scholarly journals Multiple light-induced NO linkage isomers in the dinitrosyl complex [RuCl(NO)2(PPh3)2]BF4unravelled by photocrystallographic and IR analysis

IUCrJ ◽  
2015 ◽  
Vol 2 (1) ◽  
pp. 35-44 ◽  
Author(s):  
Nicolas Casaretto ◽  
Sebastien Pillet ◽  
El Eulmi Bendeif ◽  
Dominik Schaniel ◽  
Anna K. E. Gallien ◽  
...  
Keyword(s):  
Metastable State ◽  
Variable Temperature ◽  
Binding Mode ◽  
Electronic Configuration ◽  
Kinetic Measurements ◽  
X Ray ◽  
Linkage Isomers ◽  
Metastable Structure ◽  
Ir Analysis ◽  
And Shifts

Multiple light-induced reversible metastable NO linkage isomers (PLIs) have been detected in the dinitrosyl compound [RuCl(NO)2(PPh3)2]BF4by a combination of photocrystallographic and IR analysis. The IR signature of three PLI states has been clearly identified, with estimated populations of 59% (PLI-1), 8% (PLI-2) and 5% (PLI-3) for a total population of the metastable state of 72%. The structural configuration of the major component (PLI-1) has been derived by X-ray photocrystallography. In the ground state, the structure is characterized by a bent and a linear nitrosyl, the bent one being oriented towards the linear equatorial nitrosyl with an Ru—N—O angle of 133.88 (9)°. X-ray Fourier difference maps indicate a selectivity of the photo-isomerization process in PLI-1: only the bent NO ligand changes its position, while the linear NO is unaffected. After irradiation at 405 nm, the orientation is changed by rotation towards the Cl ligand opposite the linear NO, with an Ru—N—O angle in this new position of 109 (1)°. The photocrystallographic analysis provides evidence that, in the photo-induced metastable state, the bent NO group is attached to the Ru atom through the N atom (Ru—N—O), rather than in an isonitrosyl Ru—O—N binding mode. In the IR spectra, the asymmetric NO vibrational band shifts by −33 cm−1to a lower value, whereas the symmetric band splits and shifts by 5 cm−1to a higher value and by −8 cm−1to a lower value. The down shift is a clear indication of the structural change, and the small upward shift in response to the new electronic configuration of the metastable structure. Variable-temperature IR kinetic measurements in the range 80–114 K show that the decay of the PLI-1 state follows an Arrhenius behaviour with an activation energy of 0.22 eV.

Synthesis and Evaluation of Levulinic Ester as Biodiesel Additives

2020 ◽  
Vol 71 (8) ◽  
pp. 21-26
Author(s):  
Elena-Emilia Oprescu ◽  
Cristina-Emanuela Enascuta ◽  
Elena Radu ◽  
Vasile Lavric
Keyword(s):  
Maximum Yield ◽  
Strength Distribution ◽  
Point Of View ◽  
Reaction Parameters ◽  
X Ray ◽  
Ethyl Levulinate ◽  
Ft Ir ◽  
Ir Analysis ◽  
Biodiesel Blend ◽  
Acid Strength Distribution

In this study, the SO42-/TiO2-La2O3-Fe2O3 catalyst was prepared and tested in the conversion of fructose to ethyl levulinate . The catalyst was characterized from the point of view of the textural analysis, FT-IR analysis, acid strength distribution, X-ray powder diffraction and pyridine adsorption IR spectra. The influence of the reaction parameters on the ethyl levulinate yield was study. The maximum yield of 37.95% in levulinate esters was obtained at 180 �C, 2 g catalyst and 4 h reaction time. The effect of ethyl levulinate addition to diesel-biodiesel blend in different rates, i.e, 0.5, 1, 2.5, 5 (w.t %) on density, kinematic viscosity and flash point was evaluated and compared with the European specification.

scholarly journals Born out of Fire and Ice: Polymorph Studies of the Antiviral Famciclovir

Crystals ◽  
2021 ◽  
Vol 11 (2) ◽  
pp. 129
Author(s):  
Liana Vella-Zarb ◽  
Ulrich Baisch
Keyword(s):  
Variable Temperature ◽  
Chemical Properties ◽  
Crystal Form ◽  
X Ray Diffraction ◽  
Crystal Forms ◽  
X Ray ◽  
Physical Chemical ◽  
Diffraction Patterns ◽  
Crystalline Forms

There is much interest and focus on solid forms of famciclovir. However, in spite of the abundance of reported differences in oral bioavailability, compressibility, and other physical–chemical properties of the various crystal forms of this drug, very little precise structural analysis is available in the literature to date. The form used in the commercial formulation is the anhydrous form I. Patents and patent applications report three different anhydrous crystalline forms on the basis of unindexed powder diffraction patterns. Single-crystal and variable-temperature X-ray diffraction experiments using the commercially available anhydrous form of famciclovir were carried out and led not only to the crystal structure determination of the anhydrous form I, but also to discovery of a new crystal form of anhydrous famciclovir from powder data.

scholarly journals Powder study of 3-azabicyclo[3.3.1]nonane-2,4-dione form 2

2006 ◽  
Vol 62 (7) ◽  
pp. o3046-o3048 ◽  
Author(s):  
Ashley T Hulme ◽  
Philippe Fernandes ◽  
Alastair Florence ◽  
Andrea Johnston ◽  
Kenneth Shankland
Keyword(s):  
Crystal Structure ◽  
Simulated Annealing ◽  
Hydrogen Bonds ◽  
Powder Diffraction ◽  
Title Compound ◽  
Variable Temperature ◽  
Polycrystalline Sample ◽  
Asymmetric Unit ◽  
X Ray ◽  
Compound C

A polycrystalline sample of a new polymorph of the title compound, C8H11NO2, was produced during a variable-temperature X-ray powder diffraction study. The crystal structure was solved at 1.67 Å resolution by simulated annealing from laboratory powder data collected at 250 K. Subsequent Rietveld refinement yielded an R wp of 0.070 to 1.54 Å resolution. The structure contains two molecules in the asymmetric unit, which form a C 2 2(8) chain motif via N—H...O hydrogen bonds.

scholarly journals Investigation of Solvatomorphism and Its Photophysical Implications for Archetypal Trinuclear Au3(1-Methylimidazolate)3

Molecules ◽  
2021 ◽  
Vol 26 (15) ◽  
pp. 4404
Author(s):  
Shengyang Guan ◽  
David C. Mayer ◽  
Christian Jandl ◽  
Sebastian J. Weishäupl ◽  
Angela Casini ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Solid State ◽  
Density Functional ◽  
Bulk Material ◽  
Variable Temperature ◽  
Active Phase ◽  
Solvent Free ◽  
X Ray Diffraction ◽  
X Ray ◽  
Aurophilic Interactions

A new solvatomorph of [Au3(1-Methylimidazolate)3] (Au3(MeIm)3)—the simplest congener of imidazolate-based Au(I) cyclic trinuclear complexes (CTCs)—has been identified and structurally characterized. Single-crystal X-ray diffraction revealed a dichloromethane solvate exhibiting remarkably short intermolecular Au⋯Au distances (3.2190(7) Å). This goes along with a dimer formation in the solid state, which is not observed in a previously reported solvent-free crystal structure. Hirshfeld analysis, in combination with density functional theory (DFT) calculations, indicates that the dimerization is generally driven by attractive aurophilic interactions, which are commonly associated with the luminescence properties of CTCs. Since Au3(MeIm)3 has previously been reported to be emissive in the solid-state, we conducted a thorough photophysical study combined with phase analysis by means of powder X-ray diffraction (PXRD), to correctly attribute the photophysically active phase of the bulk material. Interestingly, all investigated powder samples accessed via different preparation methods can be assigned to the pristine solvent-free crystal structure, showing no aurophilic interactions. Finally, the observed strong thermochromism of the solid-state material was investigated by means of variable-temperature PXRD, ruling out a significant phase transition being responsible for the drastic change of the emission properties (hypsochromic shift from 710 nm to 510 nm) when lowering the temperature down to 77 K.

Crystal Structures and Superconductivity in the La1.5−xBa1.5+Cu7+ySystem

1987 ◽  
Vol 99 ◽  
Author(s):  
JE. Greedan ◽  
A. H. O'Reilly ◽  
C. V. Stager ◽  
F. Razavi ◽  
W. Abriel
Keyword(s):  
Crystal Structures ◽  
Variable Temperature ◽  
Meissner Effect ◽  
Powder Diffraction Data ◽  
Solution System ◽  
X Ray ◽  
Neutron Powder Diffraction Data ◽  
Solid Solution System ◽  
Copper Valence ◽  
Flowing Oxygen

ABSTRACTMembers of the solid solution system La1.5−xBa1.5+Cu7+ywith x = 0, 0.125, 0.25. 0.375 and 0.5 have been prepared both in air and under one atmosphere of flowing oxygen. In general, except for x =0, the oxygen annealed compounds are superconducting while the air-annealed samples are semiconductors. Tc's measured by Meissner effect and resistivity data range to 70K. The crystal symmetry in all cases is apparently tetragonal as verified for x = 0.375 by variable temperature Guinier x-ray experiments at temperatures down to 8K. Crystal structures have been refined from neutron powder diffraction data. A correlation is noted between Cu-0 distances which connect adjacent Cu planes - the average copper valence and the occurrence of superconductivity.

Recent insights into lytic polysaccharide monooxygenases (LPMOs)

2018 ◽  
Vol 46 (6) ◽  
pp. 1431-1447 ◽  
Author(s):  
Tobias Tandrup ◽  
Kristian E. H. Frandsen ◽  
Katja S. Johansen ◽  
Jean-Guy Berrin ◽  
Leila Lo Leggio
Keyword(s):  
Active Site ◽  
Room Temperature ◽  
Experimental Studies ◽  
Binding Mode ◽  
Structural Features ◽  
Oxygen Species ◽  
Animal Kingdom ◽  
X Ray ◽  
Lytic Polysaccharide Monooxygenases ◽  
Polysaccharide Monooxygenases

Lytic polysaccharide monooxygenases (LPMOs) are copper enzymes discovered within the last 10 years. By degrading recalcitrant substrates oxidatively, these enzymes are major contributors to the recycling of carbon in nature and are being used in the biorefinery industry. Recently, two new families of LPMOs have been defined and structurally characterized, AA14 and AA15, sharing many of previously found structural features. However, unlike most LPMOs to date, AA14 degrades xylan in the context of complex substrates, while AA15 is particularly interesting because they expand the presence of LPMOs from the predominantly microbial to the animal kingdom. The first two neutron crystallography structures have been determined, which, together with high-resolution room temperature X-ray structures, have putatively identified oxygen species at or near the active site of LPMOs. Many recent computational and experimental studies have also investigated the mechanism of action and substrate-binding mode of LPMOs. Perhaps, the most significant recent advance is the increasing structural and biochemical evidence, suggesting that LPMOs follow different mechanistic pathways with different substrates, co-substrates and reductants, by behaving as monooxygenases or peroxygenases with molecular oxygen or hydrogen peroxide as a co-substrate, respectively.

W-Doped VO2 (M) with Tunable Phase Transition Temperature

2013 ◽  
Vol 320 ◽  
pp. 483-487 ◽  
Author(s):  
Ming Li ◽  
Deng Bing Li ◽  
Jing Pan ◽  
Guang Hai Li
Keyword(s):  
Electron Microscopy ◽  
Phase Transition ◽  
Transition Temperature ◽  
Phase Transition Temperature ◽  
Variable Temperature ◽  
X Ray Diffraction ◽  
X Ray ◽  
Infrared Transmittance ◽  
Transmission Electron ◽  
Potential Applications

W-doped VO2 (B) nanoneedles were successfully synthesized by solgel combing with hydrothermal treatment, in which the polyethylene glycol (PEG) was used as both surfactant and reducing. The metastable VO2 (B) was completely transformed to thermochromic VO2 (M) after annealing at high purity N2 atmosphere. The DSC results exhibit a strong crystallographic transition, and the phase transition temperature of VO2 (M) can be reduced to about 38 °C by W-doping. Field emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HR-TEM) were used to characterize the morphology and crystalline structure of the samples. The variable-temperature infrared transmittance spectra of VO2 (M) demonstrate their potential applications in energy saving field.

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