Polychromatic neutron phase-contrast imaging of weakly absorbing samples enabled by phase retrieval.

The use of a phase-retrieval technique for propagation-based phase-contrast neutron imaging with a polychromatic beam is demonstrated. This enables imaging of samples with low absorption contrast and/or improving the signal-to-noise ratio to facilitate e.g. time-resolved measurements. A metal sample, designed to be close to a phase pure object, and a bone sample with canals partially filled with D2O were used for demonstrating the technique. These samples were imaged with a polychromatic neutron beam followed by phase retrieval. For both samples the signal-to-noise ratios were significantly improved and, in the case of the bone sample, the phase retrieval allowed for separation of bone and D2O, which is important for example for in situ flow experiments. The use of deuteration contrast avoids the use of chemical contrast enhancement and makes neutron imaging an interesting complementary method to X-ray imaging of bone.

High-resolution 3D X-ray diffraction microscopy: 3D mapping of deformed metal microstructures.

Three-dimensional X-ray diffraction microscopy, 3DXRD, has become an established tool for orientation and strain mapping of bulk polycrystals. However, it is limited to a finite spatial resolution of ∼1.5-3 µm. Presented here is a high-resolution modality of the technique, HR-3DXRD, for 3D mapping of submicrometre-sized crystallites or subgrains with high spatial and angular resolution. Specifically, the method is targeted to visualization of metal microstructures at industrially relevant degrees of plastic deformation. Exploiting intrinsic crystallographic properties of such microstructures, the high resolution is obtained by placing a high-resolution imaging detector in between the near-field and far-field regimes. This configuration enables 3D mapping of deformation microstructure by determining the centre of mass and volume of the subgrains and generating maps by tessellation. The setup is presented, together with a data analysis approach. Full-scale simulations are used to determine limitations and to demonstrate HR-3DXRD on realistic phantoms. Misalignments in the setup are shown to cause negligible shifts in the position and orientation of the subgrains. Decreasing the signal-to-noise ratio is observed to lead primarily to a loss in the number of determined diffraction spots. Simulations of an α-Fe sample deformed to a strain of ε vM = 0.3 and comprising 828 subgrains show that, despite the high degree of local texture, 772 of the subgrains are retrieved with a spatial accuracy of 0.1 µm and an orientation accuracy of 0.0005°.

Improved dynamic imaging of multiphase flow by constrained tomographic reconstruction.

Dynamic tomography has become an important technique to study fluid flow processes in porous media. The use of laboratory X-ray tomography instruments is, however, limited by their low X-ray brilliance. The prolonged exposure times, in turn, greatly limit temporal resolution. We have developed a tomographic reconstruction algorithm that maintains high image quality, despite reducing the exposure time and the number of projections significantly. Our approach, based on the Simultaneous Iterative Reconstruction Technique, mitigates the problem of few and noisy exposures by utilising a high-quality scan of the system before the dynamic process is started. We use the high-quality scan to initialise the first time step of the dynamic reconstruction. We further constrain regions of the dynamic reconstruction with a segmentation of the static system. We test the performance of the algorithm by reconstructing the dynamics of fluid separation in a multiphase system. The algorithm is compared quantitatively and qualitatively with several other reconstruction algorithms and we show that it can maintain high image quality using only a fraction of the normally required number of projections and with a substantially larger noise level. By robustly allowing fewer projections and shorter exposure, our algorithm enables the study of faster flow processes using laboratory tomography instrumentation but it can also be used to improve the reconstruction quality of dynamic synchrotron experiments.

Real Time 3D Observations of Portland Cement Carbonation at CO2 Storage Conditions.

Depleted oil reservoirs are considered a viable solution to the global challenge of CO2 storage. A key concern is whether the wells can be suitably sealed with cement to hinder the escape of CO2. Under reservoir conditions, CO2 is in its supercritical state, and the high pressures and temperatures involved make real-time microscopic observations of cement degradation experimentally challenging. Here, we present an in situ 3D dynamic X-ray micro computed tomography (µ-CT) study of well cement carbonation at realistic reservoir stress, pore-pressure, and temperature conditions. The high-resolution time-lapse 3D images allow monitoring the progress of reaction fronts in Portland cement, including density changes, sample deformation, and mineral precipitation and dissolution. By switching between flow and nonflow conditions of CO2-saturated water through cement, we were able to delineate regimes dominated by calcium carbonate precipitation and dissolution. For the first time, we demonstrate experimentally the impact of the flow history on CO2 leakage risk for cement plugging. In-situ µ-CT experiments combined with geochemical modeling provide unique insight into the interactions between CO2 and cement, potentially helping in assessing the risks of CO2 storage in geological reservoirs.

Canalicular Junctions in the Osteocyte Lacuno-Canalicular Network of Cortical Bone.

The osteocyte lacuno-canalicular network (LCN) is essential for bone remodeling because osteocytes regulate cell recruitment. This has been proposed to occur through liquid-flow-induced shear forces in the canaliculi. Models of the LCN have thus far assumed that it contains canaliculi connecting the osteocyte lacunae. However, here, we reveal that enlarged spaces occur at places where several canaliculi cross; we name these spaces canalicular junctions. We characterize them in detail within mice cortical bone using synchrotron nanotomography at two length scales, with 50 and 130 nm voxel size, and show that canalicular junctions occur at a density similar to that of osteocyte lacunae and that canalicular junctions tend to cluster. Through confocal laser scanning microscopy, we show that canalicular junctions are widespread as we have observed them in cortical bone from several species, even though the number density of the canalicular junctions was not universal. Fluid flow simulations of a simple model system with and without a canalicular junction clearly show that liquid mass transport and flow velocities are altered by the presence of canalicular junctions. We suggest that these canalicular junctions may play an important role in osteocyte communication and possibly also in canalicular fluid flow. Therefore, we believe that they constitute an important component in the bone osteocyte network.

Acids 'generally recognized as safe' affect morphology and biocompatibility of electrospun chitosan/polyethylene oxide nanofibers.

Electrospinning of neat chitosan is currently achieved by using strong acids or organic solvents, which limits the use of chitosan nanofibers as biocompatible scaffolds for drug delivery and tissue engineering. The aim was to elucidate the effect of specific acids generally recognized as safe (GRAS) on the properties of electrospun chitosan-based nanofibers. Electrospinning chitosan in dilute acetic acid or succinic acid with polyethylene oxide resulted in white and separated nanofibers, whereas nanofibers electrospun in dilute citric acid were transparent and interconnected. Including succinic or citric acid in the spinning process induced disintegration of the fiber mat after four hours in water, and a concentration-dependent effect on epithelial cell viability. Chitosan nanofibers electrospun in acetic acid maintained their shape and fibrous structure after four hours in water, and showed no effect on cell viability. This study demonstrates that the choice of GRAS acid highly determines the properties of electrospun chitosan nanofibers.

Hierarchically porous, ultra-strong reduced graphene oxide-cellulose nanocrystal sponges for exceptional adsorption of water contaminants.

Self-assembly of graphene oxide (GO) nanosheets into porous 3D sponges is a promising approach to exploit their capacity to adsorb contaminants while facilitating the recovery of the nanosheets from treated water. Yet, forming mechanically robust sponges with suitable adsorption properties presents a significant challenge. Ultra-strong and highly porous 3D sponges are formed using GO, vitamin C (VC), and cellulose nanocrystals (CNCs) - natural nanorods isolated from wood pulp. CNCs provide a robust scaffold for the partially reduced GO (rGO) nanosheets resulting in an exceptionally stiff nanohybrid. The concentration of VC as a reducing agent plays a critical role in tailoring the pore architecture of the sponges. By using excess amounts of VC, a unique hierarchical pore structure is achieved, where VC grains act as soft templates for forming millimeter-sized pores, the walls of which are also porous and comprised of micron-sized pores. The unique hierarchical pore structure ensures the interconnectivity of pores even at the core of large sponges as evidenced by micro and nano X-ray computed tomography. The unique pore architecture translates into an exceptional specific surface area for adsorption of a wide range of contaminants, such as dyes, heavy metals, pharmaceuticals and cyanotoxin from water.

Comparison between theoretically and experimentally determined electronic properties: applications to two-photon singlet oxygen sensitizers.

A series of oligo-phenylenevinylenes are investigated by spectroscopic measurements and calculations with the aim to rationalize the correlation between the electronic structure of the molecules and their efficiency as two-photon singlet oxygen sensitizers. The band-shape functions of selected two-photon absorption processes are analyzed and the corresponding spectra are deconvoluted. This analysis allows for a comparison between calculated and measured two-photon absorption cross sections where a reasonable agreement is found.

4-Bromo-seleno-anisole.

The title compound, 1-bromo-4-methyl-seleno-benzene, C(7)H(7)BrSe, was prepared by methyl-ation of 4-bromo-seleno-phenolate with methyl iodide, and crystals suitable for structure determination were obtained by sublimation. The mol-ecule is essentially planar; the Se-Me bond is rotated by only 2.59 (19)° out of the least-squares plane of the benzene ring. The most pronounced intermolecular interactions are two hydrogen bonds of the type C-H⋯π, which determine a herring-bone pattern in the crystal packing.

1,4-Bis(4-chloro-phenyl-seleno)-2,5-di-methoxy-benzene.

The title compound, C(20)H(16)Cl(2)O(2)Se(2), utilizes the symmetry of the crystallographic inversion center. Mol-ecular chains are formed through symmetric C-H⋯Cl inter-actions around inversion centers, mimicking the commonly observed symmetric hydrogen-bonded dimer pattern often found in carboxylic acids.

(E,E,E)-1,3,5-Tris[4-(acetylsulfanyl)styryl]benzene toluene hemisolvate.

The first crystal structure of a three-terminal sulfur end-capped oligophenylenevinylene, C36H30O3S3 x 0.5C7H8, has been determined at 122 (1) K. The molecular threefold symmetry is not utilized in the crystal structure. It is confirmed that the double bonds have been fully transformed into a trans configuration by iodine treatment.

Structure refinement of a twinned pseudo-symmetric crystal of [Mn(C10H24N4)(NCO)2]+*ClO4-.

The crystal studied is a 0.545 (1):0.455 twin, space group C\bar 1, Z = 16, and is a commensurate occupational and displacive modulation of a Z = 4 idealized parent structure with the space group A2/a and a(p) = a/2, b(p) = b/2, c(p) = c. A hierarchical approach to solution and refinement led sequentially to structures in the space groups A2/a, P2(1)/n, P\bar 1 and finally C\bar 1. The major and minor components of the reflection intensities could be identified using irreducible representations of A2/a and P2(1)/n, which in turn suggested suitable constraints and restraints for optimizing the refinement pathway. Comparative refinement was used to show the correctness of the final structure solution and how appropriately chosen constrained refinement allowed an escape from a false minima.

Two square-pyramidal chromium(V)-nitride complexes: bis(2-methylquinolin-8-olato)nitridochromium(V) and nitridobis(2-sulfidopyridine N-oxide)chromium(V).

Two new chromium(V)-nitride complexes with a coordination sphere completed by bidentate ligands have been synthesized and structurally characterized. Bis(2-methylquinolin-8-olato)nitridochromium(V), [Cr(C10H8NO)2(N)], has the coordination sphere completed by an equatorial N2O2 set of ligators. The compound crystallizes with the five-coordinate complexes at sites with twofold rotational symmetry and all Cr-N bond directions aligned with the crystallographic b axis. Nitridobis(2-sulfidopyridine N-oxide)chromium(V), [Cr(C5H4NOS)2(N)], crystallizes with the molecules on general positions and has an equatorial S2O2 coordination environment, which is unprecedented among nitride complexes of the first-row transition metals. In both systems, Cr[triple-bond]N bonds are short at ca 1.56 A.

Facile cobalt(III) template synthesis of novel branched hexadentate polyamine monocarboxylates.

New hexadentate polyamine monocarboxylate ligands, 11-amino-9-(2-aminoethyl)-3,6,9-triazaundecanoate (tren-engly-), 12-amino-10-(2-aminoethyl)-3,7,10-triazadodecanoate (tren-tngly-) and 13-amino-11-(2-aminoethyl)-3,8,11-triazatridecanoate (tren-bngly-), were synthesized by intramolecular coupling of tetradentate tris(2-aminoethyl)amine (tren) and didentate N-([small omega]-formylalkyl)glycinates, OCH(CH2)nNHCH2CO2-, in easily and stereoselectively assembled cobalt(III) templates, p-[Co(tren){(RO)2CH(CH2)nNHCH2CO2}](O3SCF3)2, n = 1-3 (R = Me or Et). The reaction sequences comprised assembly of the template from [Co(tren)(O3SCF3)2]O3SCF3 (1) and (RO)2CH(CH2)nNHCH2CO2Et, deprotection of the pendant acetal in acid, intramolecular condensation of the resulting aldehyde with a coordinated primary amine at intermediate pH to form the imine and reduction of this by NaBH4. For n= 1, imine formation occurred exclusively at the primary amine trans to the carboxylate producing the hexadentate 11-amino-9-(2-aminoethyl)-3,6,9-triazaundeca-5-enoato (tren-enimgly-) complex, i-[Co(tren-enimgly)]Cl2.3.5H2O. In all instances, subsequent imine reduction gave the s isomer complex, exclusively. Complexes p-[Co(tren){(MeO)2CHCH2gly}](O3SCF3)2 (3), i-[Co(tren-enimgly)]ZnCl4.H2O (5), s-[Co(tren-engly)]ZnCl(4)(s-6), s-[Co(tren-tngly)]ZnCl4.H2O (s-7) and s-[Co(tren-bngly)ZnCl3]2ZnCl4 (s-8) were structurally characterized by X-ray crystallography. Charcoal-catalyzed equilibration of s-[Co(tren-engly)]Cl(2).2H(2)O dissolved in water produced the s- (s-6), p- (p-6) and t-[Co(tren-engly)]2+ (t-6) isomers in comparable amounts. p-6 and t-6 were also structurally characterized as their tetrachlorozincate and chloride salts, respectively. In base-catalyzed reactions, s-6 and t-6 each also formed p-6. Reduction of s-[Co(tren-engly)]Cl2.2H2O with (NH4)2S and acidification liberated the pentaamino carboxylic acid ligand which was isolated as the hydrochloride salt.

Modeling of the nuclear parameters for H atoms in X-ray charge-density studies.

Extensive and precise X-ray diffraction data for xylitol have been used to test different approaches to estimate nuclear parameters for H atoms in charge-density studies. The parameters from a neutron diffraction study of the same compound were taken as a reference. The resulting static charge densities obtained for the different approaches based on a multipole model were subjected to a topological analysis. The comparative analysis led to the following results. The procedure of extending the X-H bond to match bond lengths from neutron diffraction studies provides the best agreement with the neutron positional parameters. An isotropic model for the atomic displacements of H atoms is highly unsatisfactory and leads to significant deviations for the properties of the bond critical points including those that only involve non-H atoms. Anisotropic displacement parameters for H atoms can be derived from the X-ray data that are in agreement with the values from the neutron study, and the resulting charge-density models are in good agreement with the reference model. The anisotropic displacement parameters for H atoms are derived from the X-ray data as a sum of the external (rigid-body) and internal vibrations. The external vibrations are obtained from a TLS analysis of the ADPs of the non-H atoms and the internal vibrations from analysis of neutron diffraction studies of related compounds. The results from the analysis of positional and thermal parameters were combined to devise a 'best anisotropic' model, which was employed for three other systems where X-ray and neutron data were available. The results from the topological analysis of these systems confirm the success of the 'best anisotropic' model in providing parameters for the H atoms that give charge densities in agreement with the reference models based on H-atom parameters derived from neutron diffraction.

Rationalisation of weak ferromagnetism in manganese(III) chains: the relation between structure and ordering phenomena.

The synthesis, structure and magnetic properties of the one-dimensional chain compounds [Mn(cyclam)(SO4)]ClO4.H2O (1) and [Mn(cyclam)(HCOO)](CF3SO3)(ClO4) (2) are reported. Cyclam is the cyclic tetradentate ligand 1,4,7,11-tetraazacyclotetradecane. Both chain compounds exhibit antiferromagnetic interactions within the chains. A magnetic ordering phase transition at 5.5 K in (1) is investigated by magnetisation measurements along the three principal crystallographic axes of a single crystal and the results show unambiguously that the ferromagnetic ordering is only taking place along one crystallographic axis. The spin structure of the magnetic ordered phase and the magnitude of the ferromagnetic moment are correlated with the crystal structure and symmetry of the compound.

Aqueous solubility study of salts of benzylamine derivatives and p-substituted benzoic acid derivatives using X-ray crystallographic analysis.

Twenty two p-substituted benzoic acid derivates were used to prepare salts of N-methylbenzylamine (II) and N,N-dimethylbenzylamine (III), respectively. Only five salts of (II) and two salts of (III) were obtained in a crystalline state. The solubility of these salts was orders of magnitude higher than those reported for the corresponding salts of benzylamine (I). Thermal analysis indicated that the increased solubility was caused by reduced crystal lattice energy, which was most likely due to the reduced number of strong hydrogen bonds of the salt of (II) and (III). X-ray crystallographic analysis of p-hydroxybenzoic acid salt of (I), (II) and (III) suggested that the reduced number of hydrogen bonds caused the apparent higher solubility. Further analyses of seven salts of (I) were performed. It was not possible to identify any relationship between the number of hydrogen bonds and the corresponding solubility of the salts.

Simultaneous variation of multipole parameters and Gram-Charlier coefficients in a charge-density study of tetrafluoroterephthalonitrile based on X-ray and neutron data.

Difficulties encountered in modelling the scattering of fluorine in organic compounds have been investigated through refinements of accurate X-ray and neutron diffraction data measured on tetrafluoroterephthalonitrile, TFT, at 122.4 K. Multipole refinements led to a highly contracted octopole on fluorine. The subsequent analysis revealed that fluorine does not possess a valence octopole but exhibits anharmonic thermal motion that can be modelled by the octopole multipole parameters. The scattering contribution from the octopole shows the same cubic dependence in the scattering vector as the Gram-Charlier expansion of the nuclear displacements to third order. The analysis also showed that refinement of third-order Gram-Charlier coefficients on fluorine requires data to at least 0.93 A(-1) resolution in sinthetas/lambda. The X-ray data extending to 1.27 A(-1) were of sufficient resolution to include third-order Gram-Charlier coefficients for N, F and the cyano C atoms in the refinement, whereas the neutron data only enabled refinement of the third-order Gram-Charlier coefficients for nitrogen. The refinements of the neutron and X-ray diffraction data yielded identical atomic displacement parameters for all the atoms. Though inclusion of anharmonic motion for N and F atoms provides the best model, it does not affect the crystal electron density, and all intramolecular bond critical points have identical features. Application of the anharmonic model, however, leads to small differences in the intermolecular interactions, which is illustrated by the electrostatic potential adjacent to the N atom. The characteristics of the C-F bond were elucidated by the topological analysis of the crystal electron density, which also supported the proposed quinonoid structure of the benzene ring.

Hydrogen bonding in enantiomeric versus racemic mono-carboxylic acids; a case study of 2-phenoxypropionic acid.

The structural and thermodynamic backgrounds for the crystallization behaviour of racemates have been investigated using 2-phenoxypropionic acid (PPA) as an example. The racemate of PPA behaves normally and forms a racemic compound that has a higher melting point and is denser than the enantiomer. Low-temperature crystal structures of the pure enantiomer, the enantiomer cocrystallized with n-alkanes and the racemic acid showed that hydrogen-bonded dimers that form over crystallographic symmetry elements exist in all but the structure of the pure enantiomer. A database search for optically pure chiral mono-carboxylic acids revealed that the hydrogen-bonded cyclic dimer is the most prevalent hydrogen-bond motif in chiral mono-carboxylic acids. The conformation of PPA depends on the hydrogen-bond motif; the antiplanar conformation relative to the ether group is associated with a catemer hydrogen-bonding motif, whereas the more abundant synplanar conformation is found in crystals that contain cyclic dimers. Other intermolecular interactions that involve the substituent of the carboxylic group were identified in the crystals that contain the cyclic dimer. This result shows how important the nature of the substituent is for the crystal packing. The differences in crystal packing have been related to differences in melting enthalpy and entropy between the racemic and enantiomeric acids. In a comparison with the equivalent 2-(4-chlorophenoxy)-propionic acids, the differences between the crystal structures of the chloro and the unsubstituted acid have been identified and related to thermodynamic data.

trans-Bis(cyano-kappaC)(1,4,8,11-tetraazacyclotetradecane-kappa4N)manganese(III) perchlorate, a low-spin manganese(III) complex.

The crystal structure of the low-spin (S = 1) MnIII complex [Mn(CN)(2)(C(10)H(24)N(4))]ClO(4), or trans-[Mn(CN)(2)(cyclam)](ClO(4)) (cyclam is the tetradentate amine ligand 1,4,8,11-tetraazacyclotetradecane), is reported. The structural parameters in the Mn(cyclam) moiety are found to be insensitive to both the spin and the oxidation state of the Mn ion. The difference between high- and low-spin Mn(III) complexes is that a pronounced tetragonal elongation of the coordination octahedron occurs in high-spin complexes and a slight tetragonal compression is seen in low-spin complexes, as in the title complex.