Crystal State Research Articles

Study of Curie Temperature, Ferromagnetism, and thermoelectric properties BaCo2Z4 (Z = S, Se, Te) for spintronic and energy applications

Spintronics is an emerging technology that harnesses electron spin to speed up data transfer, manipulation, and storage. In our thorough examination of BaCo2Z4 (Z = S, Se, Te), we have probed into electronic behaviour, Curie temperature, ferromagnetism, and thermoelectric behaviour. Our optimization analysis underscored the superior energy release of ferromagnetic states over antiferromagnetic counterparts, a finding substantiated by formation energy. We calculated spin polarization and Curie temperature using the Heisenberg model, confirming that ferromagnetism is prevalent at temperatures higher than room temperature. Including hybridization, crystal field energy, states density, band structures, exchange constants and energies, and the double exchange model, the investigation examined the complex nature of ferromagnetism. Importantly, shifting the magnetic moment away from Co and toward Ba and S/Se/Te sites revealed that electron spin, not clustering of Co’s magnetic ions, is the fundamental property of ferromagnetism. We also investigated thermoelectric metrics such as the Seebeck coefficient, conductivities, and power factor for spin (↑) and spin (↓), which helped us to understand the complex role of electron spin at high temperatures and their role in energy harvesting applications.

Surface states in one-dimensional graphene-dielectric photonic crystal

Surface states in one-dimensional graphene-dielectric photonic crystal

Quantitative Analysis of Amorphous Form in Indomethacin by Near Infrared Spectroscopy Combined with Partial Least Squares Regression Analysis

Indomethacin (INDO) is a synthetic non-steroidal antipyretic, analgesic, and anti-inflammatory drug that commonly exists in both amorphous and crystalline states. Its amorphous state (A-INDO) is utilized by pharmaceutical companies as an active pharmaceutical ingredient (API) in the production of INDO drugs due to its higher apparent solubility and bioavailability. The crystal state also encompasses various crystal forms such as the α-crystal form (α-INDO) and γ-crystal form (γ-INDO), with the highly crystalline and insoluble γ-INDO being commercially available. A-INDO, existing in a thermodynamically high-energy state, is susceptible to several factors during the preparation, storage, and transportation of API leading to its conversion into γ-INDO, thus impacting the bioavailability and efficacy of INDO drugs. Therefore, quantitative analysis of the A-INDO/γ-INDO content in INDO API becomes essential for controlling the production quality of INDO. The primary objective of this study is to investigate the feasibility of NIR for the quantitative analysis of A-INDO in INDO API, and to further elucidate its quantitative analysis mechanism. The NIR spectral data were collected for A-INDO and γ-INDO binary mixture samples with different resolutions, and these spectra were then selected and reconstructed using the interval partial least square (iPLS) method. Different pretreatment methods were employed to enhance the reconstructed spectra by highlighting relevant eigen information while eliminating invalid information caused by environmental factors or physical characteristics of samples. The most suitable PLSR model for quantitative analysis of A-INDO within the range of 0.0000–100.0000% w/w% was established, screened, and validated. From various perspectives, including distribution of spectral effective information, impact of resolution on PLSR model performance, variance contribution/cumulative variance contribution of PLSR model principal components (PCs), PCI loadings, relationship between spectral scores, and A-INDO content, feasibility assessment was conducted for the quantitative analysis of A-INDO in INDO using NIR spectroscopy. Additionally, a detailed investigation on the quantitative analysis mechanism of the optimal PLSR model was undertaken including the correlation between the characteristic peaks of spectra and information regarding hydrogen groups or hydrogen bonds in A-INDO or γ-INDO molecules. This study aims to provide theoretical support for the quantitative analysis of A-INDO in INDO API as well as serve as a reliable reference method for API quantification and quality control in similar drugs.

Characterization of the enzyme for 5-hydroxymethyluridine production and its role in silencing transposable elements in dinoflagellates

Dinoflagellate chromosomes are extraordinary, as their organization is independent of architectural nucleosomes unlike typical eukaryotes and shows a cholesteric liquid crystal state. 5-hydroxymethyluridine (5hmU) is present at unusually high levels and its function remains an enigma in dinoflagellates chromosomal DNA for several decades. Here, we demonstrate that 5hmU contents vary among different dinoflagellates and are generated through thymidine hydroxylation. Importantly, we identified the enzyme, which is a putative dinoflagellate TET/JBP homolog, catalyzing 5hmU production using both in vivo and in vitro biochemical assays. Based on the near-chromosomal level genome assembly of dinoflagellate Amphidinium carterae, we depicted a comprehensive 5hmU landscape and found that 5hmU loci are significantly enriched in repeat elements. Moreover, inhibition of 5hmU via dioxygenase inhibitor leads to transcriptional activation of 5hmU-marked transposable elements, implying that 5hmU appears to serve as an epigenetic mark for silencing transposon. Together, our results revealed the biogenesis, genome-wide landscape, and molecular function of dinoflagellate 5hmU, providing mechanistic insight into the function of this enigmatic DNA mark.

Organic Materials with Ultrabright Phosphorescence at Room Temperature under Physiological Conditions for Bioimaging

AbstractIn contrast to the high efficiency of room temperature phosphorescence in crystal states, the generally utilized nanoparticles of organic materials in bioimaging demonstrated sharply decreased performance by orders of magnitude under physiological conditions, badly limiting the realization of their unique advantages. This case, especially for organic red/near‐infrared (NIR) phosphorescence materials, is not only the challenge present in reality but more importantly, for the theoretical problem of deeply understanding and avoiding the quenching effect by oxygen and water toward excited triplet states. Herein, thanks to the intelligent molecular design by the introduction of abundant hydrophobic chains and highly‐branched structures, bright and persistent red/NIR phosphorescence under physiological conditions has been realized, which demonstrated the shielding effect towards oxygen, and the strengthened intermolecular interactions to suppress the non‐radiative transitions. Accordingly, the record phosphorescence intensity of nanoparticles in bioimage, up to 8.21±0.36×108 p s−1 cm−2 sr−1, was achieved, to realize the clear phosphorescence imaging of liver and tumors in living mice, even lymph nodes in rabbit models with high SBRs. This work afforded an efficient way to achieve the bright red/NIR phosphorescence nanoparticles, guiding their further applications in biology and medicine.

Multiple Structural and Phase Transformations of MOF and Selective Hydrocarbon Gas Separation in its Amorphous, Glass Phase States

AbstractThe first wide‐view image of multiple structural and phase transformations for MOFs, ranging from crystal state transformations to the extreme limit approaching liquid/glass phase, was presented. The process involves i) an initial crystalline transformation from square‐layer framework [Co2(pybz)2(CH3COO)2] ⋅ DMF (Co2) to a 3‐fold interpenetrated and ordered vacancies contained framework [Co(pybz)2(CH3OH)2] ⋅ 2CH3OH (CoM) due to in situ disassemble‐reassemble, ii) thermal induced departure of a pair of cis‐form coordinated methanol in CoM leads to amorphous framework a‐dCoM, iii) glass transition to super‐cooled liquid scl‐dCoM, iv) obtaining MOF glass g‐dCoM upon quenching the super‐cooled liquid, and v) re‐crystallization of super‐cooled liquid generates 6‐fold interpenetrated dia‐net framework [Co(pybz)2]6n (rec‐dCoM) under further heating. The access to glass from CoM, provides a new self‐perturbation strategy to create MOF glasses without melting. The wider pore size distribution in amorphous/glassy MOFs than crystalline precursor achieved the first time selective hydrocarbon gas separation by breakthrough experiments, which bring efficient separation of 1 : 99 C2H2/C2H4 by either a‐dCoM or g‐dCoM and produce polymer grade C2H4 with purity≥99.5 % after a single adsorption process. Furthermore, the mixture of 50 : 50 C3H6/C3H8 can be separated by a‐dCoM.

Impact of oxygen vacancies on the structural, electronic, and optical properties of Cu<i>2</i>O and nitrogen-doped Cu<sub>2</sub>O for optoelectronic applications: a first-principles study

This study utilizes Density Functional Theory (DFT) within the Quantum ESPRESSO framework to explore the effects of oxygen vacancies and nitrogen doping on the electronic structure and optical properties of cuprous oxide (Cu2O). Pristine Cu2O, an intrinsic p-type semiconductor, typically exhibits a direct band gap. Introducing an oxygen vacancy in the absence of a dopant broadens the band structure, leading to both direct and indirect band gap characteristics. In contrast, nitrogen doping transforms the band gap into a direct one, significantly reducing it from 1.97 eV to 1.09 eV, which deviates from previous findings due to potential variations in the initial state of the Cu2O host crystal. Furthermore, spin-polarization effects indicate spin-dependent behaviour within the material. The study also examines the absorption properties of pristine, defective, and nitrogen-doped Cu2O systems using the complex dielectric function. The results show distinct absorption peaks and transitions, with nitrogen-doped Cu2O exhibiting strong absorption in the visible light range, underscoring its potential for solar cell applications.

Multiple Broadband Infrared Topological Photonic Crystal Valley States Based on Liquid Crystals.

Spectral tunable technology has to meet the requirements of strong robustness and wide spectral range. We propose a method for the transmission and manipulation of infrared topological photonic crystal valley states based on tunable refractive index method that exhibits broad-spectrum and multi-band characteristics, along with a tunable emission angle. With this structure, different rotational directions of vortex light sources can independently excite the K valley and K' valley within the frequency band ranging from 75.64 THz to 99.61 THz. At frequencies from 142.60 THz to 171.12 THz, it is possible to simultaneously excite both the K valley and K' valley. The dual refractive index tunable design allows for the adjustment of the emission angle at a fixed frequency, enabling control over the independent excitation of either a single K valley or K' valley, as well as their simultaneous excitation. This capability has significant implications for photonic computation and tunable filtering, offering enhanced operational flexibility and expanded functionality for future optical communications and integrated optical circuits.

Rare-Earth Chalcogenides: An Inspiring Playground For Exploring Frustrated Magnetism

Abstract The rare-earth chalcogenide $ARECh_{2}$ family ($A =$ alkali metal or monovalent ions, $RE =$ rare earth, $Ch =$ chalcogen) has emerged as a paradigmatic platform for studying frustrated magnetism on a triangular lattice. The family members exhibit a variety of ground states, from quantum spin liquid to exotic ordered phases, providing fascinating insight into quantum magnetism. Their simple crystal structure and chemical tunability enable systematic exploration of competing interactions in quantum magnets. Recent neutron scattering and thermodynamic studies have revealed rich phase diagrams and unusual excitations, refining theoretical models of frustrated systems. This review provides a succinct introduction to $ARECh_{2}$ research. It summarizes key findings on crystal structures, single-ion physics, magnetic Hamiltonians, ground states, and low-energy excitations. By highlighting current developments and open questions, we aim to catalyze further exploration and deeper physical understanding on this frontier of quantum magnetism.

Effect of the position of Mg replacing Ni on O3-NaNi1/3Fe1/3Mn1/3O2 on the structural stability of cathode materials

O3-NaNi1/3Fe1/3Mn1/3O2 (NaNFM) materials are susceptible to complex phase transitions during electrical cycling leading to poor structural, capacity retention and multiplicity properties. These drawbacks hinder the application of NaNFM in sodium-ion batteries. Here, Mg2+ with larger ionic radius was used to dope its transition metal layer Ni site. The effects of Mg2+ doped NaNFM crystal structure and transition metal valence states on its electrochemical properties were investigated by XRD, SEM, and XPS. The capacity retention of NaNMFM-0.02 (84.05 %) was higher than that of NaNFM (73 %) after 200 cycles of the material at 5C. In addition, NaNMFM-0.02 achieved a first discharge specific capacity of 146.5 mAh/g at high voltage. Based on structural and electrochemical analyses, this improvement is attributed to the fact that magnesium acts as a “pillar” to stabilize the crystal structure of NaNFM, while magnesium doping reduces the Jahn-Teller effect. As a result, the material has better electrochemical properties.

Plastic deformation of [001]-oriented single-crystal iron under shock compression: Effects of void size

The thermomechanical behavior of materials is known to be sensitive to preexisting defects in their microstructure. In this paper, non-equilibrium molecular dynamics simulations have been used to investigate the effects of the microvoid size on the plastic deformation in single-crystal iron shock-compressed along the [001] crystallographic direction. The higher the microvoid radius, the faster the kinetics of dislocations. Thus, as the microvoid radius increases, the plastic activity evolves from a regime where the deformation is dominated by twin activities to a regime where both twin and dislocation activities play an essential role and then to a regime where the deformation is dominated by dislocation slip. Furthermore, in both defect-free and defective initial crystal states, the elastic precursor wave is observed to decay with propagation distance, resulting in a constitutive functional dependence of the yielding pressure, σE, on the plastic deformation rate, ε˙p. In the regime where both deformation twinning and dislocation slip play important roles, the constitutive behavior is consistent with the original Swegle–Grady model and is in overall agreement with experimental data and thermomechanical simulations.

Dual-band large-area topological edge states and higher-order corner states in a valley Hall photonic crystal

Dual-band large-area topological edge states and higher-order corner states in a valley Hall photonic crystal

Oriented crystalline structure in melt-drawn ultrahigh-molecular-weight polyethylene induced by entanglement networks

In this study, we focused on the unique structure with oblique periodicity formed by the melt-drawing of metallocene-catalyzed ultrahigh-molecular-weight polyethylene (UHMW-PE) to clarify the relationship between tight entanglements that cannot be disentangled during melt-drawing and the formation of the periodic structure. In situ X-ray measurements during the heating of the melt-drawn UHMW-PE film revealed that the disappearance of the characteristic oblique streaks that appeared tilted from the drawing direction and the orthorhombic-to-hexagonal phase transition occurred simultaneously, suggesting that the change in the tension state of extended-chain crystals due to the orthorhombic-to-hexagonal phase transition and the disappearance of order in the structure resulting in oblique streaks are related behaviors. This indicates the presence of the network structure including oriented amorphous chains in which molecular chains are fixed by tight entanglements in metallocene-catalyzed UHMW-PE melt-drawn film.

Topological edge states of acoustic zigzag tubes with triangle scatterers

Tubular geometries in phononic crystals have the advantages of hosting topological edge states without breaking the underlying symmetry of the lattice. The topological relationships between the acoustic zigzag tubes and the dispersion relation of the planar phononic crystal with a zigzag edge boundary are theoretically revealed through 2D k space analysis, circumferential pressure analysis, and lattice symmetry analysis. New cutting lines of the tubes are obtained, which link the winding number of the tubes with the dispersion relation of topological edge states in the planar phononic crystal. The eigenstates analysis shows that the circumferential periodic number of a tubular edge state is regular and corresponds to a specific wavenumber in the circumferential direction. On the basis of the unveiled topological relationships, tubular edge states with tunable properties are obtained by controlling the characteristic length of the boundary scatterers. Moreover, the tubular edge states are confirmed to be highly confined and robust along the designed transmission channel. This study may present a new way to design acoustic tubes with tunability and have potential applications in robust wave propagation and miniaturized phononic devices.

In-situ preparation of lanthanide luminescent MOF hydrogel for aldehyde detection☆

Metal-organic frameworks (MOFs) usually exist in the state of powder or crystal. When they are exposed to hydrophilic solvents, their structure will change and become unstable. Therefore, it is a challenge to construct MOF materials with tunable mechanical properties. Herein, we report in-situ growth lanthanide metal-organic framework (LnMOF) in sodium alginate (SA) and polyvinyl alcohol (PVA) hydrogel matrix. The prepared composite hydrogel not only displays characteristic lanthanide narrow-band emission under ultraviolet light, but also demonstrates excellent mechanical properties. The addition of LnMOF significantly enhances the compressive strength of the hydrogel (from 0.75 to 7.32 MPa). Furthermore, the composite hydrogel shows highly selective recognition of glutaraldehyde and gaseous formaldehyde at room temperature. The detection limits (LOD) of SP-EuMOF for glutaraldehyde and formaldehyde are 0.27 and 0.22 ppm, respectively. Based on these results, the LnMOF composite hydrogel is deemed to have significant potential as a fluorescent sensor for both glutaraldehyde and formaldehyde detection.

Investigations on the effect of arsenic and phosphorus atomic exchange on the origin of crystal potential fluctuations in InAsP/InP epilayers

The study investigates the anion exchange mechanism between the ad-atoms of arsenic and phosphorus followed by their inter-diffusion processes, in InAsP/InP hetero-structures grown by metal organic vapor phase epitaxy technique. The energetics and kinetics of the ad-atoms like arsenic and phosphorus are governed by the growth conditions. It has been found that the percolation of arsenic and phosphorus in the epilayer depends on various factors, such as gas-phase diffusion coefficients, surface reaction rates, misfit strain energy, bond energy, segregations, and the presence of defects and dislocations. Effects of anion exchange mechanisms on generating local crystal potential states that originated due to the local crystal bonding environment are further investigated. The magnitude of these local potential states strongly depends on the strain states associated with the layer thickness. If the difference between the potential minima is small (< 25 meV), it leads to distinct “S” shaped temperature-dependent luminescence/absorption spectra. In contrast, a large difference gives rise to two distinctive luminescence/absorption peaks. Thus, by controlling the strain states associated with the energetics and kinetics of ad-atoms like arsenic/phosphorus and layer thickness, such “S” shaped behavior can be controlled.

Thermal and sublimation properties of cardiovascular drugs sotalol and ivabradine hydrochlorides

The saturated vapor pressure of sotalol and ivabradine hydrochlorides was measured in the temperature range (413.15–437.15) K by the transpiration method. The sublimation thermodynamic functions (Gibbs energy, enthalpy and entropy) of the compounds were calculated from the temperature dependencies of saturated vapor pressure. The standard molar enthalpy of sublimation for sotalol and ivabradine hydrochlorides is (157.5 ± 1.4) kJ·mol−1 and (143.2 ± 1.2) kJ·mol−1, respectively. The thermal properties and crystal state of the drugs were studied by the DSC, TG/DTG and X-ray diffraction methods.

Continuous Space-Time Crystal State Driven by Nonreciprocal Optical Forces.

We show that the continuous time crystal state can arise in an ensemble of linear oscillators from nonconservative coupling via optical radiation pressure forces. This new mechanism comprehensively explains observations of the time crystal state in an array of nanowires illuminated with light [T. Liu et al., Nat. Phys. 19, 986 (2023).NPAHAX1745-247310.1038/s41567-023-02023-5]. Being fundamentally different from regimes of nonlinear synchronization, it has relevance to a wide range of interacting many-body systems, including in the realms of chemistry, biology, weather, and nanoscale matter.

Study on the mechanism of ROS-induced oxidative stress injury and the broad-spectrum antimicrobial performance of nickel ion-doped V6O13 powder

In this study, pure V6O13 and nickel ion-doped V6O13 powders were synthesized by a simple hydrothermal-calcination method, and their broad-spectrum antimicrobial properties and mechanisms were investigated. The crystal structure, morphology, and chemical state of the powders were thoroughly analyzed by XRD, SEM, TEM, XPS, and UV–Vis. Their antimicrobial properties and mechanisms were evaluated by the ring of inhibition, bio-SEM, live-dead cell staining, ROS detection, and protein leakage experiments. The results showed that nickel ion doping modulated the oxygen defects of V6O13, generating more reactive oxygen species and leading to more severe oxidative stress, resulting in a broad-spectrum and highly efficient antimicrobial effect. This study also revealed the antimicrobial mechanism based on oxygen defect -induced ROS production, which caused cellular oxidative stress damage, leading to leakage of intracellular substances and cell death. This study not only demonstrates the potential of V6O13 as an efficient antimicrobial agent but also provides a strong experimental basis and theoretical support for the engineering design and optimization of novel antimicrobial materials by modulating material defects through ion doping.

Organic Materials with Ultrabright Phosphorescence at Room Temperature under Physiological Conditions for Bioimaging.

In contrast to the high efficiency of room temperature phosphorescence in crystal states, the generally utilized nanoparticles of organic materials in bioimaging demonstrated sharply decreased performance by orders of magnitude under physiological conditions, badly limiting the realization of their unique advantages. This case, especially for organic red/near-infrared (NIR) phosphorescence materials, is not only the challenge present in reality but more importantly, for the theoretical problem of deeply understanding and avoiding the quenching effect by oxygen and water toward excited triplet states. Herein, thanks to the intelligent molecular design by the introduction of abundant hydrophobic chains and highly-branched structures, bright and persistent red/NIR phosphorescence under physiological conditions has been realized, which demonstrated the shielding effect towards oxygen, and strengthened the intermolecular interactions to suppress the non-radiative transitions. Accordingly, the record phosphorescence intensity of nanoparticles in bioimage, up to 8.21 ± 0.36 × 108 p s-1 cm-2 sr-1, was achieved, to realize the clear phosphorescence imaging of liver and tumors in living mice, even lymph nodes in rabbit models with high SBRs. This work afforded an efficient way to achieve the bright red/NIR phosphorescence nanoparticles, guiding their further applications in biology and medicine.