Nonclassical Crystallization and Core-Shell Structure Formation of Ibuprofen from Binary Solvent Solutions.

Liquid-liquidphase separation (LLPS) or dense liquid intermediates during the crystallization of pharmaceutical molecules is common; however, their role in alternative nucleation mechanisms is less understood. Herein, we report the formation of a dense liquid intermediate followed by a core-shell structure of ibuprofen crystals via nonclassical crystallization. The Raman and SAXS results of the dense phase uncover the molecular structural ordering and its role in nucleation. In addition to the dimer formation of ibuprofen, which is commonly observed in the solution phase, methyl group vibrations in the Raman spectra show intermolecular interactions similar to those in the solid phase. The SAXS data validate the cluster size differences in the supersaturated solution and dense phase. The focused-ion beam cut image shows the attachment of nanoparticles, and we proposed a possible mechanism for the transformation from the dense phase into a core-shell structure. The unstable phase or polycrystalline core and its subsequent dissolution from inside to outside or recrystallization by reversed crystal growth produces the core-shell structure. The LLPS intermediate followed by the core-shell structure and its dissolution enhancement unfold a new perspective of ibuprofen crystallization.

Experimental Study of Effective Mass and Spin-Orbital Energy of the Al2O3/NiO Nanoheterostructure Material.

The effective mass of the materials relies on exciton dynamics which is greatly dominated by energy gap of the materials. We examined the effective mass for the Al2O3/NiO nanoheterostructure material through polarization in the dielectric study. The mean optical effective mass was calculated to be mopt* = 5.69645 × 10-20 mop/m0 in the UV-visible region (1 × 106 to 5.4 × 106 Hz). From the group and phase velocity values, we observed that Al2O3/NiO is an anisotropic material. The electron spin-orbit energy splitting associated to electron in the valence band was identified using the Gaussian-confining 3D potential under normalized angular momentum (n, l = 0, 1, 2, 3). The 1S (1S1/2) and 2S (2S1/2) orbital ionization energies were calculated to be -6.08 and -5.99 eV for AlO3/NiO. The orbital ionization energies were established from the Bohr radius aB = 5.29 × 10-11 m and donor Rydberg constant Ry = 1.097 × 107 m-1 of the identical hydrogen atom. Our study gives insights into the exciton dynamics and calculation of orbital energy for the nanoheterostructure materials.

Yellow Emission from Low Coordination Site of Sr2 SiO4 :Eu2+ , Ce3+ : Influence of Lanthanide Dopants on the Electron Density and Crystallinity in Crystal Site Engineering Approach.

Lanthanide doping through a crystal site engineering approach tunes the emission wavelength suitable for LED applications, but weak emission from low coordination sites remains a huge challenge. Herein the use of a sensitizer is reported to enhance the emission strength and unravel the crystallinity and phase, as this approach demands a large amount of dopants. Doping of Eu2+ ions at SrO10 and SrO9 sites of Sr2 SiO4 (S2 S), respectively, tunes the emission from green to yellow and controlled doping of a Ce3+ sensitizer quadruples the quantum efficiency of yellow emission. Remarkably, doping of Eu2+ at the SrO9 site produces polycrystals, whereas co-doping of Ce3+ and Eu2+ at the same site produces single crystals. DFT calculations further delineate the underlying changes wherein strong interaction of dopant with its neighbours determines the electron density, and thus the crystallinity and phase, rather than usual explanation of aliovalent conditions, which is further substantiated by TEM results. Irrespective of dopant valence, use of large amounts of dopants and their interaction with the host is responsible for the crystallinity and phase change (α'-S2 S to ß-S2 S). The XPS valence band spectra experimentally evidences the changes in bonding nature of O 2p and O 2s orbitals of silicate and its electron density, due to doping at the two sites. In short, the outcomes resulting from this work could be extended for the development of other two-coordination site lanthanide-doped materials and crystallization of inorganic materials.

Role of Synthesis Method on Luminescence Properties of Europium(II, III) Ions in ß-Ca2SiO4: Probing Local Site and Structure.

The europium ion probes the symmetry disorder in the crystal structure, although the distortion due to charge compensation in the case of aliovalent dopant remains interesting, especially preparation involves low and high temperatures. This work studies the preparation of the ß-Ca2SiO4 (from here on C2S) particle from Pechini (C2SP) and hydrothermal (C2SH) methods, and its luminescence variance upon doping with Eu2+ and Eu3+ ions. The blue shift of the charge-transfer band (CTB) in the excitation spectra indicates a larger Eu3+-O2- distance in Eu3+ doped C2SH. The changes in vibrational frequencies due to stretching and bending vibrations in the FTIR and the Raman spectra and binding energy shift in the XPS analysis confirmed the distorted SiO44- tetrahedra in C2SH. The high hydrothermal temperature and pressure produce distortion, which leads to symmetry lowering although doping of aliovalent ion may slightly change the position of the Ca atoms. The increasing asymmetry ratio value from C2SP to C2SH clearly indicates that the europium ion stabilized in a more distorted geometry. It is also supported by Judd-Ofelt analysis. The concentration quenching and site-occupancy of Eu3+ ions in two nonequivalent sites of C2S were discussed. The charge state and concentration of europium ions in C2SP and C2SH were determined using X-ray photoelectron spectroscopy measurements. The C2S particles were studied by X-ray powder diffraction, FTIR, Raman, BET surface area, TGA/DTA, electron microscopy, XPS, and luminescence spectroscopy. The impact of citrate ion on the morphology and particle size of C2SH has been hypothesized on the basis of the microscopy images. This study provides insights that are needed for further understanding the structure of C2S and thereby improves the applications in optical and biomedical areas and cement hydration.

Fluorescence properties reinforced by proton transfer in the salt 2,6-diaminopyridinium dihydrogen phosphate.

Luminescent materials have many interesting applications, but it remains difficult to control the luminescence of organic materials and in particular to retain the same luminescence in solution and in the solid state, a property of interest for various imaging applications. In the present work, the fluorescent properties of the salt of 2,6-diaminopyridinium with dihydrogen phosphate have been explored. As a result of proton transfer from phosphoric acid to the pyridine nitrogen and the stabilizing effect of the two primary amines at the positions ortho to the pyridine nitrogen, the band gap between the HOMO and the LUMO is considerably diminished in comparison with that in 2,6-diaminopyridine. This is confirmed by a red shift in its absorption spectrum. Because protonation is retained in aqueous solution, the dissolved 2,6-diaminopyridinium dihydrogen phosphate salt retains a similar fluorescent spectrum as in the solid state. The crystals have been studied by single-crystal X-ray diffraction; FTIR, Raman, UV-vis-NIR, and luminescence spectroscopy; HOMO-LUMO calculations using DFT; and thermal analysis. The compound provides an example of a supramolecular motif that controls the crystal structure and the luminescence properties. In addition, the crystal exhibits negligible thermal expansion over a temperature interval of 150 °C. In short, 2,6-diaminopyridinium dihydrogen phosphate is an interesting compound for the design of luminescent devices.