Chemical Bonding and Crystal Structure Schemes in Atomic/Molecular Layer Deposited Fe-Terephthalate Thin Films.

Advanced deposition routes are vital for the growth of functional metal-organic thin films. The gas-phase atomic/molecular layer deposition (ALD/MLD) technique provides solvent-free and uniform nanoscale thin films with unprecedented thickness control and allows straightforward device integration. Most excitingly, the ALD/MLD technique can enable the in situ growth of novel crystalline metal-organic materials. An exquisite example is iron-terephthalate (Fe-BDC), which is one of the most appealing metal-organic framework (MOF) type materials and thus widely studied in bulk form owing to its attractive potential in photocatalysis, biomedicine, and beyond. Resolving the chemistry and structural features of new thin film materials requires an extended selection of characterization and modeling techniques. Here we demonstrate how the unique features of the ALD/MLD grown in situ crystalline Fe-BDC thin films, different from the bulk Fe-BDC MOFs, can be resolved through techniques such as synchrotron grazing-incidence X-ray diffraction (GIXRD), Mössbauer spectroscopy, and resonant inelastic X-ray scattering (RIXS) and crystal structure predictions. The investigations of the Fe-BDC thin films, containing both trivalent and divalent iron, converge toward a novel crystalline Fe(III)-BDC monoclinic phase with space group C2/c and an amorphous Fe(II)-BDC phase. Finally, we demonstrate the excellent thermal stability of our Fe-BDC thin films.

Tracking the formation potential of vivianite within the treatment train of full-scale wastewater treatment plants.

Phosphorus recovery is a vital element for the circular economy. Wastewater, especially sewage sludge, shows great potential for recovering phosphate in the form of vivianite. This work focuses on studying the iron, phosphorus, and sulfur interactions at full-scale wastewater treatment plants (Viikinmäki, Finland and Seine Aval, France) with the goal of identifying unit processes with a potential for vivianite formation. Concentrations of iron(III) and iron(II), phosphorus, and sulfur were used to evaluate the reduction of iron and the formation potential of vivianite. Mössbauer spectroscopy and X-ray diffraction (XRD) analysis were used to confirm the presence of vivianite in various locations on sludge lines. The results show that the vivianite formation potential increases as the molar Fe:P ratio increases, the anaerobic sludge retention time increases, and the sulfate concentration decreases. The digester is a prominent location for vivianite recovery, but not the only one. This work gives valuable insights into the dynamic interrelations of iron, phosphorus, and sulfur in full-scale conditions. These results will support the understanding of vivianite formation and pave the way for an alternative solution for vivianite recovery for example in plants that do not have an anaerobic digester.

Probing the correlation between corrosion resistance and biofouling of thermally sprayed metallic substrata in the field.

The correlation between inherent corrosion resistance and biofouling was investigated for five different metallic coatings. Steel panels thermally spray-coated with either aluminium, Monel, bronze or different aluminium alloys were tested in controlled salt mist conditions and electrochemical corrosion tests and subsequently employed at sea. The biofouling of the panels was monitored at different depths (5, 10 and 15 m) at periods ranging from 5 to 12 months. The main macrofouling organisms were quantified and analysed using permutational multivariate analysis. The results indicate a significant difference in fouling pressure between depths and the geographic sites used. No statistically significant link between high corrosion resistance and lower biofouling pressure was observed, indicating that the main marine macrofoulers settled equally well on corrosion resistant and corrosion prone metallic surfaces. This work sheds light on biofouling of thermally sprayed metallic substrata and it characterizes and compares biofouling assemblages from different biogeographical regions in Europe.

A diamagnetic iron complex and its twisted sister - structural evidence on partial spin state change in a crystalline iron complex.

We report here the syntheses of a diamagnetic Fe complex [Fe(HL)2] (1), prepared by reacting a redox non-innocent ligand precursor N,N'-bis(3,5-di-tert-butyl-2-hydroxy-phenyl)-1,2-phenylenediamine (H4L) with FeCl3, and its phenoxazine derivative [Fe(L')2] (2), which was obtained via intra-ligand cyclisation of the parent complex. Magnetic measurements, accompanied by spectroscopic, structural and computational analyses show that 1 can be viewed as a rather unusual Fe(III) complex with a diamagnetic ground state in the studied temperature range due to a strong antiferromagnetic coupling between the low-spin Fe(III) ion and a radical ligand. For a paramagnetic high-spin Fe(II) complex 2 it was found that, when crystalline, it undergoes a thermally induced process where 25% of the molecules in the material change to a diamagnetic low-spin ground state below 100 K. Single crystal X-ray studies conducted at 95 K afforded detailed structural evidence for this partial change of spin state of 2 showing the existence of crystallographically distinct molecules in a 3 : 1 ratio which exist in high- and low-spin states, respectively. Also, the magnetic behaviour of 2 was found to be related with the crystallinity of the material as demonstrated by near-IR radiation to unpaired electrons conversion ability of amorphous sample of 2.

Dynamical magnetic behavior of anisotropic spinel-structured ferrite for GHz technologies.

We have fabricated a high quality magnetic Ni0.5Zn0.5Fe2O4 ferrite powder/polymer composite sheet consisting of common and environmentally friendly elements only. The sheet was then tested for its dynamic permeability by irradiating with electromagnetic waves with frequencies up to 50 GHz. Two different originally developed methods were used for the high-frequency permeability measurements, a short-circuited microstrip line method and a microstrip line-probe method. It is challenging to measure the dynamic permeability of magnetic thin films/sheets beyond 10 GHz because of the low response signal from these materials. However, the two methods produced essentially equivalent results. In the frequency dependent permeability profile, the maximum position of the profile, [Formula: see text], shifted towards higher frequencies upon increasing an applied (strong) static external magnetic field, [Formula: see text]. A linear relationship between [Formula: see text] and [Formula: see text] for the entire range of [Formula: see text] was observed even at small [Formula: see text]. In general, the spinel-structured Ni-based ferrites exhibit low magnetic anisotropy, but the present sample showed a uniaxial-anisotropic behavior in the parallel direction of the sheet. Our Ni0.5Zn0.5Fe2O4 powder/polymer composite sheet thus exhibits high performance at GHz frequencies, and should be applicable e.g. as an anisotropic electromagnetic wave-interference material.

Fe3Se4: a possible ferrimagnetic half-metal?

Half-metallic ferromagnets show 100% spin-polarization at the Fermi level and are ideal candidates for spintronic applications. Despite the extensive research in the field, very few materials have been discovered so far. Here, we present results of electronic band structure calculations based on density functional theory and extensive physical-property measurements for Fe3Se4 revealing signatures of half-metallicity. The spin-polarized electronic band structure calculations predict half-metallic ferrimagnetism for Fe3Se4. The electrical resistivity follows exponentially suppressed electron-magnon scattering mechanism in the low-temperature regime and show a magnetoresistance effect that changes the sign from negative to positive with decreasing temperature around 100 K. Other intriguing observations include the anomalous behavior of Hall resistance below 100 K and an anomalous Hall coefficient that roughly follows the ρ 2 behavior.

Inflammatory activity and vitamin D levels in an MS population treated with rituximab.

BACKGROUND: Most multiple sclerosis patients on disease-modifying treatment at Umeå University Hospital are treated with rituximab and the prevalence of vitamin D supplementation has increased over time. Follow-up studies of these off-label treatments are needed. OBJECTIVE: To study inflammatory activity and adverse effects in rituximab-treated multiple sclerosis patients, and associations with 25-hydroxy-vitamin D levels. METHODS: Retrospectively collected data on repeated estimates of relapses, disability, side effects, magnetic resonance imaging, laboratory measures including 25-hydroxy-vitamin D levels and self-perceived health. RESULTS: In 272 multiple sclerosis patients with a mean follow-up of 43 months, we identified seven possible relapses during active rituximab treatment. On magnetic resonance imaging examination, new T2 lesions were seen in 1.3% (10 out of 792 scans), and 0.25% (two out of 785 scans) showed contrast enhancement. Adjusted 25-hydroxy-vitamin D levels in samples drawn close to all magnetic resonance images with new T2 lesions were lower compared to the remainder (62 vs. 81 nmol/l; P = 0.030). Levels of 25-hydroxy-vitamin D were associated with self-perceived health (r = 0.18, P = 0.041, n = 130) and C-reactive protein (r = -0.13, P = 0.042) but not with the risk of side effects. CONCLUSION: The inflammatory activity in this rituximab-treated multiple sclerosis population that increasingly used vitamin D supplementation was extremely low. Higher 25-hydroxy-vitamin D levels were associated with beneficial outcomes.

Unhindered copper uptake by glutaraldehyde-polyethyleneimine coatings in an artificial seawater model system with adsorbed swollen polysaccharides and competing ligand EDTA.

Shortly after a surface is submerged in the sea, a conditioning film is generally formed by adsorption of organic molecules, such as polysaccharides. This could affect transport of molecules and ions between the seawater and the surface. An artificial seawater model system was developed to understand how adsorbed polysaccharides impact copper binding by glutaraldehyde-crosslinked polyethyleneimine coatings. Coating performance was also determined when competed against copper-chelating EDTA. Polysaccharide adsorption and copper binding and distribution were investigated using advanced analytical techniques, including depth-resolved time-of-flight secondary ion mass spectroscopy, grazing incidence X-ray absorption near-edge spectroscopy, quartz crystal microbalance with dissipation monitoring and X-ray photoelectron spectroscopy. In artificial seawater, the polysaccharides adsorbed in a swollen state that copper readily penetrated and the glutaraldehyde-polyethyleneimine coatings outcompeted EDTA for copper binding. Furthermore, the depth distribution of copper species was determined with nanometre precision. The results are highly relevant for copper-binding and copper-releasing materials in seawater.

Electroactive Polyhydroquinone Coatings for Marine Fouling Prevention-A Rejected Dynamic pH Hypothesis and a Deceiving Artifact in Electrochemical Antifouling Testing.

Nanometer-thin coatings of polyhydroquinone (PHQ), which release and absorb protons upon oxidation and reduction, respectively, were tested for electrochemically induced anti-biofouling activity under the hypothesis that a dynamic pH environment would discourage fouling. Antifouling tests in artificial seawater using the marine, biofilm-forming bacterium Vibrio alginolyticus proved the coatings to be ineffective in fouling prevention but revealed a deceiving artifact from the reactive species generated at the counter electrode (CE), even for electrochemical bias potentials as low as |400| mV versus Ag|AgCl. These findings provide valuable information on the preparation of nanothin PHQ coatings and their electrochemical behavior in artificial seawater. The results further demonstrate that it is critical to isolate the CE in electrochemical anti-biofouling testing.

Magnetic properties and structural characterization of iron oxide nanoparticles formed by Streptococcus suis Dpr and four mutants.

Streptococcus suis Dpr belongs to the Dps family of bacterial and archaeal proteins that oxidize Fe(2+) to Fe(3+) to protect microorganisms from oxidative damage. The oxidized iron is subsequently deposited as ferrihydrite inside a protein cavity, resulting in the formation of an iron core. The size and the magnetic properties of the iron core have attracted considerable attention for nanotechnological applications in recent years. Here, the magnetic and structural properties of the iron core in wild-type Dpr and four cavity mutants were studied. All samples clearly demonstrated a superparamagnetic behavior in superconducting quantum interference device magnetometry and Mössbauer spectroscopy compatible with that of superparamagnetic ferrihydrite nanoparticles. However, all the mutants exhibited higher magnetic moments than the wild-type protein. Furthermore, measurement of the iron content with inductively coupled plasma mass spectrometry revealed a smaller amount of iron in the iron cores of the mutants, suggesting that the mutations affect nucleation and iron deposition inside the cavity. The X-ray crystal structures of the mutants revealed no changes compared with the wild-type crystal structure; thus, the differences in the magnetic moments could not be attributed to structural changes in the protein. Extended X-ray absorption fine structure measurements showed that the coordination geometry of the iron cores of the mutants was similar to that of the wild-type protein. Taken together, these results suggest that mutation of the residues that surround the iron storage cavity could be exploited to selectively modify the magnetic properties of the iron core without affecting the structure of the protein and the geometry of the iron core.