Synthesis, crystal structures, magnetic properties and catecholase activity of double phenoxido-bridged penta-coordinated dinuclear nickel(II) complexes derived from reduced Schiff-base ligands: mechanistic inference of catecholase activity

Three double phenoxido-bridged dinuclear nickel(II) complexes, namely [Ni-2(L-1)(2)(NCS)(2)] (1), [Ni-2(L-2)(2)(NCS)(2)] (2), and [Ni-2(L-3)(2)(NCS)(2)] (3) have been synthesized using the reduced tridentate Schiff-base ligands 2-[1-(3-methylamino-propylamino)-ethyl]-phenol (HL1), 2-[1-(2-dimethylamino-ethylamino)-ethyl]-phenol (HL2), and 2-[1-(3-dimethylarnino-propylamino)-ethyl]-phenol (HL3), respectively. The coordination compounds have been characterized by X-ray structural analyses, magnetic-susceptibility measurements, and various spectroscopic methods. In all complexes, the nickel(II) ions are penta-coordinated in a square-pyramidal environment, which is severely distorted in the case of 1 (Addison parameter tau = 0.47) and 3 (tau = 0.29), while it is almost perfect for 2 (tau = 0.03). This arrangement leads to relatively strong antiferromagnetic interactions between the Ni(II) (S = 1) metal centers as mediated by double phenoxido bridges (with J values of -23.32 (1), -35.45 (2), and -34.02 (3) cm(3) K mol(-1), in the convention H = -2JS(1)S(2)). The catalytic activity of these Ni compounds has been investigated for the aerial oxidation of 3,5-di-tert-butylcatechol. Kinetic data analysis following Michaelis-Menten treatment reveals that the catecholase activity of the complexes is influenced by the flexibility of the ligand and also by the geometry around the metal ion. Electrospray ionization mass spectroscopy (ESI-MS) studies (in the positive mode) have been performed for all the coordination compounds in the presence of 3,5-DTBC to characterize potential complex-substrate intermediates. The mass-spectrometry data, corroborated by electron paramagnetic resonance (EPR) measurements, suggest that the metal centers are involved in the catecholase activity exhibited by the complexes.

Liquid AP-UV-MALDI enables stable ion yields of multiply charged peptide and protein ions for sensitive analysis by mass spectrometry

In biological mass spectrometry (MS), two ionization techniques are predominantly employed for the analysis of larger biomolecules, such as polypeptides. These are nano-electrospray ionization [1, 2] (nanoESI) and matrix-assisted laser desorption/ionization [3, 4] (MALDI). Both techniques are considered to be “soft”, allowing the desorption and ionization of intact molecular analyte species and thus their successful mass-spectrometric analysis. One of the main differences between these two ionization techniques lies in their ability to produce multiply charged ions. MALDI typically generates singly charged peptide ions whereas nanoESI easily provides multiply charged ions, even for peptides as low as 1000 Da in mass. The production of highly charged ions is desirable as this allows the use of mass analyzers, such as ion traps (including orbitraps) and hybrid quadrupole instruments, which typically offer only a limited m/z range (< 2000–4000). It also enables more informative fragmentation spectra using techniques such as collisioninduced dissociation (CID) and electron capture/transfer dissociation (ECD/ETD) in combination with tandem MS (MS/MS). [5, 6] Thus, there is a clear advantage of using ESI in research areas where peptide sequencing, or in general, the structural elucidation of biomolecules by MS/MS is required. Nonetheless, MALDI with its higher tolerance to contaminants and additives, ease-of-operation, potential for highspeed and automated sample preparation and analysis as well as its MS imaging capabilities makes it an ionization technique that can cover bioanalytical areas for which ESI is less suitable. [7, 8] If these strengths could be combined with the analytical power of multiply charged ions, new instrumental configurations and large-scale proteomic analyses based on MALDI MS(/MS) would become feasible.

Energetic charged particles above thunderclouds

The French government has committed to launch the satellite TARANIS to study transient coupling processes between the Earth’s atmosphere and near-Earth space. The prime objective of TARANIS is to detect energetic charged particles and hard radiation emanating from thunderclouds. The British Nobel prize winner C.T.R. Wilson predicted lightning discharges from the top of thunderclouds into space almost a century ago. However, new experiments have only recently confirmed energetic discharge processes which transfer energy from the top of thunderclouds into the upper atmosphere and near-Earth space; they are now denoted as transient luminous events, terrestrial gamma-ray flashes and relativistic electron beams. This meeting report builds on the current state of scientific knowledge on the physics of plasmas in the laboratory and naturally occurring plasmas in the Earth’s atmosphere to propose areas of future research. The report specifically reflects presentations delivered by the members of a novel Franco-British collaboration during a meeting at the French Embassy in London held in November 2011. The scientific subjects of the report tackle ionization processes leading to electrical discharge processes, observations of transient luminous events, electromagnetic emissions, energetic charged particles and their impact on the Earth’s atmosphere. The importance of future research in this area for science and society, and towards spacecraft protection, is emphasized.

MALDI MS profiling of post-DRE urine samples highlights the potential of b-Microseminoprotein as a marker for prostatic diseases

BACKGROUND. To use spectra acquired by matrix-assisted laser desorption/ionization (MALDI) mass spectrometry (MS) from pre- and post-digital rectal examination (DRE) urine samples to search for discriminating peaks that can adequately distinguish between benign and malignant prostate conditions, and identify the peaks’ underlying biomolecules. METHODS. Twenty-five participants with prostate cancer (PCa) and 27 participants with a variety of benign prostatic conditions as confirmed by a 10-core tissue biopsy were included. Pre- and post-DRE urine samples were prepared for MALDI MS profiling using an automated clean-up procedure. Following mass spectra collection and processing, peak mass and intensity were extracted and subjected to statistical analysis to identify peaks capable of distinguishing between benign and cancer. Logistic regression was used to combine markers to create a sensitive and specific test. RESULTS. A peak at m/z 10,760 was identified as b-microseminoprotein (b-MSMB) and found to be statistically lower in urine from PCa participants using the peak’s average areas. By combining serum prostate-specific antigen (PSA) levels with MALDI MS-measured b-MSMB levels, optimum threshold values obtained from Receiver Operator characteristics curves gave an increased sensitivity of 96% at a specificity of 26%. CONCLUSIONS. These results demonstrate that with a simple sample clean-up followed by MALDI MS profiling, significant differences of MSMB abundance were found in post-DRE urine samples. In combination with PSA serum levels, obtained from a classic clinical assay led to high classification accuracy for PCa in the studied sample set. Our results need to be validated in a larger multicenter prospective randomized clinical trial.

Detection of lower tropospheric responses to solar energetic particles at midlatitudes

Solar energetic particles (SEPs) occasionally contribute additional atmospheric ionization beyond that arising from the usual galactic cosmic ray background. During an SEP event associated with a solar flare on April 11, 2013, the vertical ionization rate profile obtained using a balloon-borne detector showed enhanced ionization with a 26% increase at 20 km, over Reading, United Kingdom. Fluctuations in atmospheric electrical parameters were also detected at the surface, beneath the balloon’s trajectory. As no coincident changes in geomagnetism occurred, the electrical fluctuations are very likely to be associated with increased ionization, as observed by the balloon measurements. The lack of response of surface neutron monitors during this event indicates that energetic particles that are not detected at the surface by neutron monitors can nevertheless enter and influence the atmosphere’s weather-generating regions.

Sondrestrom and EISCAT radar observations of poleward-moving auroral forms

During many magnetospheric substorms, the auroral oval near midnight is observed to expand poleward in association with strong negative perturbations measured by local ground magnetometers. We show Sondrestrom and EISCAT incoherent scatter radar measurements during three such events. In each of the events, enhanced ionization produced by the precipitation moved northward by several degrees of latitude within 10–20 min. The electric fields measured during the three events were significantly different. In one event the electric field was southward everywhere within the precipitation region. In the other two events a reversal in the meridional component of the field was observed. In one case the reversal occurred within the precipitation region, while in the other case the reversal was at the poleward boundary of the precipitation. The westward electrojet that produces the negative H-perturbation in the ground magnetic field has Hall and Pedersen components to varying degrees. In one case the Hall component was eastward and the Pedersen component was westward, but the net magnetic H-deflection on the ground was negative. Simultaneous EISCAT measurements made near the dawn meridian during one of the events show that the polar cap boundary moved northward at the same time as the aurora expanded northward at Sondrestrom. Most of the differences in the electrodynamic configuration in the three events can be accounted for in terms of the location at which the measurements were made relative to the center of the auroral bulge.

Comparisons between EISCAT observations and model calculations of the high latitude ionosphere

Calculations using a numerical model of the convection dominated high latitude ionosphere are compared with observations made by EISCAT as part of the UK-POLAR Special Programme. The data used were for 24–25 October 1984, which was characterized by an unusually steady IMF, with Bz < 0 and By > 0; in the calculations it was assumed that a steady IMF implies steady convection conditions. Using the electric field models of Heppner and Maynard (1983) appropriate to By > 0 and precipitation data taken from Spiroet al. (1982), we calculated the velocities and electron densities appropriate to the EISCAT observations. Many of the general features of the velocity data were reproduced by the model. In particular, the phasing of the change from eastward to westward flow in the vicinity of the Harang discontinuity, flows near the dayside throat and a region of slow flow at higher latitudes near dusk were well reproduced. In the afternoon sector modelled velocity values were significantly less than those observed. Electron density calculations showed good agreement with EISCAT observations near the F-peak, but compared poorly with observations near 211 km. In both cases, the greatest disagreement occurred in the early part of the observations, where the convection pattern was poorly known and showed some evidence of long term temporal change. Possible causes for the disagreement between observations and calculations are discussed and shown to raise interesting and, as yet, unresolved questions concerning the interpretation of the data. For the data set used, the late afternoon dip in electron density observed near the F-peak and interpreted as the signature of the mid-latitude trough is well reproduced by the calculations. Calculations indicate that it does not arise from long residence times of plasma on the nightside, but is the signature of a gap between two major ionization sources, viz. photoionization and particle precipitation.

Oblique h.f. radiowave propagation in the main trough region of the ionosphere

The propagation of 7.335 MHz, c.w. signals over a 5212 km sub-auroral, west-east path is studied. Measurements and semi-empirical predictions are made of the amplitude distributions and Doppler shifts of the received signals. The observed amplitude distribution is fitted with one produced by a numerical fading model, yielding the power losses suffered by the signals during propagation via the predominating modes. The signals are found to suffer exceptionally low losses at certain local times under geomagnetically quiet conditions. The mid-latitude trough in the F2 peak ionization density is predicted by a statistical model to be at the latitudes of this path at these times and at low Kp values. A sharp cut-off in low-power losses at a mean Kp of 2.75 strongly implicates the trough in the propagation of these signals. The Doppler shifts observed at these times cannot be explained by a simple ray-tracing model. It is shown however, that a simple extension of this model to allow for the trough can reproduce the form of the observed diurnal variation.

Direct observations of the full Dungey convection cycle in the polar ionosphere for southward interplanetary magnetic field conditions

Tracking the formation and full evolution of polar cap ionization patches in the polar ionosphere, we directly observe the full Dungey convection cycle for southward interplanetary magnetic field (IMF) conditions. This enables us to study how the Dungey cycle influences the patches’ evolution. The patches were initially segmented from the dayside storm enhanced density plume at the equatorward edge of the cusp, by the expansion and contraction of the polar cap boundary due to pulsed dayside magnetopause reconnection, as indicated by in situ Time History of Events and Macroscale Interactions during Substorms(THEMIS) observations. Convection led to the patches entering the polar cap and being transported antisunward, while being continuously monitored by the globally distributed arrays of GPS receivers and Super Dual Auroral Radar Network radars. Changes in convection over time resulted in the patches following a range of trajectories, each of which differed somewhat from the classical twin-cell convection streamlines. Pulsed nightside reconnection, occurring as part of the magnetospheric substorm cycle, modulated the exit of the patches from the polar cap, as confirmed by coordinated observations of the magnetometer at Tromsø and European Incoherent Scatter Tromsø UHF radar. After exiting the polar cap, the patches broke up into a number of plasma blobs and returned sunward in the auroral return flow of the dawn and/or dusk convection cell. The full circulation time was about 3 h.

Preface

The ‘soft’ ionization technique matrix-assisted laser desorption/ionization (MALDI) is without doubt one of the great success stories of modern mass spectrometry (MS). In particular, the further development of MALDI and in general ‘soft’ laser ionization, focusing on their unique characteristics and advantages in areas such as speed, spatial resolution, sample preparation and low spectral complexity, have led to great advances in mass spectral profiling and imaging with an extremely auspicious future in (bio)medical analyses.

Ionic liquids and other liquid matrices for sensitive MALDI MS analysis

Although liquid matrix-assisted laser desorption/ionization (MALDI) has been used in mass spectrometry (MS) since the early introduction of MALDI, its substantial lack of sensitivity compared to solid (crystalline) MALDI was for a long time a major hurdle to its analytical competitiveness. In the last decade, this situation has changed with the development of new sensitive liquid matrices, which are often based on a binary matrix acid/base system. Some of these matrices were inspired by the recent progress in ionic liquid research, while others were developed from revisiting previous liquid MALDI work as well as from a combination of these two approaches. As a result, two high-performing liquid matrix classes have been developed, the ionic liquid matrices (ILMs) and the liquid support matrices (LSMs), now allowing MS measurements at a sensitivity level that is very close to the level of solid MALDI and in some cases even surpasses it. This chapter provides some basic information on a selection of highly successful representatives of these new liquid matrices and describes in detail how they are made and applied in MALDI MS analysis.

Coupling liquid MALDI MS to liquid chromatography

Matrix-assisted laser desorption/ionisation (MALDI) coupled with time-of-flight (TOF) mass spectrometry (MS) is a powerful tool for the analysis of biological samples, and nanoflow high-performance liquid chromatography (nanoHPLC) is a useful separation technique for the analysis of complex proteomics samples. The off-line combination of MALDI and nanoHPLC has been extensively investigated and straightforward techniques have been developed, focussing particularly on automated MALDI sample preparation that yields sensitive and reproducible spectra. Normally conventional solid MALDI matrices such as α-cyano-4-hydroxycinnamic acid (CHCA) are used for sample preparation. However, they have limited usefulness in quantitative measurements and automated data acquisition because of the formation of heterogeneous crystals, resulting in highly variable ion yields and desorption/ ionization characteristics. Glycerol-based liquid support matrices (LSM) have been proposed as an alternative to the traditional solid matrices as they provide increased shot-to-shot reproducibility, leading to prolonged and stable ion signals and therefore better results. This chapter focuses on the integration of the liquid LSM MALDI matrices into the LC-MALDI MS/MS approach in identifying complex and large proteomes. The interface between LC and MALDI consists of a robotic spotter, which fractionates the eluent from the LC column into nanoliter volumes, and co-spots simultaneously the liquid matrix with the eluent fractions onto a MALDI target plate via sheath flow. The efficiency of this method is demonstrated through the analysis of trypsin digests of both bovine serum albumin (BSA) and Lactobacillus plantarum WCFS1 proteins.

Investigation and optimization of parameters affecting the multiply charged ion yield in AP-MALDI MS

Liquid matrix-assisted laser desorption/ionization (MALDI) allows the generation of predominantly multiply charged ions in atmospheric pressure (AP) MALDI ion sources for mass spectrometry (MS) analysis. The charge state distribution of the generated ions and the efficiency of the ion source in generating such ions crucially depend on the desolvation regime of the MALDI plume after desorption in the AP-tovacuum inlet. Both high temperature and a flow regime with increased residence time of the desorbed plume in the desolvation region promote the generation of multiply charged ions. Without such measures the application of an electric ion extraction field significantly increases the ion signal intensity of singly charged species while the detection of multiply charged species is less dependent on the extraction field. In general, optimization of high temperature application facilitates the predominant formation and detection of multiply charged compared to singly charged ion species. In this study an experimental setup and optimization strategy is described for liquid AP-MALDI MS which improves the ionization effi- ciency of selected ion species up to 14 times. In combination with ion mobility separation, the method allows the detection of multiply charged peptide and protein ions for analyte solution concentrations as low as 2 fmol/lL (0.5 lL, i.e. 1 fmol, deposited on the target) with very low sample consumption in the low nL-range.

Earth's ion upflow associated with polar cap patches: global and in-situ observations

We report simultaneous global monitoring of a patch of ionization and in situ observation of ion upflow at the center of the polar cap region during a geomagnetic storm. Our observations indicate strong fluxes of upwelling O+ ions originating from frictional heating produced by rapid antisunward flow of the plasma patch. The statistical results from the crossings of the central polar cap region by Defense Meteorological Satellite Program F16–F18 from 2010 to 2013 confirm that the field-aligned flow can turn upward when rapid antisunward flows appear, with consequent significant frictional heating of the ions, which overcomes the gravity effect. We suggest that such rapidly moving patches can provide an important source of upwelling ions in a region where downward flows are usually expected. These observations give new insight into the processes of ionosphere-magnetosphere coupling.