Change In Space Group Research Articles

Water and chloride as allosteric inhibitors in WNK kinase osmosensing.

Osmotic stress and chloride regulate the autophosphorylation and activity of the WNK1 and WNK3 kinase domains. The kinase domain of unphosphorylated WNK1 (uWNK1) is an asymmetric dimer possessing water molecules conserved in multiple uWNK1 crystal structures. Conserved waters are present in two networks, referred to here as conserved water networks 1 and 2 (CWN1and CWN2). Here we show that PEG400 applied to crystals of dimeric uWNK1 induces de-dimerization. Both the WNK1 the water networks and the chloride binding site and are disrupted by PEG400. CWN1 is surrounded by a cluster of pan-WNK-conserved charged residues. Here we mutagenized these charges in WNK3, a highly active WNK isoform kinase domain, and WNK1, the isoform best studied crystallographically. Mutation of E314 in the Activation Loop of WNK3 (WNK3/E314Q and WNK3/E314A, and the homologous WNK1/E388A) enhanced the rate of autophosphorylation, and reduced chloride sensitivity. Other WNK3 Cluster mutants reduced the rate of autophosphorylation activity coupled with greater chloride sensitivity than wild-type. The water and chloride regulation thus appear linked. The lower activity of some mutants may reflect effects on catalysis. Crystallography showed that activating mutants introduced conformational changes in similar parts of the structure to those induced by PEG400. WNK activating mutations and crystallography support a role for CWN1 in WNK inhibition consistent with water functioning as an allosteric ligand.

Symmetry-breaking-enhanced power conversion efficiency of 2D van der Waals heterostructures

Symmetry-breaking plays a crucial role in determining the property and functionality of materials. Here, we demonstrate that symmetry-breaking can dramatically enhance the power conversion efficiency (PCE) of a two-dimensional (2D) van der Waals (vdW) heterostructure solar cell by taking a γ-phosphorus-carbide (PC)-based vdW heterostructure as a model. Thanks to its four-atom-layer structure of γ-PC, both alternately arranging P and C atoms to form a Janus structure and sliding C atom layer to change space group are two effective methods to break the symmetry. We find that in comparison with a symmetric configuration, the PCE of γ-PC/MoS2N4 with symmetry-breaking could be increased by 257.2% and 270% via forming a Janus structure and the change in space group, respectively. Particularly, the PCE of symmetry-broken γ-PC/MoSi2N4 can be further increased to 21.35% under an appropriate tensile strain, which could be attributed to small conduction band offset between constituent monolayers and suitable donor bandgap. Our study showcases that tuning the symmetry of multi-atom-layer 2D materials is an effective strategy to realize enhancement of the performance for 2D materials-based optoelectronic devices.

Ab-initio investigation of the structural, electronic and optical properties of CsPbBr3 perovskite under pressure using the DFT-1/2 method

Pressure-induced phase transitions in metal halide perovskites lead to significantly different material properties and offer great potential for diverse applications. The electronic, structural, and optical properties of Cesium lead bromide (CsPbBr3) crystals are investigated using density functional theory (DFT) to draw an integrated picture of orbital morphology, absorption spectra, and band gap values. Spin-orbit coupling and DFT-1/2 correction are used to gain a better insight into electronic properties and band splitting in the cubic phase. Calculations of pressure-induced phase transitions, electronic band gap engineering, and manipulation of optical absorption edges of CsPbBr3 are conducted. In the cubic and tetragonal crystal lattices, a band gap closure and opening occurs demonstrating a Dirac cone upon application and increase of pressure. Indeed, in the tetragonal lattice of CsPbBr3, a topological band occurs. Orthorhombic perovskite crystal lattice undergoes successive direct-indirect and indirect-direct band gap transitions, followed by a space group change at extreme pressures. However, under pressure, orthorhombic non-perovskite lattice experiences a sudden band gap breakdown. Phase and band gap transitions are explained by orbital hybridizations and structural symmetry evolution (e.g., bond length contraction/dilation and octahedral cage rotation/distortion). These results provide comprehensive guidelines for further experimental studies on pressure engineering, advanced photovoltaic and optoelectronic applications, discovering and understanding new topological band structures of perovskite materials.

Charge density waves tuned by biaxial tensile stress.

The precise arrangement and nature of atoms drive electronic phase transitions in condensed matter. To explore this tenuous link, we developed a true biaxial mechanical deformation device working at cryogenic temperatures, compatible with x-ray diffraction and transport measurements, well adapted to layered samples. Here we show that a slight deformation of TbTe3 can have a dramatic influence on its Charge Density Wave (CDW), with an orientational transition from c to a driven by the a/c parameter, a tiny coexistence region near a = c, and without space group change. The CDW transition temperature Tc displays a linear dependence with while the gap saturates out of the coexistence region. This behaviour is well accounted for within a tight-binding model. Our results question the relationship between gap and Tc in RTe3 systems. This method opens a new route towards the study of coexisting or competing electronic orders in condensed matter.

Chiral Substitution on Spaced Cations Lead to Improved Properties and Reversible Phase Transition, Broadband Emission in Parent Compound (3APr)PbBr4

AbstractHybrid organic‐inorganic perovskites (HOIP) due to their excellent optoelectronic properties and flexible structure have attracted enthusiastic interest. In particular, introducing chirality is a method to enhance compound performance. Herein, we report a multifunctional compound: (3APr)PbBr4 (1) (3APr=3‐Pyrrolidinamine) and corresponding enantiomer R and S‐(3APr)PbBr4 (R/S‐2). Compound 1 show reversible solid‐state phase transition, step‐like dielectric anomaly and broadband yellow emission under uv light excitation. Accompany with phase transition, structure dimension transition from 2D to 1D without space group change. Through introduce chirality, the R/S‐2 display mirror image 1D structural relationship, increased quantum yield from 3.43 % (1) to 13.65 % (R/S‐2) and exhibits corresponding CD signals. Then combine to first‐principles analysis, it was found that fluorescence is attributed to the formation of instantaneous defects during excitation, leading to the formation of self‐trapped excitons (STEs). This finding will further promote the development of multifunctional compound and the study of chiral substitution enhance compound properties.

Minasgeraisite-(Y) discredited as an ordered intermediate between datolite and hingganite-(Y)

AbstractMinasgeraisite-(Y) is discredited on the basis of it being an ordered intermediate between datolite and hingganite-(Y) (IMA-CNMNC Proposal 23-F). An idealised formula is (Ca2Y2)□2(Be2B2)Si4O16(OH)4, which corresponds to Ca2□B2Si2O8(OH)2 (datolite) + Y2□Be2Si2O8(OH)2 (hingganite-(Y)). The type material is rich in Bi, the Bi-richest portion yet discovered from the type locality is shown to be an intermediate member between datolite, hingganite-(Y) and a hypothetical end-member phase yet to be found of composition Bi2□Be2Si2O8(OH)2. Minasgeraisite-(Y) has a different space group to datolite and hingganite-(Y). This lowering of symmetry to an acentric triclinic system is caused by different element occupancies on the A site of the gadolinite supergroup structure, which for minasgeraisite-(Y) becomes four individual sites. Such an order–disorder of elements is not considered as species-defining criteria despite the change in space group. Therefore, minasgeraisite-(Y) is discredited.

A room temperature ferroelectric material with photoluminescence: (1,3-dicyclohexylimidazole)2MnCl4.

Molecular ferroelectric materials have been widely used in capacitors and sensors due to their low cost, light weight, flexibility and good biocompatibility. Organic-inorganic hybrid complexes, on the other hand, have received a great deal of attention in the luminescence field due to their low cost and simple preparation. The combination of ferroelectricity and photoluminescence in organic-inorganic hybrid materials not only leads to tunable optical properties, but also enriches potential applications of multifunctional ferroelectrics in optoelectronic devices. Here, we report a new luminescent ferroelectric material (1,3-dicyclohexylimidazole)2MnCl4 (DHIMC). Thermogravimetric analysis (TGA) was used to measure the mass change of the material at a measurement rate of 20 K min-1 from room temperature to 900 K, and we found that this material has good thermostability, which is up to 383 K. Meanwhile, UV-vis measurements showed that it is also a fluorescent material emitting a strong green fluorescence at the wavelength of 525 nm. The ferroelectricity of the crystal was determined by two different methods: the Sawyer-Tower method and the double-wave method (DWM). Particularly, the single crystal experiences a phase transition from the ferroelectric phase to the paraelectric phase during the heating/cooling process at 318 K/313 K and the space group changes from P1̄ (centrosymmetric) to P1 (non-centrosymmetric). This work will enrich multifunctional luminescent ferroelectric materials and their application in display and sensing.

Stepwise dehydration of thomsonite (THO) with disordered Si/Al distribution: A new partially hydrated phase

The structural transformations occurring as a function of increasing temperature in zeolites are of interest because the porous structure, and therefore the physical properties, can significantly change.Zeolites with THO framework type are small-pore materials, which received attention because of their applications in catalytic processes. The majority of THO zeolites (synthetic and natural) are characterized by an ordered distribution of the cations at the tetrahedral sites. To date, few cases of disordered thomsonite have been reported. In this study, we investigated the dehydration behaviour of a natural thomsonite with disordered Si/Al distribution and chemical composition Ca3·34Na2·66Si11Al9O40∙12H2O. The structure was determined from room temperature (RT) to 698 K in order to compare the thermal behaviour with that reported for the ordered variety. Accurate structural analysis was performed by in situ single crystal X-ray diffraction. The dehydration starts at 348 K. Up to 498 K, thomsonite gradually releases four H2O. From 498 to 573 K, additional four H2O are lost and the space group changes from orthorhombic (Pbmn) to monoclinic (P21/n). This partially hydrated phase is characterized by a unit-cell volume contraction of −3% with respect to the RT phase and by a rearrangement of the extraframework cations in the zeolitic pores. The thermally treated thomsonite is able to reabsorb 50% of the lost H2O and transforms to the orthorhombic phase, equivalent to that observed at lower temperatures. However, the diffraction pattern analysis indicated a high degree of mosaicity, most probably due to the residual stress accumulated during the phase transformation.

Halogen tuning toward dielectric switch and band gap engineering in one-dimensional hybrid materials

Organic-inorganic hybrids with multiple tunable functions are very attractive for potential applications in sensors, smart switches, etc. To investigate the effect of halogen tuning on the properties of hybrid materials, two new multifunctional organic-inorganic hybrid compounds [3-hydroxy-azetidinecation]2SbX5 (1: X = Cl; 2: X = Br) are successfully synthesized here by replacing halogen anions. Reversible structural phase transitions accompanied by anomalous changes in dielectric constants are found when heating (T1 = 362 K; T2 = 373 K). Both two compounds have the same space group change from P212121 (Low Temperature Phase) to Pnma (High Temperature Phase). When replacing Cl with Br, the phase transition temperature increases by ca. 10 K and the band gap changes from 3.21 eV to 2.75 eV. Based on the above properties, this work could provide an effective molecular design strategy for the exploration and construction of temperature-tunable, lower bandgap semiconductor hybrid materials.

Ferroelectric Transition of a Chiral Molecular Crystal BINOL∙2DMSO

We report dielectric, thermodynamical, acoustic, and optical properties of a chiral molecular crystal, 1,1'-bi-2-naphthol 2-dimethylsulfoxide (BINOL2DMSO). We find two successive phase transitions at Tc1=190 K and Tc2=125 K. The first transition at Tc1 is characterized by an order-disorder transition of the guest molecules DMSO along with ferroelectricity. At the second transition of Tc2, the crystal structure deforms from tetragonal to monoclinic, leading to domain formation. Low-temperature x-ray diffraction suggests that the space group changes from P4_12_12 (P4_32_12) to P4_1 (P4_3) at Tc1, and down to P112_1 at Tc2.

Effects of doping by copper on electrical properties of LaCrO3 based perovskite

The use of nickel-yttria-stabilized zirconia (Ni/YSZ) as anode material for solid oxide fuel cell (SOFC) applications, presents some limitations such as poor stability in reduction/oxidation cycling, and poor sulphur tolerance which results in carbon deposition when utilizing hydrocarbon fuels. Even though lanthanum chromite (LaCrO3 noted LCO) is an excellent alternative to Ni/YSZ, it is rarely used in SOFC applications due to its poor conductivity. In order to further progress in developing LCO materials, this work was conducted to improve the conductivity of LCO by copper doping. In particular, LaCr1-xCuxO3 compounds with x = 0, 0.1, and 0.3 were synthesized via a solid-solid method. The followed preparation process allows obtaining a cubic structure with Pm-3m space group. The substitution of Cr with Cu resulted in a slight increase in lattice parameter a, but no change in structure or space group. Whereas, the band gap energy decreased from 3.68 eV for x = 0–3.06 eV for x = 0.3. The crystallite size increases with doping level. With regard to the obtained data from electrical measurements, a thermally activated and frequency depended conductivity was obtained for all samples. Furthermore, the correlated barrier hopping mechanism was proposed as a conduction mechanism, and an electrical transition from semiconductor to metallic behavior was observed. The conductivity increased also monotonously with Cu content and shows a maximum value of 4.5 S/m for x = 0.3. Besides, the tangent loss shows a maximum value of around 104 for x = 0.1. The LaCr0.7Cu0.3O3 compound could be a good candidate for SOFC applications, while LaCr0.9 Cu0.1O3 can be used as a heating element.

Taking the Third Route for Construction of POMOFs: The First Use of Carboxylate-Functionalized MnIII Anderson–Evans POM-Hybrid Linkers and Lanthanide Nodes

The purpose of the present contribution is to illustrate how to design and grow crystals of POMOFs based on POM-hybrid linkers with lanthanide ions as nodes. Thus, the MnIII-centered Anderson–Evans polyoxometalate (Mn-A-E-POM) was functionalized with 4-(((1,3-dihydroxy-2-(hydroxymethyl)propan-2-yl)amino)methyl)benzoic acid (H4L) to afford the hybrid inorganic–organic POM [N(n-C4H9)4]4[(MnMo6O18)(HL)(L)] (1), which in turn reacts with lanthanide salts and yields two three-dimensional frameworks with the general formulas Ln(DMF)6Ln(DMF)5Ln3(DMF)10[(MnMo6O18)(L)2]3·xDMF (2; Ln = La–Nd) and [Ln(DMF)4(H2O)]2[Ln3(DMF)6][(MnMo6O18)(L)2]3·xDMF (3; Ln = Y, Sm–Lu). The differentiation in these two families results from the lanthanide contraction. The crystallization process is crucial for obtaining these two families in a bulk pure phase. Family 2 can be obtained by stirring, while for family 3 the less energy demanding layering method proved to be the most efficient pathway. Notably, the change in the ionic radii causes a change in space group (from P21 (family 2) to P21/c (family 3); however, the topology of the frameworks is unaffected.

Electronic and optical properties of Y-doped $$\hbox {BaBiO}_{3}$$

We investigate the nature of bond disproportionation in $$\hbox {BaBi}_{0.9}\hbox {Y}_{0.1}\hbox {O}_{3}$$ (BYBO) and its manifestation in the valence band and the optical absorption spectra. Our room-temperature (RT) structural results show that both the parent and the doped (BYBO) compounds stabilise in monoclinic structure but with a change in space group from I2/m to P21/n on Y doping. The Raman scattering studies suggest decrement in the breathing mode distortion of $$\hbox {BiO}_{6}$$ octahedra. The valence band spectra show an increase in the gap and close to the Fermi edge, we observe significant modifications in the fine structures on Y doping. These were studied using band structure calculations under TB-mBJ. The results show that the electronic states of the Y ions play significant role in driving the electronic structure. We also observe the importance of O 2p holes and also transfer of electrons from O 2p to Bi1 6s, Bi2 6s, and Y states to bring about bond disproportionation in the doped compound. The intensity variations and the features in the optical absorption spectra were understood based on the E vs k point calculations performed in the irreducible part of the Brillouin zone. The behaviour of the gap on doping is also in line with the calculations and optical absorption studies. The behaviour of the optical absorption spectra suggests possible use in solar cell and optical sensor applications. A composite of the doped compound with $$\hbox {BaTiO}_{3}$$ may find applications in the field of high-energy density capacitor. We believe that our results will be helpful in understanding the role of the electronic states of the dopants in superconductivity, especially in comparison with the monoclinic phase exhibited in the superconducting phase of $$\hbox {BaPb}_{0.75}\hbox {Bi}_{0.25}\hbox {O}_{3}$$ .

A polar oxyhalogen-vanadate compound (C5NH13Cl)2VOCl4 with optical and two-staged dielectric switch behavior.

Polar organic-inorganic hybrid materials have been applied in ferroelectricity, as well as in devices based on nonlinear optical and piezoelectricity properties. Here, we used a rectangular pyramid structure of [VOCl4]2- to construct a polar compound (C5NH13Cl)2VOCl4 (1). Compound 1 crystallized in the monoclinic P21 space group. Coexistence of nonlinear optical switching behavior (space-group change from P21 to P21/n) and two-staged thermosensitive dielectric switching properties could be achieved under the stimulus of temperature. Our findings provide an effective approach for construction of polar materials.

Phosphonium-Based One-Dimensional Perovskite with Switchable Dielectric Behaviors and Phase Transitions.

The one-dimensional (1D) ABX3-type perovskite [(CH3)3PCH2F]CdCl2Br (1) has been obtained on the basis of the design of an organic-inorganic hybrid. Strikingly, it experiences sequential phase transitions at around 295 and 336 K, respectively. Given the noticeable steplike dielectric anomalies in the vicinity of 295 K, 1 is identified as a promising dielectric-switchable material. According to the single-crystal structure analysis, the order-to-disorder transformation of the [(CH3)3PCH2F]+ cation is the main reason for the phase transitions and the change of space group from the orthorhombic Pnma (No. 62) to the hexagonal P63/m (No. 176). This design of a perovskite structure will inspire more advances in the ever-growing field of switchable functional materials.

Secondary Metal Coordination Using a Tetranuclear Complex as Ligand Leading to Hexanuclear Complexes with Enhanced Thermal Barriers for Electron Transfer

Postsynthesis of the paramagnetic square-shaped complex {[(Tp*Me)Fe(μ-CN)2(CN)][Co(dmbpy)2]}2(BPh4)2·6MeCN·H2O [1, Tp*Me = tris(3,4,5-trimethylpyrazole)-borate; dmbpy = 4,4′-dimethyl-2,2′-bipyridin...

Lysozyme crystals dyed with bromophenol blue: where has the dye gone?

Protein crystals can easily be coloured by adding dyes to their mother liquor, but most structures of these protein-dye complexes remain unsolved. Here, structures of lysozyme in complex with bromophenol blue obtained by soaking orthorhombic and tetragonal crystals in a saturated solution of the dye at different pH values from 5.0 to 7.5 are reported. Two different binding sites can be found in the lysozyme-bromophenol blue crystals: binding site I is located near the amino- and carboxyl-termini, while binding site II is located adjacent to helices α1 (residues 4-15) and α3 (residues 88-100). In the orthorhombic crystals soaked at pH 7.0, binding of the dye takes place in both sites without significant changes in the unit cell. However, soaking tetragonal crystals with bromophenol blue results in two different complexes. Crystals soaked at pH 5.5 (HEWL-T1) show a single dye molecule bound to site II, and the crystals belong to space group P43212 without significant changes in the unit cell (a = b = 78.50, c= 37.34 Å). On the other hand, crystals soaked at pH 6.5 in the presence of imidazole (HEWL-T2) show up to eight molecules of the dye bound to site II, and display changes in space group (P212121) and unit cell (a = 38.00, b = 76.65, c= 84.86 Å). In all of the structures, the dye molecules are placed at the surface of the protein near to positively charged residues accessible through the main solvent channels of the crystal. Differences in the arrangement of the dye molecules at the surface of the protein suggest that the binding is not specific and is mainly driven by electrostatic interactions.

Stress-Induced Domain Wall Motion in a Ferroelastic Mn3+ Spin Crossover Complex.

Domain wall motion is detected for the first time during the transition to a ferroelastic and spin state ordered phase of a spin crossover complex. Single‐crystal X‐ray diffraction and resonant ultrasound spectroscopy (RUS) revealed two distinct symmetry‐breaking phase transitions in the mononuclear Mn3+ compound [Mn(3,5‐diBr‐sal2(323))]BPh4, 1. The first at 250 K, involves the space group change Cc→Pc and is thermodynamically continuous, while the second, Pc→P1 at 85 K, is discontinuous and related to spin crossover and spin state ordering. Stress‐induced domain wall mobility was interpreted on the basis of a steep increase in acoustic loss immediately below the the Pc‐P1 transition

Stress‐Induced Domain Wall Motion in a Ferroelastic Mn3+ Spin Crossover Complex

AbstractDomain wall motion is detected for the first time during the transition to a ferroelastic and spin state ordered phase of a spin crossover complex. Single‐crystal X‐ray diffraction and resonant ultrasound spectroscopy (RUS) revealed two distinct symmetry‐breaking phase transitions in the mononuclear Mn3+ compound [Mn(3,5‐diBr‐sal2(323))]BPh4, 1. The first at 250 K, involves the space group change Cc→Pc and is thermodynamically continuous, while the second, Pc→P1 at 85 K, is discontinuous and related to spin crossover and spin state ordering. Stress‐induced domain wall mobility was interpreted on the basis of a steep increase in acoustic loss immediately below the the Pc‐P1 transition

Structural Change and Morphological Surface Degradation upon Electrochemical Li Extraction from a Single Crystal of Spinel-type LiNi0.5Mn1.5O4

The space-group change and surface degradation of spinel-type LiNi0.5Mn1.5O4 upon the Li extraction reaction at 4.9 V were investigated using single-crystal samples. The stoichiometric LiNi0.5Mn1.5...