Vibrational Raman Spectroscopy Research Articles

Coordination Networks from [Te4]2+ Clusters and Polynitriles

AbstractThe reactions of a series of organic polynitriles with [Te4][AsF6]2 in liquid SO2 solution lead either to reduction of [Te4]2+ to elemental tellurium or to the formation of coordination polymers. With 1,3‐dicyanobenzene (1,3‐DCB), 1,4‐dicyanobenzene (1,4‐DCB), 1,2,4,5‐tetracyanobenzene (TCB), tetracyanoethylene (TCNE) and tetracyanochinodimethane (TCNQ) the coordination complexes [Te4][AsF6]2 ⋅ 2(1,3‐DCB), [Te4][AsF6]2 ⋅ 3(1,4‐DCB) ⋅ 2SO2, [Te4][AsF6]2 ⋅ TCB, [Te4][AsF6]2 ⋅ TCNE and [Te4][AsF6]2 ⋅ TCNQ ⋅ 8 SO2 were isolated and characterized by crystal structure analyses and vibrational Raman spectroscopy. The nitriles are coordinated to the square‐planar clusters forming 1D chains, 2D arrangements and 3D networks. Tetrakis(dicyanomethylene)cyclobutendiide [C4(C{CN}2)4]2− is oxidized by [Te4]2+ to the neutral cyanocarbon C4(C{CN}2)4, structurally representing a 4[radialene]. The ionization potentials and electron affinities of the cyanamide anion, cyanogen, 1,2‐DCB, 1,3‐DCB, 1,4‐DCB, TCB, C4(C{CN}2)4, TCNE and TCNQ and those polynitriles, which cause reduction of [Te4]2+, were calculated at coupled‐cluster level of theory in order to examine possible reasons for the stability of the coordination polymers based on electronic properties of the nitriles.

Structural, vibrational, and luminescent properties of pure and Ce-doped magnesium lithium aluminoborate glass

The objective of this work was to study the properties of new vitreous samples of pure BAlMgLi and Ce-doped BAlMgLi produced by the melt-quenching method. The structural and vibrational characteristics of the samples were analyzed using x-ray diffraction (XRD), vibrational Raman spectroscopy, and vibrational Fourier transform infrared spectroscopy (FTIR). Optically stimulated luminescence (OSL) and thermoluminescence (TL) techniques were also used to identify whether the samples showed a response to ionizing radiation. XRD analyses confirmed the predominance of the amorphous phase of the samples. The Raman spectra revealed that the atomic bonds present in the material matrix are of the pyroborate and metaborate type, enabling stretching vibrations in isolated BO4 and/or Al–O or Al–O–B units. The band at approximately 810 cm−1 is characteristic of the formation of the boroxol ring, indicating that the presence of other elements in the matrix does not affect its glassy characteristics. The FTIR analyses reinforce the results found by Raman spectroscopy, because bands characteristic of low hygroscopic glasses were observed, due to the conversion of BO3 units into BO4 in triborate, tetraborate, and pentaborate groups. This conversion is due to dopant entrainment, which contributes to the high optical transparency of the samples. Their OSL and TL signals were reproducible with intensities dependent on the dopant concentration and radiation dose, with the most intense emissions resulting from 0.5% Ce concentrations.

Molecular H2 in silicate melts

A series of hydrothermal diamond anvil cell experiments was conducted to constrain the equilibrium distribution of molecular H2 between H2O-saturated sodium aluminosilicate melts and H2O at elevated temperatures (600–800 °C) and pressures (317–1265 MPa). The distribution of H2 between the silicate liquid and the aqueous fluid was achieved through real-time monitoring of the H-H stretching vibration under in situ conditions using Raman vibrational spectroscopy. Results show that the solubility of H2 in silicate melts saturated with H2O decreases as the temperature increases, with control exerted by the mole fraction of H2O in the melt. The dissolution of H2 in the hydrous silicate melts appears to follow Henrian behavior, resembling that of an inert, neutral non-polar species. To express species solubility as a function of temperature (T in K) an empirical equation was developed:ln Km/f = 11.4 (±1.3) *1000 / T (K) − 18.7 (±1.1)where Km/f is the equilibrium constant for the reaction H2(g) = H2(melt). This equation was derived by integrating data from the current and prior experimental studies that include silicate melts with varying H2O saturation levels. It should be deemed applicable within the temperature range of 600–1450 °C and pressures ranging from 0.3 to 3 GPa. The implications are extended into developing an understanding of the H partitioning between H2-rich atmospheres blanketing magma oceans in the early history of planetary bodies. For example, transferring H from primordial atmospheric envelopes to the interior of rocky exoplanets may be less efficient than previously believed, which should be considered in models of volatile retention. Experimental data also suggest that minimal amounts of solar nebula H2 are likely to dissolve in the molten surface of primitive objects in the protoplanetary disk (∼10−5 to 10−9 mol faction H2 in melt), contradicting the highly reducing conditions observed in chondrule mineral compositions.

Hydrogen-Bonded Network of Water in Phase-Separated Biomolecular Condensates.

Biomolecular condensates formed via phase separation of intrinsically disordered proteins/regions (IDPs/IDRs) and nucleic acids are associated with cell physiology and disease. Water makes up for ∼60-70% of the condensate volume and is thought to influence the complex interplay of chain-chain and chain-solvent interactions, modulating the mesoscale properties of condensates. The behavior of water in condensates and the key roles of protein hydration water in driving the phase separation remain elusive. Here, we employ single-droplet vibrational Raman spectroscopy to illuminate the structural redistribution within protein hydration water during the phase separation of neuronal IDPs. Our Raman measurements reveal the changes in the water hydrogen bonding network during homotypic and heterotypic phase separation governed by various molecular drivers. Such single-droplet water Raman measurements offer a potent generic tool to unmask the intriguing interplay of sequence-encoded chain-chain and chain-solvent interactions governing macromolecular phase separation into membraneless organelles, synthetic condensates, and protocells.

TiO2 Nanoparticles with Adjustable Phase Composition Prepared by an Inverse Microemulsion Method: Physicochemical Characterization and Photocatalytic Properties.

Titania nanoparticles (NPs) find wide application in photocatalysis, photovoltaics, gas sensing, lithium batteries, etc. One of the most important synthetic challenges is maintaining control over the polymorph composition of the prepared nanomaterial. In the present work, TiO2 NPs corresponding to anatase, rutile, or an anatase/rutile/brookite mixture were obtained at 80 °C by an inverse microemulsion method in a ternary system of water/cetyltrimethylammonium bromide/1-hexanol in a weight ratio of 17:28:55. The only synthesis variables were the preparation of the aqueous component and the nature of the Ti precursor (Ti(IV) ethoxide, isopropoxide, butoxide, or chloride). The materials were characterized with X-ray diffraction, scanning/transmission electron microscopy, N2 adsorption-desorption isotherms, FTIR and Raman vibrational spectroscopies, and diffuse reflectance spectroscopy. The synthesis products differed significantly not only in phase composition, but also in crystallinity, textural properties, and adsorption properties towards water. All TiO2 NPs were active in the photocatalytic decomposition of rhodamine B, a model dye pollutant of wastewater streams. The mixed-phase anatase/rutile/brookite nanopowders obtained from alkoxy precursors showed the best photocatalytic performance, comparable to or better than the P25 reference. The exceptionally high photoactivity was attributed to the advantageous electronic effects known to accompany multiphase titania composition, namely high specific surface area and strong surface hydration. Among the single-phase materials, anatase samples showed better photoactivity than rutile ones, and this effect was associated, primarily, with the much higher specific surface area of anatase photocatalysts.

Plasma-Sprayed Osseoconductive Hydroxylapatite Coatings for Endoprosthetic Hip Implants: Phase Composition, Microstructure, Properties, and Biomedical Functions

This contribution attempts to provide a state-of-the-art account of the physicochemical and biomedical properties of the plasma-sprayed hydroxylapatite (HAp) coatings that are routinely applied to the surfaces of metallic endoprosthetic and dental root implants designed to replace or restore the lost functions of diseased or damaged tissues of the human body. Even though the residence time of powder particles of HAp in the plasma jet is extremely short, the high temperature applied induces compositional and structural changes in the precursor HAp that severely affect its chemical and physical properties and in turn its biomedical performance. These changes are based on the incongruent melting behavior of HAp and can be traced, among many other analytical techniques, by high resolution synchrotron X-ray diffraction, vibrational (Raman) spectroscopy, and nuclear magnetic resonance (NMR) spectroscopy. In vivo reactions of the plasma-sprayed coatings to extracellular fluid (ECF) can be assessed and predicted by in vitro testing using simulated body fluids (SBFs) as proxy agents. Ways to safeguard the appropriate biological performance of HAp coatings in long-term service by controlling their phase content, porosity, surface roughness, residual stress distribution, and adhesion to the implant surface are being discussed.

Crossroads of vibrational (infrared and Raman) spectroscopy and X-ray powder diffraction in identification and characterization of some minerals – advantages and limitations. A review

Many analytical methods have been successfully employed for the study of minerals, in particular, vibrational infrared (FTIR) and Raman spectroscopies and X-ray powder diffraction (XRPD). The advantages of the vibrational spectroscopic techniques for identifying and characterizing minerals include: rapid and versatile use; qualitative and quantitative chemical signatures; distinctive chemical fingerprint of a material; indirect determination of the crystal features (polymorphism, isomorphism, coordination, degree of deformation of structural polyhedra); small sample quantity (area less than 1 μm2 for Raman); wide coverage of 4,000 – 50 cm−1 region in a single scan; in situ and direct measurements without sample preparation; nondestructive use; etc. On the other hand, XRPD is a destructive technique that, depending on the method used and the density of the material, requires from a few micrograms up to around 5 grams of sample quantity for analysis. In spite of that, it is a rapid and powerful technique used in mineral studies with relatively straightforward interpretation of the results. During the last decade, portable X-ray powder diffractometers for the nondestructive analysis of art and archeological materials have been developed along with the portable and hand-held vibrational spectroscopy instrument. Here, some advantages and limitations in the process of the complementary use of FTIR and Raman vibrational spectroscopy and XRPD for identification and characterization of minerals are outlined.

Solvent Effect on the Structural, Optical, Morphology, and Antimicrobial Activity of Silver Phosphate Microcrystals by Conventional Hydrothermal Method.

The design of particle size and morphology are a promising approach to investigating the properties exhibited by different types of materials. In the present study, the silver phosphate microcrystals (Ag3PO4) were first time synthesized using the hydrothermal and solvothermal method by combination of the solvents water/isopropyl alcohol (SP-IA), water/acetone (SP-AC), water/ammonium hydroxide (AP-AH), all in a ratio of 1:1 (v/v). The synthesized materials were structurally characterized by X-ray diffraction (XRD), Rietveld refinement, and Raman vibrational spectroscopy, where it was confirmed that the pure phase was achieved for all prepared samples. The study of the optical properties by UV-vis diffuse reflectance spectroscopy (UV-vis/DRS) and colorimetry revealed that the obtained materials have an optical bandgap between 2.30 and 2.32 eV. The FE-SEM images collected revealed different morphologies for the synthesized materials, with a predominance of tetraploid-shaped microcrystals for the SP-AC sample, rods for the SP-IA sample, cubes and polyhedral for the SP-WT sample and condensed polyhedral for the SP-AH sample. The photocatalytic performance against the Rhodamine B dye (RhB) was 100%, 98.2%, 94.2%, and 87.8%, using the samples SP-AC, SP-IA, SP-WT, and SP-AH as photocatalyst at time of 12 min. On the other hand, the antimicrobial performance of SP-AC sample showed superior performance, resulting in the minimum inhibitory concentration-MIC of 7.81 μg mL-1 for the strain of E. coli, 7.81 μg mL-1 for the strain of E. aureus, 15.62 μg mL-1 for the strain of P. auruginosa, and 15.62 μg mL-1 for the strains of C. albicans. In this way, was synthesized a promissory antimicrobial and photocatalyst material, through an easy and cost-effective method.

Phase Separation in Cold Para-H_{2} D_{2} Clusters.

Low temperature phase separation in mixtures of ^{3}He and ^{4}He isotopes is a unique property of quantum fluids. Hydrogen has long been considered as another potential quantum liquid and has been predicted to be superfluid at T≤1 K, well below freezing temperature of ≈14 K. Phase separation has also been predicted in mixtures of para-H_{2} and D_{2} at temperatures ≤3 K. To defer the freezing, we produced clusters containing para-H_{2} and D_{2} at an estimated temperature of ≈2 K whose state was studied by vibrational Raman spectroscopy. The results indicate that the clusters are liquid and show the phase separation of the isotopes. The phase separation is further corroborated by the quantum molecular dynamics simulation.

Intrinsic conformational preference in the monomeric protein governs amyloid polymorphism.

The inherent stochasticity associated with the hierarchical self-assembly of either native-like or partially-unfolded protein monomers leads to the formation of transient, morphologically-diverse prefibrillar species resulting in structurally-distinct polymorphic protein aggregates. High-resolution structural characterization of mature aggregates has revealed heterogeneous supramolecular packing of protofibrils within amyloid polymorphs. However, little is known about whether initial monomeric protein conformers engender polymorphism at the onset of aggregation. Here, we show that intrinsic conformational preference in aggregation-competent monomeric ovalbumin, an archetypal serpin, dictates fibrillar polymorphism by modulating aggregation pathways. Using fluorescence, FT-IR, and vibrational Raman spectroscopy coupled with dynamic light scattering and electron microscopy, we demonstrate that conformationally-diverse amyloidogenic monomers, formed via an interplay of electrostatic and hydrophobic interactions before the commencement of aggregation, play a crucial role in promoting amyloid polymorphism. Moreover, the monomeric conformational fingerprints, accrued at the onset of aggregation, persist and propagate during the formation of polymorphic amyloids. Our results delineate essential conformational characteristics of the monomeric protein preceding aggregation, which will have broad implications in the mechanistic understanding of amyloid strain diversity observed in disease-related proteins.

β-SnWO4 as yellow lead-free pigment by ball milling method: Rietveld refinement, morphology, optical and colorimetric properties

The article presents a new route of synthesis of tin tungstate (β-SnWO4) by high-energy ball milling (HEBM), starting from the precursors metallic tin (Sn) and tungsten trioxide (WO3). After 4 h of grinding, the pure phase was obtained for the beta (β-SnWO4) of cubic structure and space group P213, with a high crystallinity was confirmed by X-ray diffraction (XRD), Rietveld refinement, Raman vibrational spectroscopy. All the characteristic elements of tin tungstate (Sn, W and O) were identified in the analysis by energy dispersive X-ray spectroscopy (EDX). The optical band gap values for the synthesised materials at 4 and 5 h were 2.82 and 2.50 eV, respectively. Finally, the colorimetric properties obtained of sample SW-5h are promising in applications involving pigments free of lead-based compounds, which exhibits colorimetric coordinates L*, a* and b* of 26.52, 0.62 e 17.8, respectively.

Vibrational Analysis of Constrained Molecular Systems.

Vibrational spectroscopy, including infrared (IR), Raman spectroscopy, and vibrational circular dichroism, is instrumental in determining the structure and composition of molecules. These techniques are highly sensitive to molecular conformations. However, full molecular optimization, necessary for theoretical vibrational spectra, can lead to unintended conformational changes, especially in large biomolecules like polypeptides. To address this, dihedral angle constraints can be imposed during optimization to preserve the molecule's native conformation. Constraint-optimized molecular geometries, not being true stationary points in the full configurational space, pose challenges for traditional vibrational analysis. We address this by considering such geometries as subspace minima, reformulating vibrational analysis to incorporate constraints. Normal modes and spectra consistent with these constraints are obtained by projecting the force constant matrix onto a space orthogonal to the constrained coordinates. This method, illustrated by the example of enkephalin, yields 3N - 6 - m nonzero frequencies after constraint projection, demonstrating its applicability to biomolecules with flexible conformations. Our approach offers a comprehensive mathematical framework to compute vibrational spectra of molecules with conformationally flexible subunits under environmental constraints.

Opto-Lipidomics of Tissues.

Lipid metabolism and signaling play pivotal functions in biology and disease development. Despite this, currently available optical techniques are limited in their ability to directly visualize the lipidome in tissues. In this study, opto-lipidomics, a new approach to optical molecular tissue imaging is introduced. The capability of vibrational Raman spectroscopy is expanded to identify individual lipids in complex tissue matrices through correlation with desorption electrospray ionization (DESI) - mass spectrometry (MS) imaging in an integrated instrument. A computational pipeline of inter-modality analysis is established to infer lipidomic information from optical vibrational spectra. Opto-lipidomic imaging of transient cerebral ischemia-reperfusion injury in a murine model of ischemic stroke demonstrates the visualization and identification of lipids in disease with high molecular specificity using Raman scattered light. Furthermore, opto-lipidomics in a handheld fiber-optic Raman probe is deployed and demonstrates real-time classification of bulk brain tissues based on specific lipid abundances. Opto-lipidomics opens a host of new opportunities to study lipid biomarkers for diagnostics, prognostics, and novel therapeutic targets.

Vibrational spectroscopy as a promising modality for diagnosing early osteoarthritis: a literature review

Background: Osteoarthritis (OA) is a joint disease caused by biological, chemical, and viscoelastic changes in the cartilage, synovium, subchondral bone, and synovial fluid. The current imaging techniques used to diagnose OA are frequently time-consuming, expensive, and damaging. Joint tissues have been examined using vibrational spectroscopy, and spectra of arthritic cartilage or subchondral bone in animals and people have revealed early chemical changes. This literature review aims to evaluate the role of vibrational spectroscopy in detecting early OA. Methods: Using the keywords "osteoarthritis," "imaging," "diagnostic," "spectroscopy," "vibrational spectroscopy," cartilage," and "synovial fluid," studies in online databases such as PubMed, the Cochrane Library, Wiley Online Library, and Google Scholar were searched for this review of the literature. After that, appropriate studies were conducted using a narrative synthesis analysis. Discussion: There are three types of vibrational spectroscopy, including near-infrared (NIR), infrared (IR), and Raman spectroscopy, which creates a vibrational spectrum from the vibrating of molecules or atomic groups brought on by electromagnetic radiation. Early OA can be identified by spectroscopic analysis of the synovial fluid, alterations in articular cartilage, and subchondral bone. The stretching and bending vibrations of C-H, N-H, and O-H bonds are visible in the NIR spectrum at wavelengths between 12,500 and 4000 cm-1. The transition between molecules' vibrational and rotational energy levels causes structural modifications in the 4000-400 cm-1 range, which are analyzed by IR spectroscopy. Raman spectroscopy uses the Raman scattering method to reflect the vibrational information between molecules. Conclusion: Vibrational spectroscopy is a promising modality for detecting early OA by analyzing synovial fluid spectrum, articular cartilage and subchondral bone changes.

Origin of Strong Hydrogen Bonding and Preferred Orientation of Water at Uncharged Polyethylene Glycol Polymer/Water Interface.

Polyethylene glycol (PEG), a water-soluble non-ionic polymer, finds diverse applications from Li-ion batteries to drug delivery. The effectiveness of PEG in these contexts hinges on water's behavior at PEG/water interfaces. Employing heterodyne-detected vibrational sum frequency generation and Raman spectroscopy along with a novel analytical approach, termed difference spectroscopy with simultaneous curve-fitting analysis, we observed that water exhibits both "hydrogen-up" and "hydrogen-down" orientations at PEG(≥400u)/water interfaces. As the molar mass of PEG increases, the contribution of the strongly hydrogen-bonded and H-up-oriented water rises. We propose that the PEG-affected interfacial water originates from the asymmetrical hydration of the surface-adsorbed PEG, as evidenced by the resemblance between the water spectra in the hydration shell of PEG and those at the PEG/water interface. These findings elucidate the molecular mechanism underlying PEG's catalytic role in water splitting at membrane interfaces.

Intermolecular Interactions in 3-Aminopropyltrimethoxysilane, N-Methyl-3-aminopropyltrimethoxysilane and 3-Aminopropyltriethoxysilane: Insights from Computational Spectroscopy

In this work, a computational spectroscopy approach was used to provide a complete assignment of the inelastic neutron scattering spectra of three title alkoxysilane derivatives—3-aminopropyltrimethoxysilane (APTS), N-methyl-3-aminopropyltrimethoxysilane (MAPTS), and 3-aminopropyltriethoxysilane (APTES). The simulated spectra obtained from density functional theory (DFT) calculations exhibit a remarkable match with the experimental spectra. The description of the experimental band profiles improves as the number of molecules considered in the theoretical model increases, from monomers to trimers. This highlights the significance of incorporating non-covalent interactions, encompassing classical NH···N, N–H···O, as well as C–H···N and C–H···O hydrogen bond contacts, to achieve a comprehensive understanding of the system. A distinct scenario emerges when considering optical vibrational techniques, infrared and Raman spectroscopy. In these instances, the monomer model provides a reasonable description of the experimental spectra, and no substantial alterations are observed in the simulated spectra when employing dimer and trimer models. This observation underscores the distinctive ability of neutron spectroscopy in combination with DFT calculations in assessing the structure and dynamics of molecular materials.

Single-molecule FRET unmasks structural subpopulations and crucial molecular events during FUS low-complexity domain phase separation

Biomolecular condensates formed via phase separation of proteins and nucleic acids are thought to be associated with a wide range of cellular functions and dysfunctions. We dissect critical molecular events associated with phase separation of an intrinsically disordered prion-like low-complexity domain of Fused in Sarcoma by performing single-molecule studies permitting us to access the wealth of molecular information that is skewed in conventional ensemble experiments. Our single-molecule FRET experiments reveal the coexistence of two conformationally distinct subpopulations in the monomeric form. Single-droplet single-molecule FRET studies coupled with fluorescence correlation spectroscopy, picosecond time-resolved fluorescence anisotropy, and vibrational Raman spectroscopy indicate that structural unwinding switches intramolecular interactions into intermolecular contacts allowing the formation of a dynamic network within condensates. A disease-related mutation introduces enhanced structural plasticity engendering greater interchain interactions that can accelerate pathological aggregation. Our findings provide key mechanistic underpinnings of sequence-encoded dynamically-controlled structural unzipping resulting in biological phase separation.

Multispecies oral biofilm and identification of components as treatment target

Endodontic infections involve a multispecies biofilm, making it difficult to choose an antimicrobial treatment. Characteristics such as the pathogens involved and number of microorganisms, nutrients, material surface to develop the biofilm, flow and oxygenation conditions are important for biofilm development using in vitro models. ObjectiveTo develop a standardized biofilm model, which replicates the main features (chemical, microbiological, and topographical) of an infected root canal tooth to detect components as treatment target. DesignClinical strains of Enterococcus faecalis, Candida albicans, and Actinomyces israelii were isolated, and a multispecies biofilm was developed using continuous laminar flow reactors under anaerobic conditions in human dental roots. The microbiological composition was determined by counting colony-forming units and scanning electron microscope micrographs. In addition, the chemical composition of the exopolymeric matrix was determined by vibrational Raman spectroscopy and liquid chromatography of biofilm supernatant treated with enzyme. ResultsE. faecalis turned out to be the main microorganism in mature biofilm, this was related to the presence of β-galactosidase detected by vibrational Raman spectroscopy. After the enzymatic treatment of the extracellular polymeric substance, the presence of mannose and glucose was established. ConclusionsThe present work contributes to better understanding of standard conditions to develop a multispecies biofilm in human dental roots, which could have an impact on the generation of new root canal disinfection techniques in endodontic pathologies.

Investigation into polymorphism within ethenzamide-ethylmalonic acid cocrystal using Raman and terahertz vibrational spectroscopy

Two cocrystal polymorphs of ethenzamide (ETZ) and ethylmalonic acid (EMA) were synthesized by solvent evaporation. Crystal structure analysis revealed that the main amide − carboxyl heterosynthon in ETZ-EMA cocrystal Form I and Form II are the same, but the crystal structure of these two polymorphs are different. Terahertz (THz) and Raman vibrational spectroscopy were used to characterize ETZ, EMA, ETZ-EMA cocrystal polymorph Form I and Form II respectively. The experimental results showed that ETZ, EMA, ETZ-EMA cocrystal Form I and ETZ-EMA cocrystal Form II exhibited completely different characteristic peaks. Both THz and Raman vibrational spectroscopy can be used to distinguish ETZ-EMA cocrystal Form I from Form II. Furthermore, the investigation of phase transition induced by temperature and solid-state grinding was also performed. In the temperature phase transition experiments, when the powder sample was heated to a temperature range of 80–82 °C, the metastable ETZ-EMA cocrystal Form I transformed into the more stable ETZ-EMA cocrystal Form II. Solid-state grinding analysis revealed that the results of the ETZ-EMA cocrystal polymorph synthesis in grinding experiments depended on the polarity of the solvents used. Grinding without solvent or with high polarity solvents tended to result in the stable ETZ-EMA cocrystal Form II. Moreover, the metastable ETZ-EMA cocrystal Form I would transform into Form II after further grinding process. These results demonstrate that THz and Raman vibrational spectroscopy have high sensitivity and accuracy in the detection of both cocrystal synthesis and cocrystal polymorph phase transitions.

Synthesis of CaNb2O6 with a Rynersonite-like Structure: Morphology, Rietveld Refinement, Optical, and Vibrational Properties.

In this study, we report the easy and low-cost synthesis of calcium niobate (CaNb2O6) with the isomorphic structure of the Rynersonite mineral for CaTa2O6. The samples were prepared by the ball milling method at room temperature at a synthesis time of 0.5, 1, 2, 3, and 4 h. The structural analysis by XRD, Rietveld refinement, and vibrational Raman spectroscopy confirms all diffraction peaks and active mode characteristics of the pure phase of CaNb2O6 for the 3-h and 4-h samples, with a crystallite size of 22.5 and 23.2 nm, respectively. The optical band gap obtained was 3.18(2) eV (3-h sample), lower than the optical band gap for niobium oxide, characteristic of materials with strong photon absorption in the UVA region of the spectrum. The surface analysis by scanning electron microscopy reveals the obtention of several agglomerates of irregular particles ranging in the submicro and micro scales. Therefore, the present approach successfully obtained calcium niobate with the formula CaNb2O6 at a short synthesis time and room temperature.