Salt enhanced solvent relaxation and particle surface area determination via rapid spin-lattice NMR

This paper demonstrates the influence of surface charge chemistry on the application of nuclear magnetic relaxation measurements (NMR relaxometry) for the in situ determination of particle surface area, in the presence of high electrolyte concentration. Specifically, dispersions of titania, calcite and silica with and without 1 M KCl were investigated. The addition of salt, showed no significant change to relaxation measurements for titanium dioxide; however, a significant rate enhancement was observed for both calcite and silica systems. These differences were attributed to counterion layers forming as a result of the particles surface charge, leading to an increase in the relaxation rate of bound surface layer water. Further, changes appeared to be more pronounced in the silica systems, due to their larger charge. No enhancement was observed for titania, which was assumed to be due to the particles being at their isoelectric point, with no resulting counterion layer formation. Solvent relaxation was further used to successfully determine the surface area of particles in a dispersion using a silica standard reference material, with results compared to Brunauer-Emmett-Teller (BET) and spherical equivalent estimations. Two different dispersions of titanium dioxide, of different crystal phases, were shown to have NMR surface area measurements in good agreement with BET. Thus showing the technique was able to measure changes in surface charge when surface chemistry remained relatively similar, due to the reference silica material also being an oxide. In contrast, the NMR technique appeared to overestimate the calcite surface areas in reference to BET, which was assumed to occur due to both better dispersion in the liquid state of nanocrystallites and potential ion enhancement from the solubility of the calcite. These results highlight the potential of this technique as a fast, non-destructive and non-invasive method for dispersion analysis, but also show the competition between surface area and surface chemistry interactions on measured relaxation rates

Observation of a One-Dimensional Spin-Orbit Gap in a Quantum Wire

Understanding the flow of spins in magnetic layered structures has enabled an increase in data storage density in hard drives over the past decade of more than two orders of magnitude1. Following this remarkable success, the field of 'spintronics' or spin-based electronics is moving beyond effects based on local spin polarisation and is turning its attention to spin-orbit interaction (SOI) effects, which hold promise for the production, detection and manipulation of spin currents, allowing coherent transmission of information within a device. While SOI-induced spin transport effects have been observed in two- and three-dimensional samples, these have been subtle and elusive, often detected only indirectly in electrical transport or else with more sophisticated techniques. Here we present the first observation of a predicted 'spin-orbit gap' in a one-dimensional sample, where counter-propagating spins, constituting a spin current, are accompanied by a clear signal in the easily-measured linear conductance of the system.Comment: 10 pages, 5 figures, supplementary informatio

Performance of the CMS Cathode Strip Chambers with Cosmic Rays

The Cathode Strip Chambers (CSCs) constitute the primary muon tracking device in the CMS endcaps. Their performance has been evaluated using data taken during a cosmic ray run in fall 2008. Measured noise levels are low, with the number of noisy channels well below 1%. Coordinate resolution was measured for all types of chambers, and fall in the range 47 microns to 243 microns. The efficiencies for local charged track triggers, for hit and for segments reconstruction were measured, and are above 99%. The timing resolution per layer is approximately 5 ns

Site-selective protein-modification chemistry for basic biology and drug development.

Nature has produced intricate machinery to covalently diversify the structure of proteins after their synthesis in the ribosome. In an attempt to mimic nature, chemists have developed a large set of reactions that enable post-expression modification of proteins at pre-determined sites. These reactions are now used to selectively install particular modifications on proteins for many biological and therapeutic applications. For example, they provide an opportunity to install post-translational modifications on proteins to determine their exact biological roles. Labelling of proteins in live cells with fluorescent dyes allows protein uptake and intracellular trafficking to be tracked and also enables physiological parameters to be measured optically. Through the conjugation of potent cytotoxicants to antibodies, novel anti-cancer drugs with improved efficacy and reduced side effects may be obtained. In this Perspective, we highlight the most exciting current and future applications of chemical site-selective protein modification and consider which hurdles still need to be overcome for more widespread use.We thank FCT Portugal (FCT Investigator to G.J.L.B.), the EU (Marie-Curie CIG to G.J.L.B. and Marie-Curie IEF to O.B.) and the EPSRC for funding. G.J.L.B. is a Royal Society University Research Fellow.This is the author accepted manuscript. The final version is available from NPG via http://dx.doi.org/10.1038/nchem.239

Current challenges in software solutions for mass spectrometry-based quantitative proteomics

This work was in part supported by the PRIME-XS project, grant agreement number 262067, funded by the European Union seventh Framework Programme; The Netherlands Proteomics Centre, embedded in The Netherlands Genomics Initiative; The Netherlands Bioinformatics Centre; and the Centre for Biomedical Genetics (to S.C., B.B. and A.J.R.H); by NIH grants NCRR RR001614 and RR019934 (to the UCSF Mass Spectrometry Facility, director: A.L. Burlingame, P.B.); and by grants from the MRC, CR-UK, BBSRC and Barts and the London Charity (to P.C.

Performance of CMS muon reconstruction in pp collision events at sqrt(s) = 7 TeV

The performance of muon reconstruction, identification, and triggering in CMS has been studied using 40 inverse picobarns of data collected in pp collisions at sqrt(s) = 7 TeV at the LHC in 2010. A few benchmark sets of selection criteria covering a wide range of physics analysis needs have been examined. For all considered selections, the efficiency to reconstruct and identify a muon with a transverse momentum pT larger than a few GeV is above 95% over the whole region of pseudorapidity covered by the CMS muon system, abs(eta) < 2.4, while the probability to misidentify a hadron as a muon is well below 1%. The efficiency to trigger on single muons with pT above a few GeV is higher than 90% over the full eta range, and typically substantially better. The overall momentum scale is measured to a precision of 0.2% with muons from Z decays. The transverse momentum resolution varies from 1% to 6% depending on pseudorapidity for muons with pT below 100 GeV and, using cosmic rays, it is shown to be better than 10% in the central region up to pT = 1 TeV. Observed distributions of all quantities are well reproduced by the Monte Carlo simulation.Comment: Replaced with published version. Added journal reference and DO

Performance of CMS muon reconstruction in pp collision events at sqrt(s) = 7 TeV

The performance of muon reconstruction, identification, and triggering in CMS has been studied using 40 inverse picobarns of data collected in pp collisions at sqrt(s) = 7 TeV at the LHC in 2010. A few benchmark sets of selection criteria covering a wide range of physics analysis needs have been examined. For all considered selections, the efficiency to reconstruct and identify a muon with a transverse momentum pT larger than a few GeV is above 95% over the whole region of pseudorapidity covered by the CMS muon system, abs(eta) < 2.4, while the probability to misidentify a hadron as a muon is well below 1%. The efficiency to trigger on single muons with pT above a few GeV is higher than 90% over the full eta range, and typically substantially better. The overall momentum scale is measured to a precision of 0.2% with muons from Z decays. The transverse momentum resolution varies from 1% to 6% depending on pseudorapidity for muons with pT below 100 GeV and, using cosmic rays, it is shown to be better than 10% in the central region up to pT = 1 TeV. Observed distributions of all quantities are well reproduced by the Monte Carlo simulation.Comment: Replaced with published version. Added journal reference and DO

Population genomics of marine zooplankton

Author Posting. © The Author(s), 2017. This is the author's version of the work. It is posted here for personal use, not for redistribution. The definitive version was published in Bucklin, Ann et al. "Population Genomics of Marine Zooplankton." Population Genomics: Marine Organisms. Ed. Om P. Rajora and Marjorie Oleksiak. Springer, 2018. doi:10.1007/13836_2017_9.The exceptionally large population size and cosmopolitan biogeographic distribution that distinguish many – but not all – marine zooplankton species generate similarly exceptional patterns of population genetic and genomic diversity and structure. The phylogenetic diversity of zooplankton has slowed the application of population genomic approaches, due to lack of genomic resources for closelyrelated species and diversity of genomic architecture, including highly-replicated genomes of many crustaceans. Use of numerous genomic markers, especially single nucleotide polymorphisms (SNPs), is transforming our ability to analyze population genetics and connectivity of marine zooplankton, and providing new understanding and different answers than earlier analyses, which typically used mitochondrial DNA and microsatellite markers. Population genomic approaches have confirmed that, despite high dispersal potential, many zooplankton species exhibit genetic structuring among geographic populations, especially at large ocean-basin scales, and have revealed patterns and pathways of population connectivity that do not always track ocean circulation. Genomic and transcriptomic resources are critically needed to allow further examination of micro-evolution and local adaptation, including identification of genes that show evidence of selection. These new tools will also enable further examination of the significance of small-scale genetic heterogeneity of marine zooplankton, to discriminate genetic “noise” in large and patchy populations from local adaptation to environmental conditions and change.Support was provided by the US National Science Foundation to AB and RJO (PLR-1044982) and to RJO (MCB-1613856); support to IS and MC was provided by Nord University (Norway)

Analysis of Adsorbed Polyphosphate Changes on Milled Titanium Dioxide, Using Low-Field Relaxation NMR and Photoelectron Spectroscopy

In this study, changes in the adsorbed amount and surface structure of sodium hexametaphosphate (SHMP) were investigated for aluminum-doped TiO₂ pigment undergoing milling. Relaxation NMR was utilized as a potential at-line technique to monitor the effect of milling on surface area and surface chemistry, while XPS was used primarily to consider the dispersant structure. Results showed that considerable amounts of weakly adsorbed SHMP could be removed with washing, and the level of dispersant removal increased with time, highlighting destructive effects of sustained high-energy milling. Nonetheless, there were no significant chemical changes to the dispersant, although increases to the bridging oxygen (BO) peak full width at half-maximum (FWHM) suggested some chemical degradation was occurring with excess milling. Relaxation NMR revealed a number of important features. Results with unmilled material indicated that dispersant adsorption could be tracked with pseudo-isotherms using the relative enhancement rate (Rsp), where the Rsp decreased with dispersant coverage, owing to partial blocking of the quadrupolar surface aluminum. Milled samples were also tracked, with very accurate calibrations of surface area possible from either T₁ or T₂ relaxation data for systems without dispersant. Behavior was considerably more complicated with SHMP, as there appeared to be an interplay between the dispersant surface coverage and relaxation enhancement from the surface aluminum. Nevertheless, findings highlight that relaxation NMR could be used as a real-time technique to monitor the extent of milling processes, so long as appropriate industrial calibrations can be achieved

Characterisation of polyphosphate coated aluminium-doped titania nanoparticles during milling

This paper investigates the characterisation of alumina-doped titania nanoparticles, milled under high-shear over time, in the presence of sodium hexametaphosphate (SHMP) dispersant. Transmission electron microscopy (TEM) indicated that prolonged milling times led to the formation of 10 nm particle fines which were electrostatically attracted to larger particles, where no change in the crystal structure was observed. The primary particle size measured by dynamic light scattering (DLS) and TEM were in agreement and showed no change in primary particle size (∼250 nm) with respect to milling time, however, there was a clear reduction in the magnitude of the slow mode decay associated to aggregates. The TiO₂ was found to have an isoelectric point (iep) in the range of pH 3 to 4.5, where an increase in milling time led to a lower pHiep, indicative of an increase in SHMP coverage, which was further supported by an intensification in phosphorus content measured by X-ray fluorescence (XRF). Phosphorus content and zeta potential analysis before and after centrifugal washing showed that SHMP was partially removed or hydrolysed for the longer milled pigment samples, whereas no change was observed for shorter milled samples. Relaxation NMR was also performed, where enhanced relaxation rates at longer milling times were associated partially to increases in surface area and exposure of Al sites, as well as physicochemical changes to SHMP density and structure. It is thought that extended milling times may lead to hydrolysis or other structural changes of the dispersant from the high energy milling conditions, allowing easier removal of SHMP for longer milled pigments