X-ray Powder Diffraction Patterns Research Articles

Comparing Microcrystal Electron Diffraction (MicroED) and X-ray crystallography as methods for structure determination of Oseltamivir phosphate

Oseltamivir phosphate is a pharmaceutical used in the treatment of influenza viruses. Panče Naumov et al. took two years of dedicated single crystal cultivation and successfully obtained low-quality single crystals through a diffusion method. Cultivation of Oseltamivir phosphate single crystals was proved to be difficult and can extend over several months or more. We employed microcrystalline electron diffraction (MicroED) for direct powder measurements, eliminating the need for lengthy single-crystal cultivation, and the time to obtain the molecular structure of Oseltamivir phosphate was shortened from several months to five hours. Comparative analyses of single crystal (Crystal 1) and MicroED (Crystal 2) results revealed equivalent crystal structures, with minimal differences in hydrogen bond distances, identical powder X-ray diffraction patterns, and negligible variations in Hirshfeld surface analysis. The differential scanning calorimetry (DSC) analysis showcased a higher melting point of Oseltamivir phosphate (206.0 °C) than Oseltamivir (110.7 °C), indicating that Oseltamivir phosphate had high temperature stability, and may result in the selection of Oseltamivir phosphate as a formulation form. The study establishes and verifies a congruence between MicroED detection and traditional single-crystal detection methods and may be applied in the elucidation of compound structures and the surveillance of drug polymorphism.

Enhancing thermoelectric behavior of Bismuth Selenide crystal via substitution of Sulfur and Tellurium

Sulfur and Tellurium substituted Bismuth Selenide (Bi2Se3-x-ySxTey, x = y = 0, 0.1, 0.15, 0.2) quaternary alloy crystals were synthesized by using vertical Bridgman technique. Energy dispersive analysis of X-rays confirmed elemental composition and purity of the grown crystals. Field emission scanning electron microscopy showed that the growth of crystals has occurred by layer growth mechanism. Rhombohedral crystal structure is validated through analysis of powder X-ray diffraction pattern. Thermoelectric parameters such as electrical conductivity, Seebeck coefficient and thermal conductivity were calculated from 303 K to 773 K and from that power factor as well as figure of merit have been determined for all grown crystals. Electrical conductivity significantly increased due to Sulfur and Tellurium incorporation and maximum value obtained is 147.72 S/cm at 503 K for Bi2Se2.6S0.2Te0.2. Seebeck coefficient and thermal conductivity showed decrement with incorporation of Sulfur and Tellurium. Reduction in thermal conductivity and enhancement in electrical conductivity resulted in the improvement of figure of merit. Sulfur and Tellurium substitution showed considerable improvement in ZT from 0.31 (533 K) for pristine Bi2Se3 to 1.28 (523 K) for Bi2Se2.6S0.2Te0.2.

Synthesis, spectroscopic and biological characterizations of platinum(IV), ruthenium(III) and iridium(III) theophylline complexes

This study used micro-analyses, (FTIR, UV-Vis) spectra, magnetic, thermogravimetric, X-ray powder diffraction (XRD) patterns, and transmittance electron microscopy (TEM) techniques to characterize three synthesized theophylline (TPH) complexes with ruthenium(III), platinum(IV), and iridium(III) metal ions. The metal ions indicated above were found to align with the TPH drug chelate as a mono-dentate ligand via the deprotonated NH group at the nitrogen atom position N7, as verified by FTIR measurements. Additionally, the complexes conductivity and magnetic susceptibility were examined. The octahedral geometry for the synthesized complexes was proposed by the current data. Except for the iridium(III) complex, which has a non-electrolytic nature due to the presence of a chlorine atom inside the chelation sphere, the molar conductivity of the complexes in DMSO solution was electrolyte in nature. Theophylline complexes with a (metal: ligand) stoichiometry of 1:2 were produced. The TPH complexes have also been tested in vitro against G(+) bacteria (Bacillus subtilis and Staphylococcus Aureus) and G(-) bacteria (Pseudomonas aeruginosa and Escherichia coli) to evaluate their antibacterial efficacy. Human breast and liver cancer cell lines were used as a test for the TPH complexes in vitro anti-cancer properties.
 KEY WORDS: Theophylline, Metal ions, Chelation, Octahedral, Spectral analysis, Nano-particles, Biological evaluation
 Bull. Chem. Soc. Ethiop. 2024, 38(3), 725-738. 
 DOI: https://dx.doi.org/10.4314/bcse.v38i3.14

Green route to prepare zinc oxide nanoparticles using Moringa oleifera leaf extracts and their structural, optical and impedance spectral properties

This article investigates biosynthesis of zinc oxide (ZnO) nanoparticles (NPs) from Moringa oleifera leaves extract using an eco-friendly preparation method. The crystalline structure, optical properties, morphology and impedance characteristics of ZnO NPs were analyzed using impedance spectroscopy, powder X-ray diffraction (XRD), scanning electron microscopy, Fourier transform infrared spectroscopy (FTIR) and ultraviolet spectroscopy (UV-vis). The powder XRD pattern confirmed the crystallinity of the prepared samples as well as enabled determining their crystallite size and pure phase portion. The FTIR study confirmed the presence of functional groups responsible for reduction metal ions into ZnO NPs. UV-vis absorption spectra contained the absorption peak corresponding to ZnO NPs. Impedance spectroscopy of the prepared ZnO NPs revealed the grain boundaries in them and confirmed their semiconducting nature.

CHARACTERISATION, EVALUATION AND DENSITY FUNCTIONAL ANALYSIS OF CILNIDIPINE-NICOTINAMIDE COCRYSTALS DEVELOPED BY LIQUID ASSISTED GRINDING TECHNIQUE: A SUSTAINABLE APPROACH FOR ENHANCED SOLUBILITY

Objective: Improving the solubility of poorly water-soluble drugs has always been a challenge in drug development. This study aimed to enhance the aqueous solubility of a poorly water-soluble drug, Cilnidipine, by cocrystallisation method using liquid-assisted grinding (LAG) technique with Nicotinamide as the coformer. The study also aimed to understand the mechanism of cocrystal formation by quantum mechanical calculations. Methods: The Cilnidipine-Nicotinamide cocrystals were prepared in various stoichiometric ratios using the liquid-assisted grinding (LAG) technique. The cocrystals obtained were characterised by vibrational spectroscopy, thermal methods such as differential scanning calorimetry (DSC), powder X-ray diffraction (PXRD) and surface morphology by field emission scanning electron microscopy (FE-SEM). The cocrystals were evaluated for saturation solubility, and the mechanistic study of cocrystal formation was performed using the Gaussian 09 software package. Results: FT-IR spectra of the formulated cocrystal indicated the intermolecular hydrogen bond formation between-N-H of Nicotinamide and the nitro group of Cilnidipine. DSC analysis showed a single endotherm at 96.76 °C, PXRD patterns were different from that of the reactants, and FE-SEM analysis revealed the changes in the surface morphology of the obtained cocrystal. The prepared cocrystal showed a 26.36-fold enhancement in the aqueous solubility of Cilnidipine. The DFT study demonstrated the formation of a strong intermolecular hydrogen bonding between the nitro-oxygen atom of Cilnidipine and the amide hydrogen atom of Nicotinamide in cocrystal formed. Conclusion: This study highlights the potential of the liquid-assisted grinding method for preparing cocrystals as a sustainable and reliable approach to address the challenges posed by poorly water-soluble drugs.

Perchiazziite, Co2(CO3)(OH)2, a New Member of the Rosasite–Malachite Group from the Monte Ramazzo Mine, Italy

ABSTRACT Perchiazziite, ideally Co2(CO3)(OH)2, is a new mineral discovered at the Monte Ramazzo Mine, Genova Province, Liguria, Italy. It occurs as globular aggregates up to 0.1 mm in diameter, composed of very thin fibers. These develop on a matrix composed mostly of goethite and magnetite, in association with calcite and Co-bearing malachite. Aggregates of perchiazziite are pale orange-pink on their outer surfaces but white in thin section. It is translucent with white streak, silky luster, brittle tenacity, and uneven fracture. No cleavage and parting are observed. The Mohs hardness is ∼4. Dcalc. = 3.970 g/cm3. The mean refractive index calculated using the Gladstone-Dale equation is 1.77. The main bands in the Raman spectrum are at 154, 511, 707, 1085, 1526, 3304, aXnd 3479 cm−1. The chemical composition (by electron microprobe; CO2 and H2O by stoichiometry) of perchiazziite is (in wt.%): MgO 1.81, CaO 0.41, MnO 0.32, FeO 0.12, CoO 32.45, NiO 4.02, CuO 5.40, ZnO 25.60, CO2 20.63, H2O 8.42, total 99.18. The empirical formula calculated on the basis of 5 O apfu is: (Co0.93Zn0.67Cu0.15Ni0.12Mg0.10Ca0.02Mn0.01)Σ2.00(CO3)(OH)2. The crystal structure was refined by the Rietveld method. Perchiazziite is monoclinic, space group P21/a, a = 12.1832(16) Å, b = 9.3187(16) Å, c = 3.1570(3) Å, β = 97.165(15)°, V = 355.62(8) Å3, and Z = 4. The strongest lines of the X-ray powder diffraction pattern [d, Å (I, %) (hkl)] are 6.040 (22) (200), 5.073 (38) (210), 3.694 (53) (220), 2.599 (100) (021), 2.535 (26) (420), 2.480 (27) (221̄), 2.140 (26) (231̄), 1.561 (25) (202̄). Perchiazziite is a new member of the rosasite–malachite group.

Ho3+ -doped BaGd2 ZnO5 green-emitting phosphor for solid-state lighting: synthesis, characterization, and photoluminescence properties.

In this work, we present the synthesis of a green-emitting series of BaGd2 ZnO5 :xHo3+ (0.5-3mol%) phosphors using a high-temperature solid-state reaction method. Phase purity and crystal structure information were evaluated through X-ray powder diffraction patterns. Optical properties were examined through diffuse reflectance spectra, revealing that the prepared phosphor exhibited a band gap of 4.65 eV. The effect of Ho3+ doping on the morphology and ion distribution on the surface was assessed using scanning electron microscopy and time-of-flight secondary ion mass spectrometry techniques, respectively. The excitation spectra of the synthesized phosphor exhibited a charge transfer band and strong absorption transitions. The emission spectra displayed typical holmium emission characteristics, featuring a strong green emission band associated with f-f transitions from 5 F4 + 2 S2 → 5 I8 . Decay dynamics of the synthesized phosphor exhibited a single-exponential decay pattern, with lifetimes ranging from 0.103 to 0.053 ms. The intrinsic radiative lifetime, calculated through Auzel's fitting was determined to be 0.14 ms. Using the emission spectra, colorimetric behaviour was analyzed, revealing that the Commission Internationale de l'éclairage (CIE) coordinates exclusively lay within the green region at (0.285, 0.705), with an impressive colour purity of 99.6%. Given these marked properties, the synthesized phosphor exhibits great potential for a wide range of green-emitting applications, including displays, white light-emitting diodes, and security signage.

Determination of two structures of the solvent 3-hydroxypropionitrile crystallized at low temperatures

The title compound, 3-hydroxypropionitrile, was crystallized repeatedly in situ inside a quartz capillary using a liquid nitrogen cryostream. The X-ray powder diffraction patterns obtained indicated the presence of two distinct crystalline phases. The cleanest datasets for each of the phases were used to solve the crystal structures via simulated annealing, followed by refinement and optimization via dispersion-corrected density functional theory (DFT) calculations, with a final Rietveld refinement against the experimental data. The two structures appear to correspond to those proposed in a 1960s literature vibrational spectroscopy paper, one being the more stable with a gauche molecular conformation and the second metastable phase more complex with mixed conformations. Dispersion-corrected DFT computation using lattice parameters for both phases obtained from a single 84 K dataset with co-existing phases shows the stable and metastable phases to differ in energy by less than 0.5 kJ mol−1. A comparison of experimental far infrared spectra published in the 1960s with those calculated from the proposed crystal structures provides some independent supporting evidence for the proposed structures.

Testibiopalladite, PdSbTe: A Valid Mineral and Sb-Analogue of Michenerite

Abstract Testibiopalladite was reported from two unnamed deposits in China by Anonymous (1974) to be ideally PdSbTe. The description of the mineral included an indexed X-ray powder diffraction pattern, space group determination, electron probe micro-analyses, reflectance, and micro-indentation hardness measurements. This description was published without prior submission to the IMA, which was the norm at the time before China became a member. It is unknown as to why the Commission for New Minerals and Mineral Names (CMNMN) did not examine and vote on the mineral as had been done for all other Chinese mineral descriptions published at the time. It is surprising because the chairman of the CMNMN at the time had reviewed the mineral (Fleischer et al. 1976) and concluded it was a valid species, i.e., the Sb analogue of michenerite (PdBiTe). Further, the same article included a description of “hexastibiopanickelite” which was voted on and rejected by the CMNMN in 1976. From 1981 to 2021 there were many papers published reporting testibiopalladite from several deposits in different countries (e.g., Hudson et al. 1978, Chen et al., 1993, Stepanets et al. 2019, 2020), as well as a single-crystal structure analysis of synthetic PdSbTe which confirmed the assigned space group (Foecker & Jeitschko 2001). The published data (e.g., Barkov et al. 2002, Liang et al. 2019, 2023) suggest that testibiopalladite is a valid mineral species, ideally PdSbTe, and is the Sb analogue of michenerite, PdBiTe, both crystallizing in space group P213. Both the name testibiopalladite and the mineral, ideally PdSbTe, were approved by the Commission of New Minerals, Nomenclature and Classification of the International Mineralogical Association (CNMNC-IMA), Nomenclature Voting Proposal 23-H. Liang et al. (2019, 2023) studied samples from the type locality (Yangliuping deposit, PRC) that are to be considered as a neotype.

Crystal chemistry and molar volume of potassic-chloro-hastingsite

Abstract. Several geological processes such as crustal and mantle metasomatism, high-grade metamorphism, and the formation of ore deposits involve the exchange of halogens, especially chlorine, between silicate minerals and fluids. It is well established that the presence of octahedral iron is vital to the process of Cl incorporation into amphiboles. However, other compositional controls on Cl incorporation, such as the effect of TAl, ANa, AK, and A-site occupancy are not as well constrained. This study reports on the compositional and structural relationships amongst a suite of 25 synthetic calcium amphiboles with a diverse range of Cl contents (0–1.68 atoms per formula unit (apfu)). Most amphiboles were synthesized along the potassic-hastingsite–potassic-chloro-hastingsite join (KCa2(Fe4Fe3+)(Al2Si6)O22(OH,Cl)2). Additional work involved substitution of Na for K, variable Al content, and substitution of Mg for Fe2+ in the bulk composition to explore these compositional effects on Cl incorporation. The relationship between pressure and the Cl content of amphiboles was also explored over the pressure range 0.3–2.0 GPa. Otherwise, synthesis conditions were 700 °C and 0.3 GPa with fO2 near Ni–NiO. Iron (II) chloride was used as the source of Cl. Some experiments used variably concentrated FeCl2 brines (0–100 molal), while others were nominally anhydrous, containing only the water absorbed by the hygroscopic FeCl2. All amphiboles were characterized by Rietveld refinements of powder X-ray diffraction patterns, electron microprobe analysis, and Mössbauer spectroscopy, the latter to determine Fe3+ fraction. This study finds a positive relationship between pressure and the Cl content of the amphibole. Both Fe2+ and Fe3+ are positively correlated with Cl among amphiboles with variable Fe#, but the correlation is poor to nonexistent for Mg-free amphiboles. Results indicate that the substitution of CFe2+,3+ for CMg and CFe2+,3+ for CAl facilitate Cl incorporation, with the former having a larger effect. The A-site occupancy is positively correlated with Cl in all amphiboles except those synthesized in dilute FeCl2 brines (≤ 6 m), which are negatively correlated. No correlation is observed between the Cl content of the amphibole and either the species of A cation (K vs. Na) or TAl. The composition vs. unit cell parameter data were analyzed using multivariate linear regression to better understand the process of Cl incorporation and to predict the molar volume of endmember chloro-amphiboles. The regression indicates an expansion of 0.181 Å (0.99 %) and 0.048 Å (0.90 %) along the b and c edges respectively, a reduction in β by 0.76° (0.72 %), and a contraction of 0.060 Å (0.59 %) along a when fully substituting Cl for OH in potassic-hastingsite. The multivariate linear regression equations allow the prediction of molar volumes for select endmember chloro-amphiboles, such as potassic-chloro-hastingsite = 964.63 ± 1.29 Å3 or 290.5 ± 0.4 cm3 mol−1.

Enricofrancoite, KNaCaSi4O10, a new Ca–K–Na silicate from Somma–Vesuvius volcano, southern Italy

Abstract Enricofrancoite (IMA2023–002), ideally KNaCaSi4O10, is a new litidionite-group member found as the product of high-temperature alteration of hosting silicates with the enrichment by Cu-bearing fluids at the rock–fumaroles interface related to the 1872 eruption of Somma–Vesuvius volcano, southern Italy. It occurs as euhedral and platy crystals or crusts together with litidionite, tridymite, wollastonite and Al- and Fe-bearing diopside, kamenevite, perovskite, rutile, Ti-rich magnetite and colourless Si-glass. Single crystals of enricofrancoite are transparent colourless or light blue with a vitreous lustre. Mohs hardness is 5.5. Dmeas is 2.63(3) g/cm3 and Dcalc is 2.63 g/cm3. The mineral is optically biaxial (−), α = 1.542(5), β = 1.567(5),γ = 1.575(5); 2V(meas) = 60(2)° and 2Vcalc = 58°. The mean chemical composition (wt.%, electron-microprobe data) is: SiO2 64.81, Al2O3 0.03, TiO2 0.08, FeO 0.07, MgO 1.71, CaO 10.64, CuO 2.22, Na2O 8.56, K2O 11.41, total 99.94. The empirical formula based on 10 O apfu is: K0.90Na1.03(Ca0.71Mg0.16Cu0.10)Σ0.97Si4.02O10. The Raman spectrum contains bands at 133, 248, 265, 290, 335, 400, 438, 510, 600, 690 and 1120 cm–1 and the wavenumbers of the IR absorption bands are: 424, 470, 492, 530, 600, 630, 690, 750, 788, 970, 1040 and 1160 cm–1. The eight strongest lines of the powder X-ray diffraction pattern are [d, Å (I, %) hkl]: 6.75 (42) 01 $\bar{1}$ , 3.65 (20) 11 $\bar{2}$ , 3.370 (100) 02 $\bar{2}$ , 3.210 (52) 102, 3.051 (18) 111, 3.033 (25) 2 $\bar{1}\bar{2}$ , 2.834 (22) 02 $\bar{3}$ and 2.411 (72) 03 $\bar{2}$ . Enricofrancoite is triclinic, space group P $\bar{1}$ , unit-cell parameters refined from the single-crystal data are a = 7.0155(4) Å, b = 8.0721(4) Å, c = 10.0275(4) Å, α = 104.420(4)°, β = 99.764(4)°, γ = 115.126(5)° and V = 472.74(5) Å3. The crystal structure has been refined from single-crystal X-ray diffraction data to R1 = 0.035 on the basis of 2078 independent reflections with Fo > 4σ(Fo). Enricofrancoite is an H2O-free analogue of calcinaksite with 5-coordinated Ca2+ at the M site.

An effective material for solar steam generation applications: Gradient graphene sponge

The efficient use of solar energy for clean water is a renewable and environmentally-friendly route to solve global water scarcity. For this, we report the preparation of light, mechanically durable, and effective photothermal material. A simple acid impregnation method was applied to graphene sponge material (GSM) possessing hydrophobic character to gain partial hydrophilicity to obtain a gradient structure. The morphological and structural properties of the gradient graphene sponge material (GGSM) were carried out using scanning electron microscopy, X-ray photoelectron spectroscopy, Raman spectroscopy, X-ray powder diffraction patterns, Fourier-transformed infrared spectroscopy, and water drop contact angle measurements. GGSM showed fast and effective water vapor conversion performance due to the gradient structure, as well as the high rate of sunlight absorption and photothermal conversion thanks to graphene. With the advantageous feature of gradient structure, GGSM achieved a high water vapor conversion capacity (1.79 kg/m2h) and solar thermal efficiency of 57% compared to GSM (1.58 kg/m2h; 45%). This new material provides a novel approach to solar energy applications.

Mckelveyite group minerals – Part 3: Bainbridgeite-(YCe), Na2Ba2YCe(CO3)6 ⋅ 3H2O, a new species from Mont Saint-Hilaire, Canada

Abstract. The new mckelveyite group mineral bainbridgeite-(YCe), ideally Na2Ba2YCe(CO3)6 ⋅ 3H2O, was found at Mont Saint-Hilaire, Quebec, Canada. Bainbridgeite-(YCe) occurs as pseudotrigonal and pseudohexagonal hemimorphic crystals that show platy, columnar, tabular, cone-shaped, barrel-shaped, saucer-shaped, or spindle-shaped habit. They often form stacked or parallel growth aggregates, rosettes, and groups of radiating crystals. The crystals are usually less than 1 mm in size. Bainbridgeite-(YCe) varies in colour from pale yellow to yellow, grey to almost black, bluish grey, green-grey, or white. The streak is white; the lustre is vitreous. The mineral has no cleavage. The Mohs hardness is 3. Dcalc is 3.49 g cm−3. Bainbridgeite-(YCe) is optically biaxial (+), α= 1.572(2), β= 1.586(2), γ= 1.628(2), 2 V (calc.) = 62∘, 2 V (meas.) = 45(4)∘(589 nm). The IR spectrum is reported. The composition (wt %, average of five analyses) is Na2O 6.86, CaO 0.59, SrO 4.01, BaO 25.71, Y2O3 8.24, La2O3 4.96, Ce2O3 8.38, Pr2O3 0.48, Nd2O3 1.87, Sm2O3 0.23, Gd2O3 0.67, Tb2O3 0.07, Dy2O3 1.38, Ho2O3 0.32, Er2O3 0.94, Tm2O3 0.08, Yb2O3 0.49, CO2 27.03, H2O 5.67, total 97.98. The empirical formula of the holotype calculated on the basis of six cations is as follows: Na2.11Ca0.10Sr0.37Ba1.60Y0.70La0.29Ce0.49Pr0.03Nd0.11Sm0.01Gd0.03Dy0.07Ho0.02Er0.05 Yb0.02(CO3)5.86(H2O)3.00. The mineral is triclinic, P1, a= 9.1079(2) Å, b= 9.1066(3) Å, c= 6.9332(2) Å, α= 102.861(2)∘, β= 116.148(2)∘, γ= 60.181(2)∘, V= 447.85(2) Å3, and Z= 1. The strongest reflections of the powder X-ray diffraction pattern [d,Å(I)(hkl)] are 6.22(42)(001, 1‾1‾1, 1‾01), 4.430(100)(01‾1, 2‾1‾1, 120), 4.094(37)(1‾2‾1, 1‾11, 210, 111), 3.263(26)(11‾1, 2‾1‾2, 121), 2.888(67)(1‾2‾2, 1‾12, 211), 2.633(38)(3‾01, 030, 3‾3‾1), 2.263(23)(2‾21, 2‾4‾1, 4‾2‾1). 2.010(20)(03‾2, 3‾3‾3, 3‾03, 301, 032, 331). The crystal structure, solved and refined from single-crystal X-ray diffraction data (R1= 0.040), is of the weloganite type.

Dmitryvarlamovite, Ti2(Fe3+Nb)O8, a new columbite-supergroup mineral related to the wolframite group

AbstractThe new columbite-supergroup mineral dmitryvarlamovite, ideally Ti2(Fe3+Nb)O8, was discovered in weathered alkaline metasomatic assemblages formed after late Riphaean sedimentary carbonate rocks of the Verkhne-Shchugorskoe deposit, Middle Timan Mts., Russia. The associated minerals are columbite-(Fe), pyrochlore-group minerals, monazite-(Ce), xenotime-(Y), baryte, pyrite, drugmanite and plumbogummite. Dmitryvarlamovite occurs as isolated anhedral equant grains up to 0.5 mm across. The colour of dmitryvarlamovite is black, the streak is black and the lustre is submetallic. The new mineral is brittle, with the mean VHN hardness of 753 kg mm–2 corresponding to the Mohs’ hardness of 6. No cleavage is observed. The fracture is conchoidal. The calculated density is 4.891 g⋅cm–3. In reflected light, dmitryvarlamovite is light grey; no pleochroism is observed. The reflectance values (Rmin, % / Rmax, % / λ, nm) are: 19.8/20.3/470, 18.3/18.9/546, 17.8/18.5/589 and 17.3/17.8/650. The chemical composition is (electron microprobe data, with iron divided into Fe2O3 and FeO based on the charge balance, wt.%): MnO 0.11, FeO 1.51, V2O3 0.89, Cr2O3 0.28, Fe2O3 19.26, TiO2 37.72, Nb2O5 40.08, total 99.85. The IR and Raman spectra indicate the absence of H-, C- and N-bearing groups. The empirical formula is (Fe2+0.08V3+0.05Cr3+0.01Fe3+0.92Ti1.79Nb1.15)Σ4.00O8. The crystal structure was determined using single-crystal X-ray diffraction data and refined to R = 0.048. Dmitryvarlamovite is orthorhombic, space group P21212, a = 4.9825(6), b = 4.6268(4), c = 5.5952(6) Å and V = 5.5952(6) Å3 (Z = 1). The structure is related to those of wolframite-group minerals but differs in the scheme of cation ordering. The crystal-chemical formula derived based on the structural data is (Ti0.57Nb0.21Fe3+0.15Fe2+0.04V0.02Cr0.01)2(Nb0.36Ti0.33Fe3+0.31)2O8. The strongest lines of the powder X-ray diffraction pattern [d, Å (I, %) (hkl)] are: 3.58 (40) (011), 2.911 (100) (111), 2.809 (40) (002), 2.497 (38) (020), 2.447 (29) (103), 1.7363 (32) (103) and 1.7047 (29) (220). Dmitryvarlamovite is named after Dmitry Anatol'evich Varlamov (b. 1965).

Impact of transparent conducting substrates on structural and optical of Titanium(IV) phthalocyanine dichloride (TiPcCl2) thin films

This study investigates the impact of transparent conducting substrates, specifically indium-doped tin oxide (ITO) and fluorine-doped tin oxide (FTO), on the structural and optical characteristics of thermally evaporated Titanium phthalocyanine chloride (TiPcCl2) thin films. The crystalline structure of TiPcCl2/quartz thin films was verified by X-ray powder diffraction (XRD) patterns while amorphous phases were detected in TiPcCl2/ITO and TiPcCl2/FTO thin films. Field emission scanning electron microscopy (FESEM) images provided evidence that the morphology of TiPcCl2 thin films may be affected by a lattice mismatch between TiPcCl2 and substrates. Fourier-transform infrared spectroscopy (FT-IR) also showed that the substrates did not change the molecular structure of TiPcCl2. UV–Vis-NIR spectroscopy demonstrated that the substrates had a significant influence on the optical gap, optical constants, dielectric constant dielectric loss functions and optical conductivity of TiPcCl2 thin films. Lastly, the nonlinear susceptibility χ(3), the nonlinear refractive index n2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${{\\varvec{n}}}_{2}$$\\end{document} and the nonlinear absorption coefficient β(c) for TiPcCl2/ITO, TiPcCl2/FTO, and TiPcCl2/quartz were obtained using a semi-empirical approach. The changes seen in optical properties could be due to changes in the crystal structure and morphology, which are closely connected to the properties of the substrate material. Overall, the results for TiPcCl2 thin films are promising, and they are appropriate for novel optoelectronic device applications.

Using synchrotron high-resolution powder X-ray diffraction for the structure determination of a new cocrystal formed by two active principle ingredients.

The crystal structure of a new 1:1 cocrystal of carbamazepine and S-naproxen (C15H12N2O·C14H14O3) was solved from powder X-ray diffraction (PXRD). The PXRD pattern was measured at the high-resolution beamline CRISTAL at synchrotron SOLEIL (France). The structure was solved using Monte Carlo simulated annealing, then refined with Rietveld refinement. The positions of the H atoms were obtained from density functional theory (DFT) ground-state calculations. The symmetry is orthorhombic with the space group P212121 (No. 19) and the following lattice parameters: a = 33.5486 (9), b = 26.4223 (6), c = 5.3651 (10) Å and V = 4755.83 (19) Å3.

Na2[Pd(saccharinate)4]: A new phosphine-free water-soluble catalyst with singular structure for modification of ribose nucleosides at room temperature

The easy synthesis of the anionic palladium catalyst containing saccharinate as only ligand Na2[Pd(saccharinate)4] (I), starting from either Na2[PdCl4] or Pd(AcO)2, is reported here, together with its complete characterization. It includes high resolution powder X-ray diffraction pattern obtained on a synchrotron source, subsequent elucidation of the crystal structure, and structural refinement using the Rietveld method. The structure consists of linear chains that are linked by non-covalent interactions, and results in a porous structure with channels. This air and light water-soluble complex has shown an outstanding performance for room temperature Pd-catalyzed Suzuki functionalization of the purine base in unprotected nucleosides, improving the best results reported to date.

Thermoelectric properties of aliovalent Zn doped Cu1.8S polycrystalline materials

Cu1.8S-based materials are regarded as promising thermoelectric materials due to their super ionic nature. The Cu1.8-xZnxS (x = 0, 0.01, 0.03, and 0.09) samples were synthesized by the hydrothermal method followed by cold pressing and sintering. The powder X-ray diffraction pattern has confirmed the phase purity and rhombohedral crystal structure of Cu1.8S. Additionally, FE-SEM micrographs along with the EDX elemental mapping detected the existence of CuS as the secondary phase in the Cu1.8S matrix and uniform distribution of the constituent elements. Upon doping the Zn atom, the Seebeck coefficient subsequently increases owing to the decrement in the carrier concentration, whereas the electrical conductivity gradually reduces. Essentially, the presence of CuS secondary phase and the defects induced by the Zn atom effectively scattered low-mid wavelength phonons, where a very low thermal conductivity of 3.65 W/mK was achieved for Cu1.71Zn0.09S at room temperature. Ultimately, an overall maximum zT of 0.07 at 573 K was observed for Cu1.77Zn0.03S, which is about 3.5 times greater than that of the pristine sample.

Pressure Dependence of the Structural and Superconducting Properties of the Bi-Based Superconductor Bi2Pd3Se2.

The structural and superconducting properties of the Bi-based compound Bi2Pd3Se2 were investigated over a wide pressure range. The prepared Bi2Pd3Se2 sample was a superconductor with a superconducting transition temperature, Tc, of approximately 3.0 K, which differed from a previous report (Tc of less than 1.0 K). At ambient pressure, the powder X-ray diffraction (XRD) pattern of the Bi2Pd3Se2 sample was consistent with that previously reported for Bi2Pd3Se2. The Rietveld method was used to refine the crystal structure, which had a space group of C2/m (No. 12), as reported previously. This compound showed no clear anomaly due to the charge-density-wave (CDW) transition, as seen from the temperature dependence of magnetic susceptibility. However, the temperature dependence of electrical resistivity indicated a clear anomaly, presumably because of the CDW transition in the low-pressure range; the CDW transition temperature was approximately 230 K. The XRD patterns of the Bi2Pd3Se2 sample were measured at 0.160-22.7 GPa, and the patterns were well analyzed by both the Le Bail and Rietveld refinement methods, showing no structural phase transitions in the above pressure range. The pressure dependence of Tc of Bi2Pd3Se2 was recorded based on the temperature dependence of the electrical resistance, which showed an almost constant Tc at 0-13.7 GPa, and the Tc-pressure (p) behavior was fully discussed.

Thermotropic Structure Phase Transitions and Two Types of Thermochromic Behaviors in a Bromoargentate Cluster [Pr-dabco]2Ag4Br6.

Organic-inorganic silver halide hybrids show abundant phase transitions and thermochromism. However, it is very rare that silver halides exhibit thermochromism related to thermotropic structure phase transition. Herein, a bromoargentate hybrid, [Pr-dabco]2Ag4Br6 (1) (Pr-dabco+ = 1-propyl-1,4-diazabicyclo-[2.2.2]octan-1-ium), with tetranuclear [Ag4Br6]2- clusters was prepared and characterized by microanalysis, ultraviolet-visible (UV-vis) diffuse reflectance spectroscopy, and thermogravimetric (TG) and differential scanning calorimetry (DSC) techniques. Interestingly, 1 undergoes an irreversible structure phase transition at ∼436 K in the first heating process, which is accompanied by an abrupt color change from colorless to yellow; however, a reversible color change between pale yellow and yellow is observed in the next heating-cooling cycles. Notably, DSC measurement revealed that a reversible phase transition is associated with the change in color between pale yellow and yellow, while the powder X-ray diffraction (PXRD) patterns corresponding to pale yellow and yellow phases are quite similar to each other. These observations demonstrate that thermochromism in the next heating-cooling runs is associated with a reversible structure phase transition, which perhaps concerns the disorder-order transformation of alkyl chains in the cationic ligand [Pr-dabco]+, and relevant to the anharmonic fluctuations of the Ag-Br and Ag-N bonds, a strong electron-phonon coupling effect is seen within the bromoargentate cluster.