Photomagnetic Switching of the Complex [Nd(dmf)4(H2O)3(μ‐CN)Fe(CN)5]⋅H2O Analyzed by Single‐Crystal X‐Ray Diffraction

X‐ray vision : Single‐crystal XRD experiments (see picture) reveal the excited‐state structure of the photomagnetic heterobimetallic title complex. The system shows a decrease in all the iron–ligand bond lengths, suggesting that photoexcitation involves a ligand‐to‐metal charge transfer or a change in the superexchange coupling between the metal centers.

     

Time‐Resolved In Situ Synchrotron X‐ray Study and Large‐Scale Production of Magnetite Nanoparticles in Supercritical Water

A general solution : In situ synchrotron X‐ray scattering in a high‐pressure pulsed injection reactor (see picture) shows that magnetite nucleation and growth are temporally separated. Gram‐scale crystalline, pure phase, superparamagnetic magnetite nanoparticles were synthesized without surfactants in supercritical water in less than one hour using a laboratory‐scale continuous‐flow reactor.

     

Crystal structures of thermoelectric n- and p-type Ba8Ga16Ge30 studied by single crystal, multitemperature, neutron diffraction, conventional X-ray diffraction and resonant synchrotron X-ray diffraction

Comprehensive single-crystal structural investigations of n- and p-type Ba8Ga16Ge30 have been carried out using multitemperature neutron and conventional X-ray diffraction as well as resonant synchrotron X-ray diffraction. The data show that the guest atom positions and dynamics are very similar in the two structures, although the barium atoms are slightly more displaced from the cage centers in the p-type structure than in the n-type structure (Deltad = 0.025 A). For both structures Fourier difference maps calculated from very high-resolution neutron diffraction data (sin theta/lambda > 2 A-1) show that the Ba nuclear density at lowest temperatures (15 K) is distributed in a torus around the crystallographic 6d site with maxima in the 24j positions. At room temperature the maxima have shifted to the 24k position. Analysis of atomic displacement parameters give Einstein temperatures of approximately 60(1) K for both structures. Thus, the fundamental difference in the low temperature thermal conductivity observed for p- and n-type Ba8Ga16Ge30 appear not to be directly related to the guest atom behavior as is commonly assumed in thermoelectric research. The neutron data and the resonant synchrotron X-ray data facilitate refinement of Ga/Ge framework occupancies. The Ga atoms have a clear preference for the 6c site with the preference being somewhat stronger for the n-type structure.     

Microwave-assisted aminolysis of vinylepoxides

Di- and trisubstituted vinylepoxides in NH₄OH were subjected to microwave irradiation affording the corresponding vicinal aminoalcohols in high yields. The reaction is stereospecific and highly regioselective for addition at the allylic carbon.     

Intercomparison on measurements of PCBs in pork fat during the Belgian PCB-crisis

During the Belgian PCB crisis (1999/2000) the quality of the data from the PCB monitoring were studied with a proficiency testing experiment. Pork fat that was spiked at the Institute for Reference Materials and Measurements (EC-JRC-IRMM) was sent out as unknown to all laboratories that participated in the monitoring. In parallel, the material was certified on the basis of the results of several leading PCB laboratories throughout Europe that did not participate in the monitoring. During the first round 15 to 25% deviation was experienced, while in the end of this multistep intercalibration procedure the average deviation for the respective PCBs was 10.9% (PCB 28), 13.1% (PCB 52), 10.1% (PCB 101), 10.7% (PCB 118), 10.7% (PCB 138), 9.1% (PCB 153), 8.1% (PCB 180) and 8.2% for the sum of the 7 PCBs. The concentrations measured for the higher volatile PCB 28 had a tendency to show lower levels, while for PCB 180 this was less pronounced. On the other hand, PCB 153 showed results rather to the higher side. During this exercise the material was also tested for stability by one of the certifying laboratories.     

A comparative CP/MAS 13C-NMR study of cellulose structure in spruce wood and kraft pulp

CP/MAS ¹³C-NMR spectroscopy in combination with spectral fitting was used to study the supermolecular structure of the cellulose fibril in spruce wood and spruce kraft pulp. During pulping, structures contributing to inaccessible surfaces in the wood cellulose are converted to the cellulose I allomorph, that is, the degree of order is increased. This increase is also accompanied by a conversion of cellulose I to cellulose I. Cellulose from wood composed of different cell types, that is, compression wood, juvenile wood, earlywood, latewood and normal wood exhibited a similar supermolecular structure. Assignments were made for signals from hemicellulose which contribute significantly to the spectral C-4 region (80–86 ppm) in kraft pulp spectra but substantially less to the corresponding region in wood spectra.     

On the accessibility and structure of xylan in birch kraft pulp

The structure of -(14)-xylan, both in isolated form and as a component of bleached birch kraft pulp, was studied employing CP/MAS ¹³C NMR spectroscopy. Bleached birch kraft pulp was treated with xylanases or alkali in order to distinguish between accessible and inaccessible xylan. In xylan which was alkali-extracted from bleached birch kraft pulp, the relative contents of xylose and 4-O-methylglucuronic acid were 99.4 and 0.6 weight %, respectively, and the degree of polymerization was 70. The supermolecular structure of xylan is very sensitive to the surrounding environment. All extracted xylan chains were accessible to water and methanol and the solvent molecules easily exchanged. In bleached birch kraft pulp, cellulose fibrils interact with xylan chains, causing these to adopt a conformation similar to one of the configurations observed for dry xylan. In birch pulp, about 1/3 of the xylan was found to be accessible to digestion by xylanases or extraction with 5% w/w potassium hydroxide (aq). A signal at 81.7ppm in the C-4 region of the CP/MAS ¹³C NMR spectrum of bleached birch kraft pulp originated from xylan at the accessible fibril surfaces. A portion of a broad signal at 83.5ppm reflected inaccessible xylan, which is probably present as co-aggregates with cellulose fibril aggregates.     

The influence of hemicellulose on fibril aggregation of kraft pulp fibres as revealed by FE-SEM and CP/MAS 13C-NMR

Three Norway spruce pulps were produced using different kraft pulping methods, in order to obtain large differences in cellulose and hemicellulose proportions at a similar lignin content. The hemicellulose content in the three pulps varied between 10% and 22%. The aim of the study was to evaluate the influence of cellulose and hemicellulose on fibre ultrastructure and correlate this with the differences observed in the mechanical properties between the pulps. The ultrastructure of the pulp fibres were studied using Field Emission Scanning Electron Microscopy (FE-SEM) and Solid-State Cross Polarisation Magic Angle Spinning Carbon-13 Nuclear Magnetic Resonance (CP/MAS ¹³C-NMR) in combination with spectral fitting. CP/MAS ¹³C-NMR measured the average bulk properties of the pulp fibres, while FE-SEM allowed for observations on the ultrastructure of fibre surfaces. The ultrastructure of the fibres varied with varying hemicellulose content. The pulp with a high hemicellulose content had a porous surface structure. In fibres with a low hemicellulose content, the fibril aggregates (macrofibrils) formed a much more compact surface structure. With CP/MAS ¹³C-NMR this change was reflected by an increase in average fibril aggregate width with decreasing hemicellulose content. Results from FE-SEM and CP/MAS ¹³C-NMR correlated well. The changes recorded in ultrastructure may explain the very different mechanical properties reported previously for pulps with different hemicellulose content.     

Synchrotron X-ray Electron Density Analysis of Chemical Bonding in the Graphitic Carbon Nitride Precursor Melamine

Melamine is a precursor and building block for graphitic carbon nitride (g-CN) materials, a group of layered materials showing great promise for catalytic applications. The synthetic pathway to g-CN includes a polycondensation reaction of melamine by evaporation of ammonia. Melamine molecules in the crystal organize into wave-like planes with an interlayer distance of 3.3 Å similar to that of g-CN. Here we present an extensive investigation of the experimental electron density of melamine obtained from modelling of synchrotron radiation X-ray single-crystal diffraction data measured at 25 K with special focus on the molecular geometry and intermolecular interactions. Both intra- and interlayer structures are dominated by hydrogen bonding and π-interactions. Theoretical gas-phase optimizations of the experimental molecular geometry show that bond lengths and angles for atoms in the same chemical environment (C−N bonds in the ring, amine groups) differ significantly more for the experimental geometry than for the gas-phase-optimized geometries, indicating that intermolecular interactions in the crystal affects the molecular geometry. In the experimental crystal geometry, one amine group has significantly more sp³-like character than the others, hinting at a possible formation mechanism of g-CN. Topological analysis and energy frameworks show that the nitrogen atom in this amine group participates in weak intralayer hydrogen bonding. We hypothesize that melamine condenses to g-CN within the layers and that the unique amine group plays a key role in the condensation process.