Defining physicochemical properties of urinary proteins that determine their inhibitory activities against calcium oxalate kidney stone formation.

We have recently reported a set of urinary proteins that inhibited calcium oxalate (CaOx) stone development. However, physicochemical properties that determine their inhibitory activities remained unknown. Herein, human urinary proteins were chromatographically fractionated into 15 fractions and subjected to various CaOx crystal assays and identification by nanoLC-ESI-Qq-TOF MS/MS. Their physicochemical properties and crystal inhibitory activities were subjected to Pearson correlation analysis. The data showed that almost all urinary protein fractions had crystal inhibitory activities. Up to 128 proteins were identified from each fraction. Crystallization inhibitory activity correlated with percentages of Ca2+-binding proteins, stable proteins, polar amino acids, alpha helix, beta turn, and random coil, but inversely correlated with number of Ox2--binding motifs/protein and percentage of unstable proteins. Crystal aggregation inhibitory activity correlated with percentage of stable proteins but inversely correlated with percentage of unstable proteins. Crystal adhesion inhibitory activity correlated with percentage of stable proteins and GRAVY, but inversely correlated with pI, instability index and percentages of unstable proteins and positively charged amino acids. However, there was no correlation between crystal growth inhibitory activity and any physicochemical properties. In summary, some physicochemical properties of urinary proteins can determine and may be able to predict their CaOx stone inhibitory activities.

Growth of Ba2CoWO6single crystals and their magnetic, thermodynamic and electronic properties.

This study explores the bulk crystal growth, structural characterization, and physical property measurements of the cubic double perovskite Ba2CoWO6(BCWO). In BCWO, Co2+ions form a face-centred cubic lattice with non-distorted cobalt octahedra. The compound exhibits long-range antiferromagnetic order belowTN= 14 K. Magnetization data indicated a slight anisotropy along with a spin-flop transition at 10 kOe, a saturation field of 310 kOe and an ordered moment of 2.17µB atT= 1.6 K. Heat capacity measurements indicate an effectivej= 1/2 ground state configuration, resulting from the combined effects of the crystal electric field and spin-orbit interaction. Surface photovoltage analysis reveals two optical gaps in the UV-Visible region, suggesting potential applications in photocatalysis and photovoltaics. The magnetic and optical properties highlight the significant role of orbital contributions within BCWO, indicating various other potential applications.

Growth of Single Crystals of (K1-xNax)NbO3 by the Self-Flux Method and Characterization of Their Phase Transitions.

In this study, single crystals of (K1-xNax)NbO3 are grown by the self-flux crystal growth method and their phase transitions are studied using a combination of Raman scattering and impedance spectroscopy. X-ray diffraction shows that single crystals have a perovskite structure with monoclinic symmetry. Single crystal X-ray diffraction shows that single crystals have monoclinic symmetry at room temperature with space group P1211. Electron probe microanalysis shows that single crystals are Na-rich and A-site deficient. Temperature-controlled Raman scattering shows that low temperature monoclinic-monoclinic, monoclinic-tetragonal and tetragonal-cubic phase transitions take place at -20 °C, 220 °C and 440 °C. Dielectric property measurements show that single crystals behave as a normal ferroelectric material. Relative or inverse relative permittivity peaks at ~-10 °C, ~230 °C and ~450 °C with hysteresis correspond to the low temperature monoclinic-monoclinic, monoclinic-tetragonal and tetragonal-cubic phase transitions, respectively, consistent with the Raman scattering results. A conduction mechanism with activation energies of about 0.5-0.7 eV was found in the paraelectric phase. Single crystals show polarization-electric field hysteresis loops of a lossy normal ferroelectric. The combination of Raman scattering and impedance spectroscopy is effective in determining the phase transition temperatures of (K1-xNax)NbO3.

An Investigation on Optical, Larvacidal and Cytotoxicity Analysis of Sulfanilic Acid Single Crystal for Optical and Biomedical Applications.

Sulfanilic acid (SFA) crystal is well known as an effective material for photonic, electro-optical, harmonic generating and biomedical applications. A well-known nonlinear optical material, a high-quality SFA single crystal made utilizing the slow evaporation solution method (SEST) is the subject of this article. A 75 days development period yielded a transparent SFA single crystal measuring 5 × 5 × 2 mm3. The grown crystal used for different characterizations like Single crystal XRD used to find out the cell parameters. Fourier transforms infrared utilized to identify the band assignments. UV-Visible analysis used to detect the absorbance of the crystal and it is utilized for optical application. Photoluminescence studies utilized to recognize the excitation and emission of the grown crystal. Fluorescence used for determining the crystallinity and purity of the sample. The quantitative analysis is verified by using Elemental Dispersive Analysis by X-Rays. Scanning Electron Microscopy utilized to identify the structural and morphological characteristics. To the best of our knowledge, this paper is the first to provide the generated crystal that was used to analyze cytotoxicity and larvacidal activity. Assessment of larvicidal activity was used to ascertain the anti-malarial efficacy. We tested the items on MCF7-Human Breast cancer cell line and MCF7 Vero cells using the MTT Assay to identify the molecular basis of their cytotoxicity in vitro. Biological and optical are two areas that could benefit from the created crystal.

Oriented Crystal Growth of Li0.33La0.557TiO3 Nanowire Induced by One-Dimensional Polymer Sheath toward Rapid Lithium-Ion Transfer.

Superionic conductor-based solid-state electrolytes with preferred crystal structures hold great promise for realizing ultrafast lithium-ion (Li+) transfer, which is urgently desired for all-solid-state lithium batteries. However, the precise control of crystal growth of superionic conductors is still challenging since the crystals always spontaneously grow to disordered structures with the lowest internal energy to ensure thermodynamic stability. Herein, a coaxial nanowire with a polyvinylpyrrolidone (PVP) sheath and a Li0.33La0.557TiO3 (LLTO) precursor core (PVP/LLTO-caNW) is prepared through coaxial electrospinning, followed by sintering into LLTO nanowire with an oriented crystal structure (LLTO-caNW). We demonstrate that the one-dimensional PVP sheath as a sacrificial layer generates uniform and the strongest adsorption ability on the (110) phase among different LLTO crystal planes, which induces the crystal to preferentially grow along the c-axis (the fastest Li+ transfer direction) during the nucleation and growth processes. As a result, the prepared LLTO-caNW displays an ultrahigh bulk ionic conductivity of 3.13 × 10-3 S cm-1, exceeding most LLTO crystals and approaching the theoretical conductivity. Meanwhile, the oriented crystal growth imparts to LLTO-caNW significantly reduced grain boundary resistance, and the grain-boundary conductivity reaches up to 1.09 × 10-3 S cm-1. This endows the composite solid electrolyte with high ionic conduction performance and superior cycle stability in the assembled all-solid-state lithium battery.

The influence of the axial group on the crystal structures of boron subphthalocyanines.

The crystal structures of 16 boron subphthalocyanines (BsubPcs) with structurally diverse axial groups were analyzed and compared to elucidate the impact of the axial group on the intermolecular π-π interactions, axial-group interactions, axial bond length and BsubPc bowl depth. π-π interactions between the isoindole units of adjacent BsubPc molecules most often involve concave-concave packing, whereas axial-group interactions with adjacent BsubPc molecules tend to favour the convex side of the BsubPc bowl. Furthermore, axial groups that contain O and/or F atoms tend to have significant hydrogen-bonding interactions, while axial groups containing arene site(s) can participate in π-π interactions with the BsubPc bowl, both of which can strongly influence the crystal packing. Bulky axial groups did tend to disrupt the π-π interactions and/or axial-group interactions, preventing some of the close packing that is seen in BsubPcs with less bulky axial groups. The atomic radius of the heteroatom bonded to boron directly influences the axial bond length, whereas the axial group has minimal impact on the BsubPc bowl depth. Finally, the crystal growth method did not generally appear to have a significant impact on the solid-state arrangement, with the exception of water occasionally being incorporated into crystal structures when hygroscopic solvents were used. These insights can help with the design and fine-tuning of the solid-state structures of BsubPcs as they continue to be developed as functional materials in organic electronics.

Programmable in-situ co-assembly of organic multi-block nanowires for cascade optical waveguides.

Organic heterostructures (OHs) with multi-segments exhibit special optoelectronic properties compared with monomeric structures. Nevertheless, the synthesis of multi-block heterostructures remains challenging due to compatibility issues between segment parts, which restricts their application in optical waveguides and integrated optics. Herein, we demonstrate programmable in-situ co-assembly engineering, combining multi-step spontaneous self-assembly processes to promote the synthesis of multi-block heterostructures with a rational arrangement of three or more segments. The rational design of segments enables exciton manipulation and ensures optical waveguides and proper output among the multi-segment OHs. This work enables the controllable growth of segments within multi-block OHs, providing a pathway to construct complex OHs for the rational development of future optical applications.

Polarized Raman Study of First-Order Phonons in Self-Flux Grown Single-Crystalline WTe2.

Bulk single crystals of WTe2 were grown by the self-flux method and characterized by X-ray diffraction, polarized micro-Raman spectroscopy, and optical microscopy. All methods revealed a high crystalline quality, thus demonstrating the advantages of the growth method used as a starting base for the synthesis of high-quality 2D materials. In each main scattering configuration, we recorded a series of Raman spectra in different sample orientations achieved by rotating the sample around the incident laser beam. In addition to the well-established case of excitation along the c crystal axis, we also applied laser excitation along the a and b axes. Thus, scattering configurations were also realized in the XZ and YZ polarization planes, for which no comparative literature data have yet been established. In these experiments, two new Raman-active phonons with B2 symmetry and frequencies of 89 cm-1 and 122 cm-1 were identified. The obtained experimental data enabled us to derive the magnitude ratios of all three tensor elements of the A1 modes and to find their phase differences.

Faceted crystal growth of cyclodextrin-oil inclusion complexes.

The spontaneous formation of cyclodextrin (CD)-oil inclusion complexes (ICs) and their further growth into patterned crystals present a bottom-up route to the fabrication of periodic macroscopic structure. Although the inclusion processes are well established for the molecules, understanding intermediate structures during the crystal growth and emerging of persistent crystalline order has been lacking. Here we build a hierarchy of oriented micro/nanostructures of CD-oil ICs in solution by choosing different oil guests including several straight-chain alkanes of C12, C14 and C16, oleic acid (OA), glycerol trioleate (TG) and soybean oil (SO), in an attempt to reveal the roles of oil guests in the formation of their crystallites. Remarkably, the ICs tend to grow into clusters and terminate at a certain finite size as long columns or lamella plates with well-defined facets, dependent on the type of oil used. For the first time, we report a non-equilibrium growth of crystallites with surface faceting directed by the guests by means of Arching and Bundling.

Hierarchical Nanostructures Constructed by Soft Epitaxial Self-Assembly of Organic-Inorganic Hybrid Giant Amphiphiles.

2D nanomaterials with ångström-scale thicknesses offer a unique platform for confining molecules at an unprecedentedly small scale, presenting novel opportunities for modulating material properties and probing microscopic phenomena. In this study, mesogen-tethered polyhedral oligomeric silsesquioxane (POSS) amphiphiles with varying numbers of mesogenic tails to systematically influence molecular self-assembly and the architecture of the ensuing supramolecular structures, are synthesized. These organic-inorganic hybrid amphiphiles facilitate precise spatial arrangement and directional alignment of the primary molecular units within highly ordered supramolecular structures. The correlation between molecular design and the formation of superlattices through comprehensive structural analyses, incorporating molecular thermodynamics and kinetics, is explored. The distinct intermolecular interactions of the POSS core and the mesogenic tails drive the preferential formation of a 2D inorganic sublattice while simultaneously guiding the hierarchical assembly of organic lamellae via soft epitaxy. The findings reveal the intricate balance between shape, size, and interaction strengths of the inorganic and organic components, and how these factors collectively influence the structural hierarchy of the superstructures, which consist of multiple sublattices. By controlling this unique molecular behavior, it is possible to modulate or maximize the anisotropy of optical, mechanical, and electrical properties at the sub-nanometer scale for nanotechnology applications.

The challenges of growing great crystals - or at least good enough ones!

The article of Sommer [Acta Cryst. (2024), C80, 337-342] provides a concise and effective introduction to the subject of growing crystals suitable for structure determination.

Exploring crystal structure-physical property relationships with pressure.

From its conception, X-ray crystallography has provided a unique understanding of the structure, bonding and electronic state of materials, which, in turn, unlocks a means of examining the properties and function of crystalline systems. Using state-of-the-art single-crystal X-ray diffraction, along with UV-Vis spectroscopy and DFT calculations, Zwolenik et al. [(2024). IUCrJ, 11, 519-527] have provided a comprehensive study of the structure-optical property relationship of 1,3-diacetylpyrene with methodologies that are increasingly accessible to non-specialist laboratories.

Selenophosphate Pb2P2Se6 Single Crystals Growth by Chemical Vapor Transport (CVT) Method for Radiation Detection.

The heavy metal selenophosphate Pb2P2Se6emerges as a promising room-temperature X-ray/γ-ray detectors due to its high resistivity, robust radiation-blocking capability, and outstanding carrier mobility-lifetime product, etc. However, the high activity of phosphides poses significant impediment to the synthesis and single crystal growth. In this work, we have prepared high-quality Pb2P2Se6 single crystals with using the chemical vapor transport (CVT) method. The XRD analysis combined with EDS result confirmed the uniform composition of the resulting as-grown single crystals, while UV-Vis-NIR transmittance spectra revealed the bandgap of 1.89 eV. Selected area electron diffraction patterns indicated the crystal belonged to the P21/c(14) space group. Additionally, the Au/Pb2P2Se6/Au device is fabricated, which exhibits a robust X-ray response with a sensitivity of 648.61 µC·Gy-1·cm-2 at 400 V·mm-1 under 50 kVp. Notably, the device also excels in alpha particle detection, boasting a resolution of ~14.48% under a bias of 400 V bias. The hole mobility-lifetime product (µτ)h of Pb2P2Se6 is estimated to be ~2.58×10-5 cm2·V-1. The results underscore potential applications of Pb2P2Se6 crystal is in the field of the semiconductor radiation detectors.

On Morphology of Aluminum-Gallium Nitride Layers Grown by Halide Vapor Phase Epitaxy: The Role of Total Reactants' Pressure and Ammonia Flow Rate.

The focus of this study was the investigation of how the total pressure of reactants and ammonia flow rate influence the growth morphology of aluminum-gallium nitride layers crystallized by Halide Vapor Phase Epitaxy. It was established how these two critical parameters change the supersaturation levels of gallium and aluminum in the growth zone, and subsequently the morphology of the produced layers. A halide vapor phase epitaxy reactor built in-house was used, allowing for precise control over the growth conditions. Results demonstrate that both total pressure and ammonia flow rate significantly affect the nucleation and crystal growth processes which have an impact on the alloy composition, surface morphology and structural quality of aluminum-gallium nitride layers. Reducing the total pressure and adjusting the ammonia flow rate led to a notable enhancement in the homogeneity and crystallographic quality of the grown layers, along with increased aluminum incorporation. This research contributes to a deeper understanding of the growth mechanisms involved in the halide vapor phase epitaxy of aluminum-gallium nitride, and furthermore it suggests a trajectory for the optimization of growth parameters so as to obtain high-quality materials for advanced optoelectronic and electronic applications.

Electric-Field Manipulation of Magnetic Chirality in a Homo-Ferro-Rotational Helimagnet.

Ferro-rotational (FR) materials, renowned for their distinctive material functionalities, present challenges in the growth of homo-FR crystals (i.e., single FR domain). This study explores a cost-effective approach to growing homo-FR helimagnetic RbFe(SO4)2 (RFSO) crystals by lowering the crystal growth temperature below the TFR threshold using the high-pressure hydrothermal method. Through polarized neutron diffraction experiments, it is observed that nearly 86% of RFSO crystals consist of a homo-FR domain. Notably, RFSO displays remarkable stability in the FR phase, with an exceptionally high TFR of ≈573 K. Furthermore, RFSO exhibits a chiral helical magnetic structure with switchable ferroelectric polarization below 4 K. Importantly, external electric fields can induce a single magnetic domain state and manipulate its magnetic chirality. The findings suggest that the search for new FR magnets with outstanding material properties should consider magnetic sulfates as promising candidates.

Bipyramidal Nanocrystals of Noble Metals: From Synthesis to Applications.

Shape control has been a major theme of nanocrystal research in terms of synthesis, property tailoring, and optimization of performance in a variety of applications. Among the possible shapes, bipyramids are unique owing to their symmetry, planar defects, and exposed facets. In this article, we focus on the colloidal synthesis of noble-metal nanocrystals featuring a triangular bipyramidal shape, together with highlights of their properties and applications. We start with a brief discussion of the general classification and requirements for the nucleation and growth of bipyramidal nanocrystals, followed by specific aspects regarding the synthetic methods with a focus on the roles of reduction, etching, and capping, as well as controls of facet, size, aspect ratio, and corner truncation. In the end, we illustrate how these aspects affect the properties of bipyramidal nanocrystals for plasmonic and catalytic applications, together with future perspectives.

How to grow crystals for X-ray crystallography.

Growing high-quality crystals remains a necessary part of crystallography and many other techniques. This article tabulates and describes several techniques and variations that will help individuals grow high-quality crystals in preparation for crystallographic techniques and other endeavors, such as form screening. The discussion is organized to focus on low-tech approaches available in any laboratory.

Investigation of structural, optical and mechanical behaviour of pure and Cr doped L-asparagine monohydrate single crystals.

Pure and chromium (Cr) doped L-asparagine monohydrate (LAM) single crystals were grown by using evaporation controlled solution growth technique. XRD analysis confirmed the orthorhombic crystal system with space group P212121 of grown crystals. Cr-incorporation decreased the cell parameters and unit cell volume of the crystals. Intermolecular interactions were analysed through Hirshfeld and fingerprint studies. SEM analysis showed the appearance of pits on the smooth surface of pure crystal due to Cr-addition. UV-Vis analysis showed high transparency, low cut-off and direct band gap of 5.42 eV and 5.51 eV for pure and Cr doped crystals, respectively. Fundamental functional groups were identified by FTIR and Raman spectroscopy. The thermal stability and melting point of the crystals were investigated using TGA/DSC analysis. The dielectric constant for doped LAM was increased to 44 as compare to dielectric constant of pure crystal which was 32. Both crystals showed low dielectric loss, having values 0.04 and 0.006 for pure LAM and doped crystals, respectively. In Vickers microhardness test, Cr doping was found to change the nature of pure LAM crystal from 'soft' to 'hard' as Meyer's index changed from 2.48 to 1.24.

Ring formation of transition metal trichalcogenide TaSe3 using vapor liquid process.

The synthesis of TaSe3 ring-shaped crystals displaying the coffee ring effect is investigated. By recrystallizing TaSe3 microcrystals dissolved in droplets of condensed Se gas, ring-shaped crystals were successfully grown. This novel method for ring formation effectively addressed the issue of connecting the edges of the crystal. Consequently, the synthesis method has the capability to grow MX3 ring-shaped crystals in any location where droplets can condense, can now be grown in specific locations, thus creating opportunities for advancements in electronic component development.

Enhanced boron removal via seed-induced crystal growth of barium perborate in sequential fluidized-bed crystallization.

Chemical oxo-precipitation (COP) is an enhanced precipitation method for boron removal with the conversion of boric acid to perborate anions. When using barium-based precipitant, the boron can be effectively precipitated as barium perborates (BaPBs). The phase transformation of BaPBs from amorphous (A-BaPB, Ba(B(OH)3OOH)2) to crystalline (C-BaPB, BaB2(OO)2(OH)4) form is crucial for effective boron removal. However, scaling up this phase transformation of BaPBs is hindered by poor diffusion. This study aims to promote the growth of C-BaPB through seed-induced crystal growth, eliminating the need for phase transformation. By examining the relationship between crystal growth rate and supersaturation, surface spiral growth was identified as the rate-limiting step of the growth of micron-sized seeds near pHpzc. To enable continuous crystal growth, granular seeds of C-BaPB were prepared and employed as the medium for fluidized-bed crystallization (FBC). The system reached steady state 3 hydraulic retention times, achieving 90% boron removal. The effect of surface loading, ionic strength, and dosages on steady-state crystal growth rate was studied, revealing a shift of the rate-limiting step in FBC to diffusion. Lastly, the system that constituted of two FBCs in-series for sequential crystallization of A-BaPB and C-BaPB was demonstrated. The integrated system provided 97.8% of boron removal from synthetic wastewater containing 500 mg-B/L, with 92.3% of boron crystallized on the granular seeds of BaPBs.