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The paper describes technical characteristics and presents the first scientific results of a novel infrared imaging system (imager) for studies of nightglow emissions coming from the hydroxyl (OH) and molecular oxygen (O2) layers in the mesopause region (80–100 km) above northern Scandinavia. The OH imager was put into operation in November 2022 at the Swedish Institute of Space Physics in Kiruna (67.86° N, 20.42° E; 400 m altitude). The OH imager records selected emission lines in the OH(3-1) band near 1500 nm to obtain intensity and temperature maps at around 87 km altitude. In addition, the OH imager registers infrared emissions coming from the O2 IR A-band airglow at 1268.7 nm in order to obtain O2 intensity maps at a slightly higher altitude, around 94 km. This technique allows the tracing of wave disturbances in both horizontal and vertical domains in the mesopause region. Validation and comparison of the OH(3-1) rotational temperature with collocated lidar and Aura Microwave Limb Sounder (MLS) satellite temperatures are performed. The first scientific results obtained from the OH imager for the first winter season (2022–2023) are discussed.

The ground-based measurements obtained from a lidar network and the 6-year OSIRIS (optical spectrograph and infrared imager system) limb-scanning radiance measurements made by the Odin satellite are used to study the climatology of the middle- and low-latitude sodium (Na) layer. Up to January 2021, four Na resonance fluorescence lidars at Beijing (40.5∘ N, 116.0∘ E), Hefei (31.8∘ N, 117.3∘ E), Wuhan (30.5∘ N, 114.4∘ E), and Haikou (19.5∘ N, 109.1∘ E) collected vertical profiles of Na density for a total of 2136 nights (19 587 h). These large datasets provide multi-year routine measurements of the Na layer with exceptionally high temporal and vertical resolution. The lidar measurements are particularly useful for filling in OSIRIS data gaps since the OSIRIS measurements were not made during the dark winter months because they utilize the solar-pumped resonance fluorescence from Na atoms. The observations of Na layers from the ground-based lidars and the satellite are comprehensively compared with a global model of meteoric Na in the atmosphere (WACCM–Na). The lidars present a unique test of OSIRIS and WACCM (Whole Atmosphere Community Climate Model), because they cover the latitude range along 120∘ E longitude in an unusual geographic location with significant gravity wave generation. In general, good agreement is found between lidar observations, satellite measurements, and WACCM simulations. On the other hand, the Na number density from OSIRIS is larger than that from the Na lidars at the four stations within one standard deviation of the OSIRIS monthly average, particularly in autumn and early winter arising from significant uncertainties in Na density retrieved from much less satellite radiance measurements. WACCM underestimates the seasonal variability of the Na layer observed at the lower latitude lidar stations (Wuhan and Haikou). This discrepancy suggests the seasonal variability of vertical constituent transport modelled in WACCM is underestimated because much of the gravity wave spectrum is not captured in the model.

Global three-dimensional data are a key to understanding gravity waves in the mesosphere and lower thermosphere. MATS (Mesospheric Airglow/Aerosol Tomography and Spectroscopy) is a new Swedish satellite mission that addresses this need. It applies space-borne limb imaging in combination with tomographic and spectroscopic analysis to obtain gravity wave data on relevant spatial scales. Primary measurement targets are O2 atmospheric band dayglow and nightglow in the near infrared, and sunlight scattered from noctilucent clouds in the ultraviolet. While tomography provides horizontally and vertically resolved data, spectroscopy allows analysis in terms of mesospheric temperature, composition, and cloud properties. Based on these dynamical tracers, MATS will produce a climatology on wave spectra during a 2-year mission. Major scientific objectives include a characterization of gravity waves and their interaction with larger-scale waves and mean flow in the mesosphere and lower thermosphere, as well as their relationship to dynamical conditions in the lower and upper atmosphere. MATS is currently being prepared to be ready for a launch in 2020. This paper provides an overview of scientific goals, measurement concepts, instruments, and analysis ideas.

In this paper we present an overview of measurements conducted during the WADIS-2 rocket campaign. We investigate the effect of small-scale processes like gravity waves and turbulence on the distribution of atomic oxygen and other species in the mesosphere–lower thermosphere (MLT) region. Our analysis suggests that density fluctuations of atomic oxygen are coupled to fluctuations of other constituents, i.e., plasma and neutrals. Our measurements show that all measured quantities, including winds, densities, and temperatures, reveal signatures of both waves and turbulence. We show observations of gravity wave saturation and breakdown together with simultaneous measurements of generated turbulence. Atomic oxygen inside turbulence layers shows two different spectral behaviors, which might imply a change in its diffusion properties.

Absolute profiles of atomic oxygen number densities with high vertical resolution have been determined in the mesosphere–lower thermosphere (MLT) region from in situ measurements by several rocket-borne solid electrolyte sensors. The amperometric sensors were operated in both controlled and uncontrolled modes and with various orientations on the foredeck and aft deck of the payload. Calibration was based on mass spectrometry in a molecular beam containing atomic oxygen produced in a microwave discharge. The sensor signal is proportional to the number flux onto the electrodes, and the mass flow rate in the molecular beam was additionally measured to derive this quantity from the spectrometer reading. Numerical simulations provided aerodynamic correction factors to derive the atmospheric number density of atomic oxygen from the sensor data. The flight results indicate a preferable orientation of the electrode surface perpendicular to the rocket axis. While unstable during the upleg, the density profiles measured by these sensors show an excellent agreement with the atmospheric models and photometer results during the downleg of the trajectory. The high spatial resolution of the measurements allows for the identification of small-scale variations in the atomic oxygen concentration.

We present a new method of analyzing measurements of mesospheric dust made with DUSTY rocket-borne Faraday cup probes. It can yield the variation in fundamental dust parameters through a mesospheric cloud with an altitude resolution down to 10 cm or less if plasma probes give the plasma density variations with similar height resolution. A DUSTY probe was the first probe that unambiguously detected charged dust and aerosol particles in the Earth's mesosphere. DUSTY excluded the ambient plasma by various biased grids, which however allowed dust particles with radii above a few nanometers to enter, and it measured the flux of charged dust particles. The flux measurements directly yielded the total ambient dust charge density. We extend the analysis of DUSTY data by using the impact currents on its main grid and the bottom plate as before, together with a dust charging model and a secondary charge production model, to allow the determination of fundamental parameters, such as dust radius, charge number, and total dust density. We demonstrate the utility of the new analysis technique by considering observations made with the DUSTY probes during the MAXIDUSTY rocket campaign in June–July 2016 and comparing the results with those of other instruments (lidar and photometer) also used in the campaign. In the present version we have used monodisperse dust size distributions.

Based on self-consistent rocket-borne measurements of temperature, the densities of atomic oxygen and neutral air, and the volume emission of the atmospheric band (762 nm), we examined the one-step and two-step excitation mechanism of O2b1Σg+ for nighttime conditions. Following McDade et al. (1986), we derived the empirical fitting coefficients, which parameterize the atmospheric band emission O2b1Σg+-X3Σg-0,0. This allows us to derive the atomic oxygen concentration from nighttime observations of atmospheric band emission O2b1Σg+-X3Σg-0,0. The derived empirical parameters can also be utilized for atmospheric band modeling. Additionally, we derived the fit function and corresponding coefficients for the combined (one- and two-step) mechanism. The simultaneous common volume measurements of all the parameters involved in the theoretical calculation of the observed O2b1Σg+-X3Σg-0,0 emission, i.e., temperature and density of the background air, atomic oxygen density, and volume emission rate, is the novelty and the advantage of this work.

The question of whether mesospheric OH(v) rotational population distributions are in equilibrium with the local kinetic temperature has been debated over several decades. Despite several indications for the existence of non-equilibrium effects, the general consensus has been that emissions originating from low rotational levels are thermalized. Sky spectra simultaneously observing several vibrational levels demonstrated reproducible trends in the extracted OH(v) rotational temperatures as a function of vibrational excitation. Laboratory experiments provided information on rotational energy transfer and direct evidence for fast multi-quantum OH(high-v) vibrational relaxation by O atoms. We examine the relationship of the new relaxation pathways with the behavior exhibited by OH(v) rotational population distributions. Rapid OH(high-v) + O multi-quantum vibrational relaxation connects high and low vibrational levels and enhances the hot tail of the OH(low-v) rotational distributions. The effective rotational temperatures of mesospheric OH(v) are found to deviate from local thermodynamic equilibrium for all observed vibrational levels. Dedicated to Tom G. Slanger in celebration of his 5 decades of research in aeronomy.

In summer 2013 the WADIS-1 sounding rocket campaign was conducted at the Andøya Space Center (ACS) in northern Norway (69° N, 16° E). Among other things, it addressed the question of the variability in mesosphere/lower thermosphere (MLT) turbulence, both in time and space. A unique feature of the WADIS project was multi-point turbulence sounding applying different measurement techniques including rocket-borne ionization gauges, VHF MAARSY radar, and VHF EISCAT radar near Tromsø. This allowed for horizontal variability to be observed in the turbulence field in the MLT at scales from a few to 100 km. We found that the turbulence dissipation rate, ε varied in space in a wavelike manner both horizontally and in the vertical direction. This wavelike modulation reveals the same vertical wavelengths as those seen in gravity waves. We also found that the vertical mean value of radar observations of ε agrees reasonably with rocket-borne measurements. In this way defined 〈εradar〉 value reveals clear tidal modulation and results in variation by up to 2 orders of magnitude with periods of 24 h. The 〈εradar〉 value also shows 12 h and shorter (1 to a few hours) modulations resulting in one decade of variation in 〈εradar〉 magnitude. The 24 h modulation appeared to be in phase with tidal change of horizontal wind observed by SAURA-MF radar. Such wavelike and, in particular, tidal modulation of the turbulence dissipation field in the MLT region inferred from our analysis is a new finding of this work.

We present in situ observations of meteoric smoke particles (MSP) obtained during three sounding rocket flights in December 2010 in the frame of the final campaign of the Norwegian-German ECOMA project (ECOMA = Existence and Charge state Of meteoric smoke particles in the Middle Atmosphere). The flights were conducted before, at the maximum activity, and after the decline of the Geminids which is one of the major meteor showers over the year. Measurements with the ECOMA particle detector yield both profiles of naturally charged particles (Faraday cup measurement) as well as profiles of photoelectrons emitted by the MSPs due to their irradiation by photons of a xenon-flash lamp. The column density of negatively charged MSPs decreased steadily from flight to flight which is in agreement with a corresponding decrease of the sporadic meteor flux recorded during the same period. This implies that the sporadic meteors are a major source of MSPs while the additional influx due to the shower meteors apparently did not play any significant role. Surprisingly, the profiles of photoelectrons are only partly compatible with this observation: while the photoelectron current profiles obtained during the first and third flight of the campaign showed a qualitatively similar behaviour as the MSP charge density data, the profile from the second flight (i.e., at the peak of the Geminids) shows much smaller photoelectron currents. This may tentatively be interpreted as a different MSP composition (and, hence, different photoelectric properties) during this second flight, but at this stage we are not in a position to conclude that there is a cause and effect relation between the Geminids and this observation. Finally, the ECOMA particle detector used during the first and third flight employed three instead of only one xenon flash lamp where each of the three lamps used for one flight had a different window material resulting in different cut off wavelengths for these three lamp types. Taking into account these data along with simple model estimates as well as rigorous quantum chemical calculations, it is argued that constraints on MSP sizes, work function and composition can be inferred. Comparing the measured data to a simple model of the photoelectron currents, we tentatively conclude that we observed MSPs in the 0.5–3 nm size range with generally increasing particle size with decreasing altitude. Notably, this size information can be obtained because different MSP particle sizes are expected to result in different work functions which is both supported by simple classical arguments as well as quantum chemical calculations. Based on this, the MSP work function can be estimated to lie in the range from ~4–4.6 eV. Finally, electronic structure calculations indicate that the low work function of the MSP measured by ECOMA indicates that Fe and Mg hydroxide clusters, rather than metal silicates, are the major constituents of the smoke particles.

In December 2010 the last campaign of the German-Norwegian sounding rocket project ECOMA (Existence and Charge state Of Meteoric smoke particles in the middle Atmosphere) was conducted from Andøya Rocket Range in northern Norway (69° N, 16° E) in connection with the Geminid meteor shower. The main instrument on board the rocket payloads was the ECOMA detector for studying meteoric smoke particles (MSPs) by active photoionization and subsequent detection of the produced charges (particles and photoelectrons). In addition to photoionizing MSPs, the energy of the emitted photons from the ECOMA flash-lamp is high enough to also photoionize nitric oxide (NO). Thus, around the peak of the NO layer, at and above the main MSP layer, photoelectrons produced by the photoionization of NO are expected to contribute to, or even dominate above the main MSP-layer, the total measured photoelectron current. Among the other instruments on board was a set of two photometers to study the O2 (b1Σg+−X3Σg) Atmospheric band and NO2 continuum nightglow emissions. In the absence of auroral emissions, these two nightglow features can be used together to infer NO number densities. This will provide a way to quantify the contribution of NO photoelectrons to the photoelectron current measured by the ECOMA instrument and, above the MSP layer, a simultaneous measurement of NO with two different and independent techniques. This work is still on-going due to the uncertainties, especially in the effort to quantitatively infer NO densities from the ECOMA photoelectron current, and the lack of simultaneous measurements of temperature and density for the photometric study. In this paper we describe these two techniques to infer NO densities and discuss the uncertainties. The peak NO number density inferred from the two photometers on ascent was 3.9 × 108 cm−3 at an altitude of about 99 km, while the concentration inferred from the ECOMA photoelectron measurement at this altitude was a factor of 5 smaller.

Accurate knowledge about the distribution of atomic oxygen is crucial for many studies of the mesosphere and lower thermosphere. Direct measurements of atomic oxygen by the resonance fluorescence technique at 130 nm have been made from many sounding rocket payloads in the past. This measurement technique yields atomic oxygen profiles with good sensitivity and altitude resolution. However, accuracy is a problem as calibration and aerodynamics make the quantitative analysis challenging. Most often, accuracies better than a factor 2 are not to be expected from direct atomic oxygen measurements. As an example, we present results from the NLTE (Non Local Thermodynamic Equilibrium) sounding rocket campaign at Esrange, Sweden, in 1998, with simultaneous O2 airglow and O resonance fluorescence measurements. O number densities are found to be consistent with the nightglow analysis, but only within the uncertainty limits of the resonance fluorescence technique. Based on these results, we here describe how better atomic oxygen number densities can be obtained by calibrating direct techniques with complementary airglow photometer measurements and detailed aerodynamic analysis. Night-time direct O measurements can be complemented by photometric detection of the O2 (b1∑g+−X3∑g-) Atmospheric Band at 762 nm, while during daytime the O2 (a1Δg−X3∑g-) Infrared Atmospheric Band at 1.27 μm can be used. The combination of a photometer and a rather simple resonance fluorescence probe can provide atomic oxygen profiles with both good accuracy and good height resolution.

In order to better understand noctilucent clouds (NLC) and their sensitivity to the variable environment of the polar mesosphere, more needs to be learned about the actual cloud particle population. Optical measurements are today the only means of obtaining information about the size of mesospheric ice particles. In order to efficiently access particle sizes, scattering experiments need to be performed in the Mie scattering regime, thus requiring wavelengths of the order of the particle size. Previous studies of NLC have been performed at wavelengths down to 355 nm from the ground and down to about 200 nm from rockets and satellites. However, from these measurements it is not possible to access the smaller particles in the mesospheric ice population. This current lack of knowledge is a major limitation when studying important questions about the nucleation and growth processes governing NLC and related particle phenomena in the mesosphere. We show that NLC measurements in the extreme ultraviolet, in particular using solar Lyman-α radiation at 121.57 nm, are an efficient way to further promote our understanding of NLC particle size distributions. This applies both to global measurements from satellites and to detailed in situ studies from sounding rockets. Here, we present examples from recent rocket-borne studies that demonstrate how ambiguities in the size retrieval at longer wavelengths can be removed by invoking Lyman-α. We discuss basic requirements and instrument concepts for future rocket-borne NLC missions. In order for Lyman-α radiation to reach NLC altitudes, high solar elevation and, hence, daytime conditions are needed. Considering the effects of Lyman-α on NLC in general, we argue that the traditional focus of rocket-borne NLC missions on twilight conditions has limited our ability to study the full complexity of the summer mesopause environment.

Meteoric smoke particles have been proposed as a key player in the formation and evolution of mesospheric phenomena. Despite their apparent importance still very little is known about these particles. Important questions concern the smoke number density and size distribution as a function of altitude as well as the fraction of charged particles. Sounding rockets are used to measure smoke in situ, but aerodynamics has remained a major challenge. Basically, the small smoke particles tend to follow the gas flow around the payload rather than reaching the detector if aerodynamics is not considered carefully in the detector design. So far only indirect evidence for the existence of meteoric smoke has been available from measurements of heavy charge carriers. Quantitative ways are needed that relate these measured particle population to the atmospheric particle population. This requires in particular knowledge about the size-dependent, altitude-dependent and charge-dependent detection efficiency for a given instrument. In this paper, we investigate the aerodynamics for a typical electrostatic detector design. We first quantify the flow field of the background gas, then introduce particles in the flow field and determine their trajectories around the payload structure. We use two different models to trace particles in the flow field, a Continuous motion model and a Brownian motion model. Brownian motion is shown to be of basic importance for the smallest particles. Detection efficiencies are determined for three detector designs, including two with ventilation holes to allow airflow through the detector. Results from this investigation show that rocket-borne smoke detection with conventional detectors is largely limited to altitudes above 75 km. The flow through a ventilated detector has to be relatively large in order to significantly improve the detection efficiency.

To what extent did jobless Americans benefit from unemployment insurance (UI) during the COVID-19 pandemic? This article documents geographic disparities in access to UI during 2020. We leverage aggregated and individual-level claims data to perform an integrated analysis across four measures of access to UI. In addition to the traditional UI recipiency rate, we construct rates of application among the unemployed, rates of first payment among applicants, and exhaustion rates among paid claimants. Through correlations across California counties and across states, we show that areas with more disadvantaged residents had less access to UI during the pandemic. Although these disparities are large in magnitude, cross-state analysis suggests that policy can play a salient role in mitigating them.

3D printing is envisioned to play an important role in the production of membranes for e.g., water purification and bio-separation applications due to the prospect of creating new and cleverly designed structures. Among different 3D printing techniques, direct ink writing offers the opportunity to print a wide variety of materials with high-detail resolution. There is a range of parameters that need to be optimized in order to develop robust printing techniques at that scale. In this study, cellulose acetate (CA), which is a biocompatible material, has been used as an ink. In order to examine the printability and the possibility of printing features as small as a few µm, nozzles with different diameters and inks with varying amounts and molecular weights of CA were investigated. Findings in this study indicate that, depending on the wetting on the underlaying structure, the nozzle's internal and external diameter affects the detail resolution of the printed structure. Different inks result in different widths of printed strands and generally a higher amount and higher molecular weights of CA results in higher detail resolution. However, too high amount of CA and molecular weight will increase the clogging risk in the nozzle. In this study, the internal size of the nozzle was 3 µm, and by selecting a  suitable ink, it was possible to print strands down to 1 µm size and 6 µm inter-strand distance in the air, bridging supports with limited sagging. Furthermore, wall structures consisting of 300 layers, corresponding to about 300 µm in total height, were successfully printed., (© 2023. The Author(s).)

Osmoderma eremita is a species of beetle that inhabits hollows in ancient trees, which is a habitat that has decreased significantly during the last century. In southeastern Sweden, we studied the metapopulation dynamics of this beetle over a 25 year period, using capture-mark-recapture. The metapopulation size had been rather stable over time, but in most of the individual trees there had been a positive or negative trend in population development. The probability of colonisation was higher in well-connected trees with characteristics reflecting earlier successional stages, and the probability of extinction higher in trees with larger diameter (i.e. in later successional stages), which is expected from a habitat-tracking metapopulation. The annual tree mortality and fall rates (1.1% and 0.4%, respectively) are lower than the colonisation and extinction rates (5-7%), indicating that some of the metapopulation dynamics are due to the habitat dynamics, but many colonisations and extinctions take place for other reasons, such as stochastic events in small populations. The studied metapopulation occurs in an area with a high density of hollow oaks and where the oak pastures are still managed by grazing. In stands with fewer than ten suitable trees, the long-term extinction risk may be considerable, since only a small proportion of all hollow trees harbours large populations, and the population size in trees may change considerably during a decade.

The question of whether mesospheric OH( υ ) rotational population distributions are in equilibrium with the local kinetic temperature has been debated over several decades. Despite several indications for the existence of non-equilibrium effects, the general consensus has been that emissions originating from low rotational levels are thermalized. Sky spectra simultaneously observing several vibrational levels demonstrated reproducible trends in the extracted OH( υ ) rotational temperatures as a function of vibrational excitation. Laboratory experiments provided information on rotational energy transfer and direct evidence for fast multi-quantum OH(high- υ ) vibrational relaxation by O atoms. We examine the relationship of the new relaxation pathways with the behavior exhibited by OH( υ ) rotational population distributions. Rapid OH(high- υ ) + O multi-quantum vibrational relaxation connects high and low vibrational levels and enhances the hot tail of the OH(low- υ ) rotational distributions. The effective rotational temperatures of mesospheric OH( υ ) are found to deviate from local thermodynamic equilibrium for all observed vibrational levels., Competing Interests: Competing interests. The authors declare that they have no conflict of interest.

Functionalization of biomaterials with biologically active peptides can improve their performance after implantation. By genetic fusion to self-assembling proteins, the functional peptides can easily be presented on different physical formats. Herein, a chemical-free coating method based on self-assembly of the recombinant spider silk protein 4RepCT is described and used to prepare functional coatings on various biomaterial surfaces. The silk assembly was studied in real-time, revealing the occurrence of continuous assembly of silk proteins onto surfaces and the formation of nanofibrillar structures. The adsorbed amounts and viscoelastic properties were evaluated, and the coatings were shown to be stable against wash with hydrogen chloride, sodium hydroxide, and ethanol. Titanium, stainless steel, and hydroxyapatite were coated with silk fused to an antimicrobial peptide or a motif from fibronectin. Human primary cells cultured on the functional silk coatings show good cell viability and proliferation, implying the potential to improve implant performance and acceptance by the body.

All experimental models of traumatic brain injury (TBI) result in a progressive loss of brain tissue. The extent of tissue loss reflects the injury severity and can be measured to evaluate the potential neuroprotective effect of experimental treatments. Quantitation of tissue volumes is commonly performed using evenly spaced brain sections stained using routine histochemical methods and digitally captured. The brain tissue areas are then measured and the corresponding volumes are calculated using the distance between the sections. Measurements of areas are usually performed using a general purpose image analysis software and the results are then transferred to another program for volume calculations. To facilitate the measurement of brain tissue loss we developed novel algorithms which automatically separate the areas of brain tissue from the surrounding image background and identify the ventricles. We implemented these new algorithms by creating a new computer program (SectionToVolume) which also has functions for image organization, image adjustments and volume calculations. We analyzed brain sections from mice subjected to severe focal TBI using both SectionToVolume and ImageJ, a commonly used image analysis program. The volume measurements made by the two programs were highly correlated and analysis using SectionToVolume required considerably less time. The inter-rater reliability was high. Given the extensive use of brain tissue loss measurements in TBI research, SectionToVolume will likely be a useful tool for TBI research. We therefore provide both the source code and the program as attachments to this article.

Increasing evidence suggests that interleukin-1β (IL-1β) is a key mediator of the inflammatory response following traumatic brain injury (TBI). Recently, we showed that intracerebroventricular administration of an IL-1β-neutralizing antibody was neuroprotective following TBI in mice. In the present study, an anti-IL-1β antibody or control antibody was administered intraperitoneally following controlled cortical injury (CCI) TBI or sham injury in 105 mice and we extended our histological, immunological and behavioral analysis. First, we demonstrated that the treatment antibody reached target brain regions of brain-injured animals in high concentrations (> 11 nm) remaining up to 8 days post-TBI. At 48 h post-injury, the anti-IL-1β treatment attenuated the TBI-induced hemispheric edema (P < 0.05) but not the memory deficits evaluated using the Morris water maze (MWM). Neutralization of IL-1β did not influence the TBI-induced increases (P < 0.05) in the gene expression of the Ccl3 and Ccr2 chemokines, IL-6 or Gfap. Up to 20 days post-injury, neutralization of IL-1β was associated with improved visuospatial learning in the MWM, reduced loss of hemispheric tissue and attenuation of the microglial activation caused by TBI (P < 0.05). Motor function using the rotarod and cylinder tests was not affected by the anti-IL-1β treatment. Our results suggest an important negative role for IL-1β in TBI. The improved histological and behavioral outcome following anti-IL-1β treatment also implies that further exploration of IL-1β-neutralizing compounds as a treatment option for TBI patients is warranted., (© 2011 The Authors. European Journal of Neuroscience © 2011 Federation of European Neuroscience Societies and Blackwell Publishing Ltd.)

Synthetic imidazole ligands are typically substituted at the N(1) ((1)-Im) position while natural imidazole ligands are substituted at the C(4) ((4)-Im) position. To outline the difference in coordination properties, the methyl-substituted imidazoles Me(4)-Im and Me(1)-Im were complexed with CuCl(2) and ZnCl(2) and investigated by NMR relaxometry, electron paramagnetic resonance, far-Fourier transform IR vibrational spectroscopy, and ab initio calculations. Me(4)-Im, Me(1)-Im, and Im in excess form the usual tetragonal D(4h) [CuL(4)X(2)] complexes with CuCl(2) whereas the methylated imidazoles form pseudotetrahedral C(2v) complexes instead of the usual octahedral O(h) [ZnIm(6)](2+) complex. All imidazoles display a high degree of covalence in the M-L σ- and π-bonds and the π-interaction strength affects the relative energies of complexation. Opportunities to tailor complexes by the chemical properties of the substituents are envisaged due to the role of the inductive and hyperconjugative effects, rather than position.

The adsorption behaviour of ethyl(hydroxyethyl)cellulose chemically modified with imidazole (Im-EHEC) at hydrophobic surfaces has been studied with QCM-D. The very slow adsorption isotherm was due to a continuous polymer film reconfiguration and exchange of different sized polymers. The thickness of the film was about 30 nm. The polymers adsorbed Cu(2+) ions into the film from a CuCl(2) solution and a bi-layer was formed when Im-EHEC was added a second time. The second polymer film was only 7 nm thick but highly viscoelastic. After rinsing with water the metal ions was flushed away and the second Im-EHEC layer was released. The imidazole modification of EHEC enables interaction with transition metal ions and opens up for new applications for cellulose based materials.