We report a study of the CHA-type aluminophosphate AlPO-34, prepared with six different structure-directing agents (SDAs): piperidine (pip), morpholine (mor), pyridine (pyr), 1,4,8,11-tetraazacyclotetradecane (cyclam), 1,3-dimethylimidazolium (dmim) chloride and 1-ethyl-3-methylimidazolium (emim) bromide. Using a combination of solidstate NMR spectroscopy, periodic density functional theory (DFT) calculations and synchrotron X-ray diffraction, we show that, even in crystallographically well-ordered materials such as AlPO-34 with dmim as the SDA, local disorder may be present. For such disordered structures, where it is challenging to use DFT to assign NMR spectra, we show that the 31 P isotropic chemical shift can be predicted accurately using the mean P-O bond length and P-O-Al bond angle, in an extension of previous work. Variable-temperature 27 Al NMR reveals the presence of microsecond-timescale dynamics in all forms of AlPO-34, with two different motional regimes observed, depending on whether structural H2O is also present. H2O is detected in AlPO-34 prepared with mor as the SDA, although this material was previously reported as anhydrous, suggesting that this form of AlPO-34 may be hygroscopic despite the presence of the SDAs within the pores.

This article presents an overview of Liu Kang’s (1911–2004) canvas painting supports from his early artistic phases, Paris (1929–1932) and Shanghai (1932–1937). The research was conducted on 55 artworks from the collections of the National Gallery Singapore and Liu family. The technical examination of the paintings was supplemented with archival photographs of the artist at work to elucidate his practice of preparation of painting supports. The analyses conducted with light microscopy, SEM–EDS, and FTIR allowed us to characterise the structure of the canvases and identify the natural fibres and formulation of the grounds. In addition, references to contemporary colourmen catalogues, in relation to certain materials, were made. The obtained results suggest that, in both locations, Liu Kang employed commercially prepared canvases purchased by the roll or by the metre, together with bare strainers or stretchers of standard sizes. In Paris, the artist commonly used linen canvases, while in Shanghai he preferred cotton canvases, with linen used sporadically. The identified grounds from the Paris and Shanghai canvases are white and single-layered, but their formulations vary significantly between the two locations. Hence, grounds composed predominantly of lead white with extenders and drying oil as a binder are considered as exclusive to the Paris phase. However, semi-absorbent or absorbent grounds based on chalk are typical for Shanghai phase. This research contributes to the knowledge of Liu Kang’s painting materials and working practices during the pre-war period in Paris and Shanghai.

This work explores the dynamic behavior of the three closo-carborane isomers (formula C2B10H12) using modern solid-state magic angle spinning (MAS) NMR techniques and relates the experimental measurements to theoretical results obtained using molecular dynamics simulations. At high temperatures and at B0 = 9.4 T, the (11)B MAS line widths are narrow (40-90 Hz) for the three isomers. The rotational correlation times (τc) calculated by molecular dynamics are on the picosecond time scale, showing a quasi-isotropic rotation at these temperatures, typical for liquid systems. For all three isomers, the values of the (11)B spin-lattice relaxation times (T1) show discontinuities as the temperature is decreased, confirming the phase changes reported in the literature. At low temperatures, the (11)B MAS spectra of all three isomers exhibit much broader lines. The simulations showed that the molecular reorientation was anisotropic around different symmetry axes for each isomer, and this was supported by the values of the reduced quadrupolar parameter PQ(eff) derived from "dynamic shift" measurements using (11)B MQMAS NMR spectroscopy. The behavior of PQ(eff) as a function of temperature for p-carborane suggests that molecular reorientation is about the C5 symmetry axis of the molecule at low temperatures, and this was supported by the molecular dynamics simulations.

Molecular-scale dynamics on the nanosecond timescale or faster can have a measureable influence on isotropic NMR frequencies of quadrupolar nuclei. Although previously studied in solution, where it is usually referred to as the "dynamic shift", this effect is less well known in solids. Here we demonstrate that multiple-quantum NMR measurements of isotropic quadrupolar shifts are a simple way to probe nanosecond timescale motions in solids. We measure the 11 B (spin I = 3/2) shifts of the resolved boron sites in ortho-carborane as a function of temperature and interpret the results in terms of the known rapid tumbling dynamics.3