Cell Volume Expansion Research Articles

Ion-intercalation mechanism and structural relaxation in layered iron phosphate Na3Fe3(PO4)4 cathodes

Layered Na3Fe3(PO4)4 can function as a positive electrode for both Li- and Na-ion batteries and may hold advantages from both classical layered and phosphate-based electrode materials. Using a combination of ex-situ and operando synchrotron radiation powder X-ray diffraction, void space analysis, and Mössbauer spectroscopy, we herein investigate the structural evolution of the Na3Fe3(PO4)4 framework during Li- and Na-ion intercalation. We show that during discharge, Li- and Na-intercalation into Na3Fe3(PO4)4 occurs via a solid solution reaction wherein Na-ions appear to be preferentially intercalated into the intralayer sites. The intercalation causes an expansion of the unit cell volume, however at open circuit conditions after ion-intercalation (i.e., after battery discharge), Na3+xFe3(PO4)4 and LixNa3Fe3(PO4)4 undergo a structural relaxation, wherein the unit volume contracts below that of the pristine material. Rietveld refinement suggests that the ions intercalated into the intra-layer sites diffuse to the sites in the inter-layer space during the relaxation. This behavior brings new perspectives to understanding structural relaxation and deviations between structural evolution observed under dynamic and static conditions.

Origin of the metamagnetic transitions in Y0.9Tb0.1Fe2D4.3

Deuterium insertion was used to tune the magnetic properties of Y0.9Tb0.1Fe2 Laves phase towards an itinerant electron metamagnetic (IEM) behavior. The latter is highly sensitive to chemical changes and external parameters. The structural and magnetic properties of Y0.9Tb0.1Fe2D4.3 were investigated using various neutron powder diffraction experiments in addition to magnetic measurements under steady and pulsed high magnetic fields up to 60 T. The deuteride crystallizes in a monoclinic structure (Pc space group) with 4.3 D atoms located in 18 tetrahedral interstitial sites. At zero field, it undergoes a ferrimagnetic-antiferromagnetic (FiM-AFM) transition at TM0 = 90 K, accompanied by an anisotropic magnetostriction and a negative cell volume expansion of 0.6 %. A second AFM-PM transition is observed at 146 K. Under pulsed magnetic field at 4.2 K, the deuteride displays a multistep magnetic behavior from ferrimagnetic to a ferromagnetic state, which can be attributed to a stepwise rotation of the Tb moments. The ZFC-FC magnetization curves at low fields exhibit an irreversibility below 90 K, followed by a sharp decrease in magnetization at the FM-AFM transition. Between 90 K and 130 K, the magnetization curves display an IEM behavior, with the transition field increasing linearly with temperature.

Hydrogenation of calcite and change in chemical bonding at high pressure: Diamond formation above 100 GPa

Synchrotron X-ray diffraction (XRD) and Raman spectroscopy in laser heated diamond anvil cells and first principles molecular dynamics (FPMD) calculations have been used to investigate the reactivity of calcite and molecular hydrogen (H2) at high pressures up to 120 GPa. We find that hydrogen reacts with calcite starting below 0.5 GPa at room temperature forming chemical bonds with carbon and oxygen. This results in the unit cell volume expansion; the hydrogenation level is much higher for powdered samples. Single-crystal XRD measurements at 8–24 GPa reveal the presence of previously reported III, IIIb, and VI calcite phases; some crystallites show up to 4% expansion, which is consistent with the incorporation of ≤ 1 hydrogen atom per formula unit. At 40–102 GPa XRD patterns of hydrogenated calcite demonstrate broadened features consistent with the calcite VI structure with incorporated hydrogen atoms. Above 80 GPa, the CO stretching mode of calcite splits suggesting a change in the coordination of CO bonds. Laser heating at 110 GPa results in the formation of CC bonds manifested in the crystallization of diamond recorded by in situ XRD at 300 K and 110 GPa and by Raman spectroscopy on recovered samples commenced with C13 calcite. We explored several theoretical models, which show that incorporation of atomic hydrogen results in local distortions of CO3 groups, formation of corner-shared CO polyhedra, and chemical bonding of H to C and O, which leads to the lattice expansion and vibrational features consistent with the experiments. The experimental and theoretical results support recent reports on tetrahedral C coordination in high-pressure carbonate glasses and suggest a possible source of the origin of ultradeep diamonds.

A DFT insight of the electronic, thermodynamic, and thermoelectric properties of RuO2

In this study, we explore the structural, electronic, thermodynamic, and thermoelectric properties of RuO2 using density functional theory. The derived equilibrium structural parameters agree with other theoretical and experimental results. The widely used modified Becke–Johnson (mBJ-GGA) potential is adopted for accurate electronic band gap estimation. To incorporate the effect of the extended orbital of the Ru atom, spin-orbit coupling has been used in combination with the mBJ potential. The investigation of electronic properties revealed an indirect semi-conducting nature with a band gap along the W-L symmetry. The calculated band gaps are 1.685 and 1.658 eV from mBJ and mBJ + SOC, respectively. The dynamical stability is tested and verified by calculating the phonon dispersion curve. We have employed the quasiharmonic approximation-based Gibbs2 package to determine the pressure and temperature-dependent thermodynamical parameters, such as cell volume, Debye temperature, heat capacity, entropy, and thermal expansion coefficient. This study uses the BoltzTraP simulation algorithm to determine the thermoelectric parameters such as the Seebeck coefficient, electrical conductivity, and thermal conductivity.

Effects of H-doping in Y2Fe17 compounds on the structure, magnetic properties, and Mössbauer effect

We introduce a novel water bath hydrogenation process designed to enhance the magnetic properties and hyperfine field of Y2Fe17. The core of this process lies in the successful preparation of a new compound Y2Fe17H3.5 by introducing hydrogen in a mild water bath environment, accomplished by a chemical reaction between calcium, Y2Fe17, and ammonium acetate solution at room temperature and pressure. After hydrogen doping, cell volume expansion increased from 778.511 to 795.383 Å3, and notably, lattice expansion is anisotropic. Furthermore, saturation magnetization is increased from 103 to 134.93 emu/g, Curie temperature is increased from 320 to 461 K, and the average hyperfine field is increased from 18 to 25 T. The improvement in magnetic properties is due to the increase in Fe–Fe distance, which according to the Bethe–Slater curve leads to stronger Fe–Fe exchange interactions and enhancing ferromagnetic interactions. This work not only proposes the novel rhombohedral Y2Fe17H3.5 with excellent magnetic properties, but also provides a new method for hydrogen doping in Y2Fe17 which lays the foundation of fundamental solid state physics for further research.

PbbHLH137 interacts with PbGIF1 to regulate pear fruit development by promoting cell expansion to increase fruit size.

The regulation of fruit development is a complex process and a core issue in the fruit tree industry. To investigate the role of PbGIF1 in pear fruit development, we identified a transcription factor PbbHLH137 that regulates pear (Pyrus bretschneideri) fruit development by screening a yeast library constructed from fruit cDNA. Yeast two-hybrid (Y2H), bimolecular fluorescence complementation (BiFC), and split luciferase complementation (split-LUC) assays were performed to confirm the PbbHLH137-PbGIF1 interaction. By tracing the complete fruit development process, we found that PbbHLH137 expression was closely related to fruit size and highly involved at the late pear fruit development stage. Transgenic experiments showed that heterologous expression of PbbHLH137 or PbGIF1 promoted fruit enlargement. PbbHLH137 promoted mainly the expansion of fruit cell volume, whereas PbGIF1 mainly increased the number of cells. Further LUC experiments demonstrated that PbGIF1 promoted the transcriptional activation ability of PbbHLH137. Our work identified PbbHLH137 as a transcription factor that regulates fruit development, and showed that PbGIF1 played an ongoing role during fruit development, making it a candidate gene for genetic improvement of pear fruit development.

Magnetic properties and microstructure of Ti-doped Sm-Fe-N synthesized by reduction diffusion process

Iron-rich intermetallic compound Sm2Fe17N3 is considered to be a highly promising candidate for new-generation permanent magnetic materials. Here, the Ti-substituted Sm2(Fe, Ti)17N3 alloys were synthesized using reduction-diffusion and nitridation. The microstructure and magnetic properties of Sm2(Fe, Ti)17 and its nitrides, in relation to the effect of Ti substitution, were systematically investigated through a comprehensive experimental approach combined with first-principles calculations. It was revealed that the Ti substitution is very effective in particle refinement of Sm2(Fe, Ti)17. The Rietveld analysis of X-ray data demonstrated an expansion in the unit cell volume of Sm2(Fe, Ti)17 phase with increasing Ti content. Subsequent nitridation experiments highlighted the beneficial impact of an appropriate Ti addition on the enhancement of both coercivity and remanence in Sm2(Fe, Ti)17N3 magnetic powder. The highest coercivity of 8.9 kOe was achieved in the sample with a Ti/Fe mole ratio of 0.04. Furthermore, the possible crystallographic occupancy of Ti and its effect on the phase stability are investigated using first-principles calculations. Our results indicated that the phase stability is influenced by the synergistic effect of Ti substitution atoms and interstitial N atoms. The significance of this study lies in its implications for the development of advanced permanent magnetic materials through reduction-diffusion technology.

Strain-driven high energy storage in BaTiO3-based lead-free epitaxial thin films

In this work, the epitaxial 0.85BaTiO3-0.15Bi(Mg1/2Ti1/2)O3 (BT-BMT) films with large compressive strain were fabricated on SrTiO3 (001). The expansion of the unit cell volume and out-of-plane lattice parameter and the large built-in electric field (Ebi) in BT-BMT films indicate the existence of defect dipoles. It was found that the polarization and the breakdown strength can be optimized by the strain and the defects, respectively. Ultimately, a desirable energy density of 90.3 J/cm3 with efficiency of 62.3% was achieved. It suggests that strain can serve as a practical means to modulate the energy storage performance of ferroelectric epitaxial film capacitors.

Improving photovoltaic characteristics of CdS-based hybrid solar cells through Mn incorporation

CdS thin films, both with and without Mn-doping, were grown via chemical bath deposition on indium tin oxide-coated glass substrates for application in hybrid solar cells. X-ray diffraction analysis revealed that Mn doping led to a deterioration in the crystal quality of CdS samples, evidenced by increased microstrain and dislocation density. Mn atoms were interstitially incorporated into the CdS structure, resulting in an expansion of the unit cell volume. Morphological analysis indicated a decrease in grain size from 390 nm to 140 nm for 0 % and 2 % Mn-doped CdS samples, respectively, while maintaining the spherical shape of the CdS thin films. Mn doping also increased the transmittance of CdS thin films, with the highest transparency of 95 % at 580 nm achieved for the 2 % Mn-doped CdS sample. In comparison to undoped CdS (2.38 eV), the band gap of CdS samples initially decreased to 1.84 eV for 1 % Mn doping but significantly increased to 3.03 eV for 2 % Mn-doped CdS. Photoluminescence (PL) data indicated that 2 % Mn-doped CdS thin films exhibited the lowest peak intensity, suggesting that a high concentration of Mn atoms caused non-radiative charge recombination. Additionally, efficient exciton dissociation was observed between CdS:Mn and P3HT:PCBM (poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl C61-butyric acid methyl ester (PCBM)) layers in the 2 % Mn-doped CdS-based device, as per the PL results. Photovoltaic measurements demonstrated that compared to undoped CdS, 2 % Mn doping increased the power conversion efficiency of the CdS-based device from 0.070 % to 0.202 %, indicating an almost threefold increase in hybrid solar cell efficiency. This improvement is likely attributed to the development of a better interface between the CdS:Mn and P3HT:PCBM layers.

Optimizing the White Light Emission of Pr3+ Activated SrCeO3 Perovskite by Controlling the Excitation Wavelength for High CRI wLED Applications.

The current research illustrates excitation energy-triggered photoluminescent characteristics of Pr3+ions in SrCeO3 providing a practical approach for developing high CRI wLED and its applications. SrCeO3: xPr3+ (x = 0, 0.005, 0.01, 0.02, 0.03 wt) perovskites synthesized by fuel excess gel combustion method generate high CRI (~98) for wLED applications. Crystalline phosphors with orthorhombic structures having space group Pnma were confirmed by XRD. The unit cell volume expansion occurred with an increase in Pr3+ concentration was verified through the Rietveld refinement technique. Surface morphology, particle distribution, and size were observed via FE-SEM imaging, and detected a well-defined regular distorted spherical structure with average grain size 0.826μm for Pr3+ doped SrCeO3. Elemental mapping and EDS analysis identified the uniform distribution and elemental purity of SrCeO3: 0.01 Pr3+. Further, the molecular vibrations and modes were analyzed from the Raman spectrum. Moreover, the average particle size assessed via TEM analysis was found to be ~83.2nm, consistent with XRD analysis. UV-visible absorption spectra for optical energy-band gap analysis showed a decrease in band gap energy with an increase in Pr3+ concentration, realizing an effective energy transfer from Ce4+ to Pr3+. PL measurements showed a huge variety of emission transitions, corresponding to excitations 290nm, 321nm, 373nm, and 449nm. The critical dopant concentration instigated by concentration quenching was 1 wt% Pr3+, ascribed to dipole-dipole interaction. The fluorescence lifetime of the optimal sample was 4.835μs. Commission International de I'Eclairage (CIE) diagram exposes the white light emanation of SrCeO3: Pr3+. Among which white light with high CRI (~98) and comparably low CCT (~6311K) was obtained for SrCeO3: 0.01 Pr3+ at 373nm excitation. The obtained results recommend that SrCeO3: Pr3+ perovskite as an efficient white phosphor for fabricating high-performance wLEDs.

Radical Cation Salts of Hetera‐Buckybowls: Polar Crystals, Negative Thermal Expansion and Phase Transition

AbstractRadical cation salts of π‐conjugated polycycles are rich in physical properties. Herein, two kinds of hetera‐buckybowls, ethoxy‐substituted trithiasumanene (3SEt) and triselenasumanene (3SeEt), are synthesized as electron donors. Galvanostatic oxidation of them affords radical cation salts (3SEt)5(TTFMPB)3, (3SeEt)5(TTFMPB)3, (3SEt)4PMA, and (3SeEt)4PMA, where PMA is Keggin‐type phosphomolybdate and TTFMPB is tetrakis[3,5‐bis(trifluoromethyl)‐phenyl]borate. In these salts, 3SEt/3SeEt are partially charged and show distinct conformation change with the site charge and counter anions. In TTFMPB salts, (TTFMPB)− forms hexagonal channels that accommodate the packing columns of 3SEt/3SeEt. In particular, (3SEt)5(TTFMPB)3 adopts the R3c space group and is a polar crystal with the columns of 3SEt all in the up‐bowl direction. The PMA salts of 3SEt/3SeEt are polar crystals (C2 space group) with 3SEt/3SeEt being planar and forming columnar stacks. (3SeEt)4PMA shows a structural modulation below 200 K, namely, negative thermal expansion (NTE) of the unit cell volume and enlargement of the intermolecular distances between neighboring 3SeEt molecules. The four salts are semiconductors with an activation energy of 0.18–0.38 eV. The conductivity of (3SeEt)4PMA shows a reversible transition upon cooling and heating, in accordance to the NTE structural modulation. This work paves the way toward conducting materials based on hetera‐buckybowls.

Radical Cation Salts of Hetera-Buckybowls: Polar Crystals, Negative Thermal Expansion and Phase Transition.

Radical cation salts of π-conjugated polycycles are rich in physical properties. Herein, two kinds of hetera-buckybowls, ethoxy-substituted trithiasumanene (3SEt) and triselenasumanene (3SeEt), are synthesized as electron donors. Galvanostatic oxidation of them affords radical cation salts (3SEt)5 (TTFMPB)3 , (3SeEt)5 (TTFMPB)3 , (3SEt)4 PMA, and (3SeEt)4 PMA, where PMA is Keggin-type phosphomolybdate and TTFMPB is tetrakis[3,5-bis(trifluoromethyl)-phenyl]borate. In these salts, 3SEt/3SeEt are partially charged and show distinct conformation change with the site charge and counter anions. In TTFMPB salts, (TTFMPB)- forms hexagonal channels that accommodate the packing columns of 3SEt/3SeEt. In particular, (3SEt)5 (TTFMPB)3 adopts the R3c space group and is a polar crystal with the columns of 3SEt all in the up-bowl direction. The PMA salts of 3SEt/3SeEt are polar crystals (C2 space group) with 3SEt/3SeEt being planar and forming columnar stacks. (3SeEt)4 PMA shows a structural modulation below 200 K, namely, negative thermal expansion (NTE) of the unit cell volume and enlargement of the intermolecular distances between neighboring 3SeEt molecules. The four salts are semiconductors with an activation energy of 0.18-0.38 eV. The conductivity of (3SeEt)4 PMA shows a reversible transition upon cooling and heating, in accordance to the NTE structural modulation. This work paves the way toward conducting materials based on hetera-buckybowls.

The relationship between reinforcement ratio and e-beam irradiation in Y2O3 reinforced Al6061 Alloys: A crystallographic assessment

The e-beam irradiation effect is investigated on mechanically alloyed Y2O3-Al6061 composites with different reinforcement ratios (0.25, 2, 6 % wt.). Uniform dispersion of reinforcement elements in the Al matrix is achieved according to SEM and EDS analysis in conjunction with the formation of a highly dense structure. Improvement in hardness value is observed by increasing both the amount of reinforcement species and irradiation dose, concomitantly. The samples are irradiated with 6 MeV and 18 MeV electrons, along with 2, 4, and 6 kGy radiation amounts. 6 MeV radiation has minimal effect on alloys and samples preserve structural integrity. However, electron irradiation with 18 MeV energy shows a distinguished influence on Y2O3-reinforced alloys by initiating defects and defect clusters in samples and eventually leading to expansion in unit cell volume. Finally, it is important to state that the 6 % Y2O3-Al6061 materials system is more suitable for applications where e-beam irradiation is used.

Structure and bonding in TiNiSi type LaMgSnH intermetallic hydride

The work was aimed on reaching a better understanding of the effect of magnesium as a component of the hydride-forming LaMgSn intermetallic compound crystallising with the orthorhombic TiNiSi type of structure on the hydrogenation behaviours, crystal structure and bonding interactions with hydrogen. The LaMgSn structure is significantly expanded as compared to the earlier studied isotypic LaNiSn H storage material (volume expansion of 23%), as a result of a substitution of the smaller Ni atoms by much larger Mg atoms. This significantly affects the chemistry of the interaction of the intermetallic compound with hydrogen because a transition metal, Ni, in replaced by an active hydride-forming metal, Mg. The work involved computational studies of the electronic structure of the intermetallic compound and its hydride, and experimental studies of the hydrogenation behaviour and thermal stability of the formed hydride LaMgSnH, its structural characterisation by SR XRD and neutron powder diffraction, and Mössbauer spectroscopic studies of the stannide and its hydride. These studies showed that in the system LaMgSn-H2 a monohydride LaMgSnH is a thermodynamically favourable hydride composition. PDOS levels show that hydrogen and all constituting elemental metals, La, Mg and Sn, have peaks of electron density in the range between − 6 and − 4 eV indicating their hybridisation. The results show the hybridization of H atoms not only with bonded La and Mg atoms forming H-filled tetrahedra La3Mg, but also with Sn despite its atoms do not have bonding interactions with H. This explains the high stability of the metal substructure which does not disproportionate into the binary hydrides of La and Mg even when heated to 200 °C @ 20 bar H2, but instead forms an insertion type hydride. Formation of the monohydride LaMgSnH (Sp.gr. Pnma; a=8.1628(4); b= 4.5555(3); c= 9.2391(5) Å; V= 343.56(5) Å3) causes a small (1.26%) expansion of the unit cell volume compared to LaMgSn, and mainly proceeds along the [100] direction. Hydrogen absorption-desorption cycle results in a reversible formation of the initial compound LaMgSn, with the peak of hydrogen release occurring in vacuum at 355 °C, which is intermediate between the temperatures for the vacuum decomposition of the dihydrides MgH2 and LaH2. From the combined refinements of the Synchrotron (SR) XRD and Neutron Powder Diffraction (NPD) data, deuterium atoms completely and in an ordered way fill a half of the available La3Mg interstitial sites with metal-H/D distances of Mg-D= 2.026 Å; La-D= 2.381 and 2.502 Å. The occupied La3Mg sites are smaller in size than the vacant Mg3La tetrahedra. Sn and D exhibit a nonbonding interaction with the closest Sn-D separation of 3.033 Å. 119Sn Mössbauer spectra of LaMgSn and LaMgSnH show isomer shifts of 1.98(2) and 1.99(1) mm/s which are typical for the chemically similar stannides.

Halide ions doped SrMnO3 for chemical looping oxidative dehydrogenation of ethane

AbstractThe chemical looping oxidative dehydrogenation (CL‐ODH) of ethane represents a highly effective approach for converting ethane into the value‐added product ethylene. This investigation focused on the synthesis of SrMnO3 and its halide ions doped derivatives (SrMnO3Cl and SrMnO3Br) through the sol‐gel method. The performance of these perovskites, employed as oxygen carriers in CL‐ODH of ethane, was explored. The results unveiled several advantageous outcomes arising from the incorporation of halide ions (Cl− and Br−) with larger radius into the oxygen sites of the SrMnO3 perovskite. Halide ions doping notably induced cell volume expansion and enhanced lattice fringe spacing. Furthermore, it contributed to elevated oxygen vacancy concentration, increased Mn4+/Mn3+ molar ratio, and improved oxygen ions mobility within the bulk lattice. Fixed‐bed experiments demonstrated that these redox catalysts, doped with halide ions, exhibited outstanding activity and stability during cycling tests, exhibiting enhanced both ethylene selectivity and yield in CL‐ODH of ethane. In summary, the introduction of halide ions into SrMnO3 emerges as a promising strategy for enhancing the performance of CL‐ODH in ethane conversion for SrMnO3 based oxygen carriers. © 2023 Society of Chemical Industry and John Wiley & Sons, Ltd.

Regulation of haemoglobin concentration at high altitude.

Lowlanders sojourning for more than 1 day at high altitude (HA) experience a reduction in plasma volume (PV) that increases haemoglobin concentration and thus restores arterial oxygen content. If the sojourn extends over weeks, an expansion of total red cell volume (RCV) occurs and contributes to the haemoconcentration. While the reduction in PV was classically attributed to an increased diuretic fluid loss, recent studies support fluid redistribution, rather than loss, as the underlying mechanism. The fluid redistribution is presumably driven by a disappearance of proteins from the circulation and the resulting reduction in oncotic pressure exerted by the plasma, although the fate of the disappearing proteins remains unclear. The RCV expansion is the result of an accelerated erythropoietic activity secondary to enhanced renal erythropoietin release, but a contribution of other mechanisms cannot be excluded. After return from HA, intravascular volumes return to normal values and the normalisation of RCV might involve selective destruction of newly formed erythrocytes, although this explanation has been strongly challenged by recent studies. In contrast to acclimatised lowlanders, native highlanders originating from the Tibetan and the Ethiopian plateaus present with a normal or only mildly elevated haemoglobin concentration. Genetic adaptations blunting the erythropoietic response to HA exposure have been proposed as an explanation for the absence of more pronounced haemoconcentration in these populations, but new evidence also supports a contribution of a larger than expected PV. The functional significance of the relatively low haemoglobin concentration in Tibetan and Ethiopian highlanders is incompletely understood and warrants further investigation.

Effect of Nickel doping on the Structural, Optical, and electrical properties of titanium dioxide thin films for the application of sensing devices

Thin films of pristine titanium dioxide (TiO2) and doped with different concentrations (0–8) at.% of nickel (Ni) were synthesized onto transparent glass substrates using the spray pyrolysis deposition technique. Field emission scanning electron microscopy revealed the porous and agglomerated surface morphology of the films. X-ray diffractometer demonstrated the anatase crystal structure with a nominal increment of (101) peak. The shifting of peak position revealed the expansion of the unit cell volume from 134.64 to 137.54 (Å)3 whereas crystallite size increased from 34 to 63 nm. Using the Fizeau fringes technique, the thickness of the films was determined between 165 and 190 nm. UV–Vis measurements were employed to examine the optical characteristics of the films. The red shift was observed for 2 at.% Ni content (3.38 eV) while the blue shift was observed for (4–8) at.% Ni content. The wavelength-dependent refractive index and dielectric constant showed anomalous dispersion in the absorption band, representing the transparency of the films. The 4-point probe measurement showed a decreasing trend of resistivity with increasing temperature, whereas the resistivity increased with Ni content. Activation energy indicated a higher amount of adsorbed oxygen in the films due to the high amount of Ni content.

Cell volume expansion and local contractility drive collective invasion of the basement membrane in breast cancer.

Breast cancer becomes invasive when carcinoma cells invade through the basement membrane (BM)-a nanoporous layer of matrix that physically separates the primary tumour from the stroma. Single cells can invade through nanoporous three-dimensional matrices due to protease-mediated degradation or force-mediated widening of pores via invadopodial protrusions. However, how multiple cells collectively invade through the physiological BM, as they do during breast cancer progression, remains unclear. Here we developed a three-dimensional in vitro model of collective invasion of the BM during breast cancer. We show that cells utilize both proteases and forces-but not invadopodia-to breach the BM. Forces are generated from a combination of global cell volume expansion, which stretches the BM, and local contractile forces that act in the plane of the BM to breach it, allowing invasion. These results uncover a mechanism by which cells collectively interact to overcome a critical barrier to metastasis.

New BaTi0.96Cu0.02X0.02O3 (X = V, Nb) Photocatalysts for Dyes Effluent Remediation: Broad Visible Light Response

The problem of industrial dyes depollution has pushed the scientific research community to identify novel photocatalysts with high performance. Herein, new photocatalysts composed of BaTiO3, BaTi0.96Cu0.04O3, BaTi0.96Cu0.02V0.02O3 and BaTi0.96Cu0.02Nb0.02O3 powders were prepared by solid-state reaction. The structural analysis of the samples confirmed the formation of the BaTiO3 structure. The splitting of (002) and (200) planes verified the formation of the tetragonal phase. The XRD peaks shifted, and the unit cell volume expansion verified the substitution of the Ti4+ site by Cu2+, V4+ and Nb5+ ions. The morphological measurements showed that the addition of (Cu, V) and (Cu, Nb) ions changes the particles’ morphology of BaTiO3, reducing its grains size. After the incorporation of (Cu, V) and (Cu, Nb) ions, the band gap of BaTiO3 was reduced from 3.2 to 2.84 and 2.72 eV, respectively. The modification of BaTiO3 by (Cu, Nb) ions induced superior photocatalytic properties for methyl green and methyl orange with degradation efficiencies of 97% and 94% during 60 and 90 min under sunlight irradiation, respectively. The total organic carbon results indicated that the BaTi0.96Cu0.02Nb0.02O3 catalyst has a high mineralization efficiency. In addition, it possesses a high stability during three cycles. The high photodegradation efficiency of Bi0.96La0.02Gd0.02FeO3 was related to the wide-ranging visible light absorption.

Unconventional electronic phase transition in SnBi2Te4: role of anomalous thermal expansion.

We propose SnBi2Te4to be a novel topological quantum material exhibiting temperature (T) mediated transitions between rich electronic phases. Our combined theoretical and experimental results suggest that SnBi2Te4goes from a low-Tsemimetallic phase to a high-T(room temperature) insulating phase via an intermediate metallic phase. Single crystals of SnBi2Te4are characterized by various experimental probes including synchrotron based x-ray diffraction, magnetoresistance, Hall effect, Seebeck coefficient and magnetization. X-ray diffraction data confirms an anomalous thermal expansion of the unit cell volume below ∼100 K, which significantly affects the bulk band structure and hence the transport properties. Simulated surface states are found to be topologically robust with varyingT. This indirectly supports the experimentally observed paramagnetic singularity in the entireT-range. The proposed coexistence of such rich phases is a rare occurrence, yet it facilitates a fertile ground to tune them in a material driven by structural changes.