Recognition of active ingredients in tablets by chemometric processing of X-ray diffractometric data

The paper presents an approach to use Partial Least Squares Discriminant Analysis (PLS-DA) on X-ray powder diffractometry (XRPD) dataset to build a model which recognizes a presence (or absence) of particular drug substance (acetaminophen) in unknown mixture (OTC tablet). The dataset consisted of 33 XRPD signals, measured for 12 pure substances and 21 tablets containing them in different quantitative and qualitative ratios, along with unknown excipients. The model was built with an external validation dataset chosen by Kennard-Stone algorithm. The RMSECV value was equal to 0.3461 (87.8% of explained variance) and external predictive error (RMSEP) was equal to 0.3123 (86.2% of explained variance). The result suggests that small but properly prepared training datasets give ability to construct well-working discriminant models on XRPD signals.     

Nature of isomerism of solid isothiourea salts, inhibitors of nitric oxide synthases, as studied by 1H-14N nuclear quadrupole double resonance, X-ray, and density functional theory/quantum theory of atoms in molecules

Isothioureas, inhibitors of nitric oxide synthases, have been studied experimentally in solid state by nuclear quadrupole double resonance (NQDR) and X-ray methods and theoretically by the quantum theory of atoms in molecules/density functional theory. Resonance frequencies on (14)N have been detected and assigned to particular nitrogen sites in each molecule. The crystal packings of (S)-3,4-dichlorobenzyl-N-methylisothiouronium chloride with the disordered chlorine positions in benzene ring and (S)-butyloisothiouronium bromide have been resolved in X-ray diffraction studies. (14)N NQDR spectra have been found good indicators of isomer type and strength of intra- or intermolecular N-H···X (X = Cl, Br) interactions. From among all salts studied, only for (S)-2,3,4,5,6-pentabromobenzylisothiouronium chloride are both nitrogen sites equivalent, which has been explained by the slow exchange. This unique structural feature can be a key factor in the high biological activity of (S)-2,3,4,5,6-pentabromobenzylisothiouronium salts.     

Formation of a Single‐Crystal Aluminum‐Based MOF Nanowire with Graphene Oxide Nanoscrolls as Structure‐Directing Agents

An innovative strategy is proposed to synthesize single‐crystal nanowires (NWs) of the Al³⁺ dicarboxylate MIL‐69(Al) MOF by using graphene oxide nanoscrolls as structure‐directing agents. MIL‐69(Al) NWs with an average diameter of 70±20 nm and lengths up to 2 μm were found to preferentially grow along the [001] crystallographic direction. Advanced characterization methods (electron diffraction, TEM, STEM‐HAADF, SEM, XPS) and molecular modeling revealed the mechanism of formation of MIL‐69(Al) NWs involving size‐confinement and templating effects. The formation of MIL‐69(Al) seeds and the self‐scroll of GO sheets followed by the anisotropic growth of MIL‐69(Al) crystals are mediated by specific GO sheets/MOF interactions. This study delivers an unprecedented approach to control the design of 1D MOF nanostructures and superstructures.     

Solvent Impact on the Properties of Benchmark Metal–Organic Frameworks: Acetonitrile-Based Synthesis of CAU-10, Ce-UiO-66, and Al-MIL-53

Herein is reported the utilization of acetonitrile as a new solvent for the synthesis of the three significantly different benchmark metal–organic frameworks (MOFs) CAU-10, Ce-UiO-66, and Al-MIL-53 of idealized composition [Al(OH)(ISO)], [Ce₆O₄(OH)₄(BDC)₆], and [Al(OH)(BDC)], respectively (ISO²⁻: isophthalate, BDC²⁻: terephthalate). Its use allowed the synthesis of Ce-UiO-66 on a gram scale. While CAU-10 and Ce-UiO-66 exhibit properties similar to those reported elsewhere for these two materials, the obtained Al-MIL-53 shows no structural flexibility upon adsorption of hydrophilic or hydrophobic guest molecules such as water and xenon and is stabilized in its large-pore form over a broad temperature range (130–450 K). The stabilization of the large-pore form of Al-MIL-53 was attributed to a high percentage of noncoordinating −COOH groups as determined by solid-state NMR spectroscopy. The defective material shows an unusually high water uptake of 310 mg g⁻¹ within the range of 0.45 to 0.65 p/p°. In spite of showing no breathing effect upon water adsorption it exhibits distinct mechanical properties. Thus, mercury intrusion porosimetry studies revealed that the solid can be reversibly forced to breathe by applying moderate pressures (≈60 MPa).     

Comparative AFM nanoscratching tests in air of bulk copper and electrogenerated cuprous oxide films

The normal and lateral spring constants of rectangular silicon AFM cantilevers bearing pyramidal silicon tips were accurately calibrated using a procedure that takes into account their tilt compared to horizontal orientation and their trapezoidal cross section. Such systems were used to carry out nanoscratching tests in air on technical substrates presenting a moderate roughness (RMS ≈ 40 nm) and made either from bulk copper or from cuprous oxide thin films electrogenerated on copper. The various events occurring during these nanoscratching procedures were characterized in details. In particular, the features of the scars appearing on the scratched zones and SEM observations of the AFM tips used during the nanoscratching procedures are described and exploited to establish a better understanding of the effects of the nanoscratching procedures on the targeted samples. In the case of electrodeposited Cu₂O films, these effects are discussed with the help of chemical and structural characterizations using XPS and XRD studies. All this set of information is used i) to describe the history of the nanoscratching tests and ii) to compare mechanical resistance of bulk copper and electrogenerated Cu₂O thin films using these nanoscratching tests carried out in air. The wear mechanism occurring during nanoscratching tests is discussed for both kinds of samples and compared with the one observed during erosion in erosion–corrosion tests.     

Probing the dynamics of CO2 and CH4 within the porous zirconium terephthalate UiO-66(Zr): a synergic combination of neutron scattering measurements and molecular simulations

Quasi-elastic neutron scattering (QENS) measurements combined with molecular dynamics (MD) simulations were conducted to deeply understand the concentration dependence of the self- and transport diffusivities of CH(4) and CO(2), respectively, in the humidity-resistant metal-organic framework UiO-66(Zr). The QENS measurements show that the self-diffusivity profile for CH(4) exhibits a maximum, while the transport diffusivity for CO(2) increases continuously at the loadings explored in this study. Our MD simulations can reproduce fairly well both the magnitude and the concentration dependence of each measured diffusivity. The flexibility of the framework implemented by deriving a new forcefield for UiO-66(Zr) has a significant impact on the diffusivity of the two species. Methane diffuses faster than CO(2) over a broad range of loading, and this is in contrast to zeolites with narrow windows, for which opposite trends were observed. Further analysis of the MD trajectories indicates that the global microscopic diffusion mechanism involves a combination of intracage motions and jump sequences between tetrahedral and octahedral cages.     

Low-frequency wave propagation in post-buckled structures

Nonlinear wave propagation in solids and material structures provides a physical basis to derive nonlinear canonical equations which govern disparate phenomena such as vortex filaments, plasma waves, and traveling loops. Nonlinear waves in solids however remain a challenging proposition since nonlinearity is often associated with irreversible processes, such as plastic deformations. Finite deformations, also a source of nonlinearity, may be reversible as for hyperelastic materials. In this work, we consider geometric bucking as a source of reversible nonlinear behavior. Namely, we investigate wave propagation in initially compressed and post-buckled structures with linear-elastic material behavior. Such structures present both intrinsic dispersion, due to buckling wavelengths, and nonlinear behavior. We find that dispersion is strongly dependent on pre-compression and we compute waves with a dispersive front or tail. In the case of post-buckled structures with large initial pre-compression, we find that wave propagation is well described by the KdV equation. We employ finite-element, difference-differential, and analytical models to support our conclusions.