Paradigms and paradoxes: the ionization potential of atomic astatine (Z =85), polonium (Z = 84), and some other elements—what does this value tell us about the energetics of atomic and diatomic halogens

Structural Chemistry - The newly measured ionization potential of atomic astatine is discussed and compared with that of the recently determined value for polonium and for the other atomic...     

Development and Validation of an Analytical Method for Determination of Al,Ca, Cd,Fe, Mg and P in Calcium-Rich Materials by ICP OES

Four procedures based on closed-vessel microwave-assisted wet digestion with different oxidative reagents, including HNO₃ (P1), HNO₃ + H₂O₂ (P2), aqua regia (P3) and Lefort aqua regia (P4), for preparation of calcium (Ca)-rich materials prior to determination of total concentrations of Al, Ca, Cd, Fe, Mg and P by inductively coupled optical emission spectrometry (ICP OES) were compared. It was found that digestion with Lefort aqua regia (P4) provided the best results for all examined elements, i.e., precision of 0.30–4.4%, trueness better than 2%, recoveries of added elements between 99.5–101.9%, and limits of detection within 0.08–1.8 ng g⁻¹. Reliability of this procedure was verified by analysis of relevant certified reference materials (CRMs), i.e., Natural Moroccan Phosphate Rock—Phosphorite (BCR-O32). Additionally, selection of appropriate analytical lines for measurements of element concentrations, linear dynamic ranges of calibration curves and matrix effects on the analyte response were extensively investigated. Finally, the selected procedure was successfully applied for routine analysis of other Ca-rich materials, i.e., CRMs such as NIST 1400 (Bone Ash), CTA-AC-1 (Apatite Concentrate Kola Peninsula) and NCS DC70308 (Carbonate Rock), and six natural samples, such as a dolomite, a phosphate rock, an enriched superphosphate fertilizer, pork bones, pork bones after incineration, and after steam gasification.     

Bis-periazulene: a simple Kekulé biradical with a triplet ground state

B3LYP/6-31G* calculations on bis-periazulene (cyclohepta[def]-fluorene) predict a triplet ground state for this molecule. The singlet has an aromatic 14π-electron periphery but is 2 kcal/mol higher in energy. The results agree with earlier predictions by Heilbronner. Received: 19 August 1998 / Accepted: 6 October 1998 / Published online: 23 February 1999     

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.     

Quantitative MRI analysis of structural changes in tomato tissues resulting from dehydration

A quantitative magnetic resonance imaging (MRI) analysis at 1.5T of the effects of different dehydration regimes on transverse relaxation parameters measured in tomato tissue is presented. Multi-exponential T₂ maps have been estimated for the first time, providing access to spatialized microstructural information at voxel scale. The objective was to provide a better understanding of the changes in the multi-exponential transverse relaxation parameters induced by dehydration in tomato tissues and to unravel the effects of microstructure and composition on relaxation parameters. The results led to the hypothesis that the multi-exponential relaxation signal reflects cell compartmentation and tissue heterogeneity, even at the voxel scale. Multi-exponential relaxation times provided information about water loss from specific cell compartments and seem to indicate that the dehydration process mainly affects large cells. By contrast, total signal intensity showed no sensitivity to variations in water content in the range investigated in the present study (between 95% [fresh tissue] and 90% [after dehydration]). The variation in relaxation times resulting from water loss was due to both changes in solute concentration and compartment size. The comparative analysis of the two contrasted tissues in terms of microporosity demonstrated that magnetic susceptibility effects, caused by the presence of air in the placenta tissue, significantly impact the effective relaxation and might be the dominant effect in the variations observed in relaxation times in this tissue.     

Inhibitory Effect of DMSO on Halohydrin Dehalogenase: Experimental and Computational Insights into the Influence of an Organic Co-solvent on the Structural and Catalytic Properties of a Biocatalyst

Although the application of organic solvents in biocatalysis is well explored, in-depth understanding of the interactions of solvent with proteins, in particular oligomeric ones, is still scant. Understanding these interactions is essential in tailoring enzymes for industrially relevant catalysis in nonaqueous media. In our study, the homotetrameric enzyme halohydrin dehalogenase (HHDH) from Agrobacterium radiobacter AD1 (HheC) was investigated, as a model system, in DMSO/water solvent mixtures. DMSO, the most commonly used co-solvent for biocatalytic transformations, was found to act as a mixed-type inhibitor with a prevalent competitive contribution. Even 5 % (v/v) DMSO inhibits the activity of HheC by half. Molecular dynamics (MD) simulations showed that DMSO keeps close to Ser-Tyr catalytic residues forming alternate H-bonds with them. Stability measurements paired with differential scanning calorimetry, dynamic light scattering methods and MD studies revealed that HheC maintains its structural integrity with as much as 30 % (v/v) DMSO.     

Eco-friendly rapid synthesis of 3-substituted-2-thioxo-2,3-dihydroquinazolin-4(1H)-ones in choline chloride based deep eutectic solvent

A series of 3-substituted-2-thioxo-2,3-dihydroquinazolin-4(1H)-ones and 6-iodo-3-substituted-2-thioxo-2,3-dihydroquinazolin-4(1H)-ones were synthesized in choline chloride/urea deep eutectic solvent. Substituted 2-mercapto-4(3H)-quinazolinones were synthesized from anthranilic acid or 5-iodoanthranilic acid and appropriate isothiocyanates in good to excellent yields. Isolation of final product was easy and required no further purification. Synthesis of these compounds was rapid, selective, and catalyst free, while preparation of deep eutectic solvent was easy, components are readily available, cheap, and environmentally friendly.     

Optical Response From Functionalized Atomically Thin Nanomaterials

Chemical functionalization of atomically thin nanostructures presents a promising strategy to create new hybrid nanomaterials with remarkable and externally controllable properties. Here, we review our research in the field of theoretical modeling of carbon nanotubes, graphene, and transition metal dichalcogenides located in molecular dipole fields. In particular, we provide a microscopic view on the change of the optical response of these technologically promising nanomaterials due to the presence of photo‐active spiropyran molecules. The feature article presents a review of recent theoretical work providing microscopic view on the optical response of chemically functionalized carbon nanotubes, graphene, and monolayered transition metal dichalcogenides. In particular, we propose a novel sensor mechanism based on the molecule‐induced activation of dark excitons. This results in a pronounced additional peak presenting an unambiguous optical fingerprint for the attached molecules.     

Temperature mapping in bread dough using SE and GE two-point MRI methods: experimental and theoretical estimation of uncertainty

Two-dimensional (2D)-SE, 2D-GE and tri-dimensional (3D)-GE two-point T(1)-weighted MRI methods were evaluated in this study in order to maximize the accuracy of temperature mapping of bread dough during thermal processing. Uncertainties were propagated throughout each protocol of measurement, and comparisons demonstrated that all the methods with comparable acquisition times minimized the temperature uncertainty to similar extent. The experimental uncertainties obtained with low-field MRI were also compared to the theoretical estimations. Some discrepancies were reported between experimental and theoretical values of uncertainties of temperature; however, experimental and theoretical trends with varying parameters agreed to a large extent for both SE and GE methods. The 2D-SE method was chosen for further applications on prefermented dough because of its lower sensitivity to susceptibility differences in porous media. It was applied for temperature mapping in prefermented dough during chilling prior to freezing and compared locally to optical fiber measurements.