relay and relay to destination channels are considered to be subject to double
Rayleigh fading whereas, channels between the secondary transmitters and the primary user are modelled by the
Rayleigh distribution. Exact and approximate expressions for the outage probability performance for all considered RS
policies and fading scenarios are presented. In addition to the analytical results, complementary computer simulated
performance evaluation results have been obtained by means of Monte Carlo simulations. The perfect match between
these two sets of results has verified the accuracy of the proposed mathematical analysis.

CaV channels and cancer: canonical functions indicate benefits of repurposed drugs as cancer therapeutics

The importance of ion channels in the hallmarks of many cancers is increasingly recognised. This article reviews current knowledge of the expression of members of the voltage-gated calcium channel family (CaV) in cancer at the gene and protein level and discusses their potential functional roles. The ten members of the CaV channel family are classified according to expression of their pore-forming α-subunit; moreover, co-expression of accessory α2δ, β and γ confers a spectrum of biophysical characteristics including voltage dependence of activation and inactivation, current amplitude and activation/inactivation kinetics. CaV channels have traditionally been studied in excitable cells including neurones, smooth muscle, skeletal muscle and cardiac cells, and drugs targeting the channels are used in the treatment of hypertension and epilepsy. There is emerging evidence that several CaV channels are differentially expressed in cancer cells compared to their normal counterparts. Interestingly, a number of CaV channels also have non-canonical functions and are involved in transcriptional regulation of the expression of other proteins including potassium channels. Pharmacological studies show that CaV canonical function contributes to the fundamental biology of proliferation, cell-cycle progression and apoptosis. This raises the intriguing possibility that calcium channel blockers, approved for the treatment of other conditions, could be repurposed to treat particular cancers. Further research will reveal the full extent of both the canonical and non-canonical functions of CaV channels in cancer and whether calcium channel blockers are beneficial in cancer treatment.

Multi-Device Selection Scheduling in Non-Identically Distributed Fading Channels

Multiuser selection scheduling concept has been recently proposed in the literature in order to increase the multiuser diversity gain and overcome the significant feedback requirements for the opportunistic scheduling schemes. The main idea is that reducing the feedback overhead saves per-user power that could potentially be added for the data transmission. In this work, the authors propose to integrate the principle of multiuser selection and the proportional fair scheduling scheme. This is aimed especially at power-limited, multi-device systems in non-identically distributed fading channels. For the performance analysis, they derive closed-form expressions for the outage probabilities and the average system rate of the delay-sensitive and the delay-tolerant systems, respectively, and compare them with the full feedback multiuser diversity schemes. The discrete rate region is analytically presented, where the maximum average system rate can be obtained by properly choosing the number of partial devices. They optimise jointly the number of partial devices and the per-device power saving in order to maximise the average system rate under the power requirement. Through the authors’ results, they finally demonstrate that the proposed scheme leveraging the saved feedback power to add for the data transmission can outperform the full feedback multiuser diversity, in non-identical Rayleigh fading of devices’ channels.

Posterior Probability Modeling and Image Classification for Archaeological Site Prospection: Building a Survey Efficacy Model for Identifying Neolithic Felsite Workshops in the Shetland Islands

The application of custom classification techniques and posterior probability modeling (PPM) using Worldview-2 multispectral imagery to archaeological field survey is presented in this paper. Research is focused on the identification of Neolithic felsite stone tool workshops in the North Mavine region of the Shetland Islands in Northern Scotland. Sample data from known workshops surveyed using differential GPS are used alongside known non-sites to train a linear discriminant analysis (LDA) classifier based on a combination of datasets including Worldview-2 bands, band difference ratios (BDR) and topographical derivatives. Principal components analysis is further used to test and reduce dimensionality caused by redundant datasets. Probability models were generated by LDA using principal components and tested with sites identified through geological field survey. Testing shows the prospective ability of this technique and significance between 0.05 and 0.01, and gain statistics between 0.90 and 0.94, higher than those obtained using maximum likelihood and random forest classifiers. Results suggest that this approach is best suited to relatively homogenous site types, and performs better with correlated data sources. Finally, by combining posterior probability models and least-cost analysis, a survey least-cost efficacy model is generated showing the utility of such approaches to archaeological field survey.