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Perovskite-inspired zero-dimensional (0D) hybrid halides exhibit impressive light emission properties; however, their potential in photovoltaics is hindered by the absence of interconnection between the inorganic polyhedra, leading to acute radiative recombination and insufficient charge separation. We demonstrate that incorporating closely-spaced dissimilar polyhedral units with minimal structural distortion leads to a remarkable enhancement in visible-light photodetection capability. We designed 0D C24H72N8In2Br14 (HIB) with a tetragonal crystal system, replacing the Cs+ of Cs2InBr5.H2O (CIB) with 1,6-hexanediammonium (HDA) cation. HIB comprises [InBr6]3- octahedra, and [InBr4]- tetrahedra units spaced 3.9 Å apart by the HDA linker. The [InBr4]- unit is additionally linked to HDA via intercalated bromine through hydrogen and halogen bonding interactions, respectively. This structural arrangement lowers the dielectric confinement, thereby enhancing carrier density and mobility, and increasing the diffusion coefficient compared to CIB. With 3.6% bromine vacancy within the [InBr4]- block, mid-gap states are created, reducing the direct band gap to 2.19 eV. HIB demonstrates an unprecedently high responsivity of 9975.9 ± 201.6 mA W-1 under 3 V potential bias at 485 nm wavelength, among low-dimensional hybrid halides. In the absence of potential bias, the self-powered photodetection parameters are 81.2 ± 3.0 mA W-1 and (6.98 ± 0.21) × 109 Jones.

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Photocatalytic H2 evolution by water splitting is a promising approach to address the challenges of environmental pollution and energy scarcity. Graphitic carbon nitride (g-C3N4) has emerged as a star photocatalyst because of its numerous advantages. To address the limitations of traditional g-C3N4, namely its inadequate visible light response and rapid recombination of photogenerated carriers, we employed a schiff base reaction to synthesize -C=N- doped g-C3N4. The introduction of -C=N- groups at the bridging nitrogen sites induced structural distortion in g-C3N4, facilitating n-π* electronic transitions from the lone pair electrons of nitrogen atom and extending light absorption up to 600 nm. Moreover, the presence of heterogeneous π-conjugated electron distribution effectively traps photogenerated electrons and enhances charge carrier separation. Benefiting from its expanded spectral response range, unique electronic properties, increased specific surface area, the doped g-C3N4 exhibited outstanding photocatalytic H2 evolution performance of 1050.13 µmol/g/h. The value was 5.9 times greater than the pristine g-C3N4.

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The cycling stability of LiNi0.8Co0.1Mn0.1O2 under high voltages is hindered by the occurrence of hybrid anion- and cation-redox processes, leading to oxygen escape and uncontrolled phase collapse. In this study, an interfacial engineering strategy involving a straightforward mechanical ball milling and low-temperature calcination, employing a Se-doped and FeSe2&Fe2O3-modified approach is proposed to design a stable Ni-rich cathode. Se2- are selectively adsorbed within oxygen vacancies to form O─TM─Se bond, effectively stabilizing lattice oxygen, and preventing structural distortion. Simultaneously, the Se-NCM811//FeSe2//Fe2O3 self-assembled electric field is activated, improving interfacial charge transfer and coupling. Furthermore, FeSe2 accelerates Li+ diffusion and reacts with oxygen to form Fe2O3 and SeO2. The Fe2O3 coating mitigates hydrofluoric acid erosion and acts as an electrostatic shield layer, limiting the outward migration of oxygen anions. Impressively, the modified materials exhibit significantly improved electrochemical performance, with a capacity retention of 79.7% after 500 cycles at 1C under 4.5 V. Furthermore, it provides an extraordinary capacity retention of 94.6% in 3-4.25 V after 550 cycles in pouch-type full battery. This dual-modification approach demonstrates its feasibility and opens new perspective for the development of stable lithium-ion batteries operating at high voltages.

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Covalent triazine frameworks (CTFs) with tunable structure, fine molecular design and low cost have been regarded as a class of ideal electrode materials for lithium-ion batteries (LIBs). However, the tightly layered structure possessed by the CTFs leads to partial hiding of the redox active site, resulting in their unsatisfactory electrochemical performance. Herein, two CTFs (BDMI-CTF and TCNQ-CTF) with higher degree of structural distortion, more active sites exposed, and large lattice pores were prepared by dynamic trimerization reaction of cyano. As a result, BDMI-CTF as a cathode material for LIBs exhibits high initial capacity of 186.5 mAh/g at 50 mA g-1 and superior cycling stability without capacity loss after 2000 cycles at 1000 mA g-1 compared with TCNQ-CTF counterparts. Furthermore, based on their bipolar functionality, BDMI-CTF can be used as both cathode and anode materials for symmetric all-organic batteries (SAOBs), and this work will open a new window for the rational design of high performance CTF-based LIBs.

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In this work, atomic cobalt (Co) incorporation into the Pd2Ge intermetallic lattice facilitates operando generation of a thin layer of CoO over Co-substituted Pd2Ge, with Co in the CoO surface layer functioning as single metal sites. Hence the catalyst has been titled Co1-CoO-Pd2Ge. High-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy confirm the existence of CoO, with some of the Co bonded to Ge by substitution of Pd sites in the Pd2Ge lattice. The role of the CoO layer in the oxygen evolution reaction (OER) has been verified by its selective removal using argon sputtering and conducting the OER on the etched catalyst. In situ X-ray absorption near-edge structure and extended X-ray absorption fine structure spectroscopy demonstrate that CoO gets transformed to CoOOH (Co3+) in operando condition with faster charge transfer through Pd atoms in the core Pd2Ge lattice. In situ Raman spectroscopy depicts the emergence of a CoOOH phase on applying potential and shows that the phase is stable with increasing potential and time without getting converted to CoO2. Density functional theory calculations indicate that the Pd2Ge lattice induces distortion in the CoO phase and generates unpaired spins in a nonmagnetic CoOOH system resulting in an increase in the OER activity and durability. The existence of spin density even after electrocatalysis is verified from electron paramagnetic resonance spectroscopy. We have thus successfully synthesized intermetallic supported CoO during synthesis and rigorously verified the role played by an intermetallic Pd2Ge core in enhancing charge transfer, generating spin density, improving electrochemical durability, and imparting mechanical stability to a thin CoOOH overlayer. Differential electrochemical mass spectrometry has been explored to visualize the instantaneous generation of oxygen gas during the onset of the reaction.

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Organic compounds exhibit great potential as sustainable, tailorable, and environmentally friendly electrode materials for rechargeable batteries. However, the intrinsic defects of organic electrodes, including solubility, low ionic conductivity, and restricted electroactivity sites, will inevitably decrease the cycling life and capacity. We herein designed and prepared nanostructured porous polymers (NPP) with a simple one-pot method to overcome the above defects. Theoretical calculations and experimental results demonstrate that the as-synthesized NPP exhibited low volume expansion, molecular-structural distortion, and a gradual function activation process during cycling, thus exhibiting superior, high, and durable lithium storage. The gradual molecular distortion during the lithium storage processes provides more redox-active sites for Li storage, increasing the Li-storage capacity. Ex situ spectrum studies reveal the redox reaction mechanism of Li storage and demonstrate a gradual activation process during the repeated charging/discharging until the full storage of 18 Li ions is achieved. Additionally, a real-time observation on the NPP anode by in situ transmission electron microscope reveals a slight volume expansion during the repeating lithiation and delithiation processes, ensuring its structural integrity during cycling. This quantitative work for high-durability lithium storage could be of immediate benefit for designing organic electrode materials.

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Magnesium ions are abundant and play indispensable functions in the ribosome. A decrease in Mg2+ concentration causes 70S ribosome dissociation and subsequent unfolding. Structural distortion at low Mg2+ concentrations has been observed in an immature pre50S, while the structural changes in mature subunits have not yet been studied. Here, we purified the 30S subunits of E. coli cells under various Mg2+ concentrations and analyzed their structural distortion by cryo-electron microscopy. Upon systematically interrogating the structural heterogeneity within the 1 mM Mg2+ dataset, we observed 30S particles with different levels of structural distortion in the decoding center, h17, and the 30S head. Our model showed that, when the Mg2+ concentration decreases, the decoding center distorts, starting from h44 and followed by the shifting of h18 and h27, as well as the dissociation of ribosomal protein S12. Mg2+ deficiency also eliminates the interactions between h17, h10, h15, and S16, resulting in the movement of h17 towards the tip of h6. More flexible structures were observed in the 30S head and platform, showing high variability in these regions. In summary, the structures resolved here showed several prominent distortion events in the decoding center and h17. The requirement for Mg2+ in ribosomes suggests that the conformational changes reported here are likely shared due to a lack of cellular Mg2+ in all domains of life.

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Ternary/polynary perovskite solid solutions based on binary systems are well-known for their high piezoelectric performance. In this work, a series of Pb(Ni1/3Nb2/3)O3-Pb(Sc1/2Nb1/2)O3-PbTiO3 compositions with the particularly high piezoelectric coefficient of d33* > 1000 pm/V and d33 > 700 pC/N have been developed. The optimal performance was achieved in the 0.52PNN-0.14PSN-0.34PT composition (d33* = 1120 pm/V, d33 = 804 pC/N, and Tm = 109 °C). The high piezoelectric performance of this system is reported and is superior to those of most lead-based ternary/polynary ceramics. By a combination of in situ high-energy synchrotron diffraction with transmission electron microscopy (TEM), the origin of the high piezoelectric response has been unambiguously revealed. Upon application of an external electric field, synchrotron diffraction profiles show no splitting but prominent shifting, indicating that the large intrinsic lattice strain arising from the reduced crystal anisotropy and facilitated polarization variation is associated with the high piezoelectric response. Furthermore, microscopic studies by TEM highlight a heterogeneous ferroelectric domain configuration generated by a small local structural distortion, which is also beneficial for the high piezoelectric performance in the proposed ternary piezoelectric systems. The design process of ternary perovskite solid solutions with a wide morphotropic phase boundary region and small structural distortion may be enlightening for the exploration of other high-performance polynary piezoelectrics.

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Structural distortions frequently occur in materials, either periodically (ferroelectric or antiferroelectric) or in local areas (domain boundaries, surfaces/interfaces, dislocations). Measuring atomic displacements from an average lattice is of crucial importance for analyzing structural distortions and their connections to physical properties. Conventionally, the displacements are measured atom-by-atom by fitting atomic-resolution images with two-dimensional gaussian functions. Here, we exhibit an efficient method, named Displacement Separation Analysis, DSA in short, to directly separate atomic displacements from an average lattice based on Fourier space filtering. Using antiferroelectric AgNbO3 as a model system, we demonstrate the consistence between DSA and gaussian fitting. The suppression of polarization at interfacial region of h-LuFeO3/α-Al2O3 heterostructure and the emergence of modulation structure in LuFe2O4+x is then revealed using DSA, attesting the implication of DSA in unveiling structural distortions either locally or periodically. Inspired by the simple principle of DSA, such method can be used for any atomic-resolution images, including TEM, STM, and AFM images to exhibit the atomic displacement intuitively.

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BACKGROUND: Local sequence context is known to have an impact on the mutational pattern seen in cancer. The RAS genes and a smoking carcinogen, Benzo[a]pyrene diol epoxide (BPDE), have been utilised to explore these context effects. BPDE is known to form an adduct at the guanines in a number of RAS gene sites, KRAS codons 12, 13 and 14, NRAS codon 12, and HRAS codons 12 and 14. RESULTS: Molecular modelling techniques, along with multivariate analysis, have been utilised to determine the sequence influenced differences between BPDE-adducted RAS gene sequences as well as the local distortion caused by the adducts. CONCLUSIONS: We conclude that G:C > T:A mutations at KRAS codon 12 in the tumours of lung cancer patients (who smoke), proposed to be predominantly caused by BPDE, are due to the effect of the interaction methyl group at the C5 position of the thymine base in the KRAS sequence with the BPDE carcinogen investigated causing increased distortion. We further suggest methylated cytosine would have a similar effect, showing the importance of methylation in cancer development.

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(Ca1-x Eux )WO4 (x = 0-21 mol%) phosphors were prepared using the classical solid-state reaction method. The influence of Eu3+ ion doping on lattice structure was observed using powder X-ray diffraction and Fourier transform infrared spectroscopy. Furthermore, under this influence, the luminescence properties of all samples were analyzed. The results clearly illustrated that the element europium was successfully incorporated into the CaWO4 lattice with a scheelite structure in the form of a Eu3+ ion, which introduced a slight lattice distortion into the CaWO4 matrix. These lattice distortions had no effect on phase purity, but had regular effects on the intrinsic luminescence of the matrix and the f-f excitation transitions of Eu3+ activators. When the Eu3+ concentration was increased to 21 mol%, a local luminescence centre of [WO4 ]2- groups was detected in the matrix and manifested as the decay curves of [WO4 ]2- groups and luminescence changed from single exponential to double exponential fitting. Furthermore, the excitation transitions of Eu3+ between different energy levels (such as 7 F0 →5 L6 , 7 F0 →5 D2 ) also produced interesting changes. Based on analysis of photoluminescence spectra and the chromaticity coordinates in this study, it could be verified that the nonreversing energy transfer of [WO4 ]2- →Eu3+ was efficient and incomplete.

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Cell-based assays are essential for virus functional characterization in fundamental and applied research. Overcoming the limitations of virus-labelling strategies while allowing functional assessment of critical viral enzymes, virus-induced cell-based biosensors constitute a powerful approach. Herein, we designed and characterized different cell-based switch-on split GFP sensors reporting viral proteolytic activity and virus infection. Crucial to these sensors is the effective-yet reversible-fluorescence off-state, through protein distortion. For that, single (protein embedment or intein-mediated cyclization) or dual (coiled-coils) distortion schemes prevent split GFP self-assembly, until virus-promoted proteolysis of a cleavable sequence. All strategies showed their applicability in detecting viral proteolysis, although with different efficiencies depending on the protease. While for tobacco etch virus protease the best performing sensor was based on coiled-coils (signal-to-noise ratio, SNR, 97), for adenovirus and lentivirus proteases it was based on GFP11 cyclization (SNR 3.5) or GFP11 embedment distortion (SNR 6.0), respectively. When stably expressed, the sensors allowed live cell biosensing of adenovirus infection, with sensor fluorescence activation 24 h post-infection. The structural distortions herein studied are highly valuable in the development of cellular biosensing platforms. Additionally highlighted, selection of the best performing strategy is highly dependent on the unique properties of each viral protease.

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Bismuth oxyselenide (Bi2 O2 Se), a new type of 2D material, has recently attracted increased attention due to its robust bandgap, stability under ambient conditions, and ultrahigh electron mobility. In such complex oxides, fine structural distortion tends to play a decisive role in determining the unique physical properties, such as the ferrorotational order, ferroelectricity, and magnetoelasticity. Therefore, an in-depth investigation of the fine structural symmetry of Bi2 O2 Se is necessary to exploit its potential applications. However, conventional techniques are either time consuming or requiring tedious sample treatment. Herein, a noninvasive and high-throughput approach is reported for characterizing the fine structural distortion in 2D centrosymmetric Bi2 O2 Se by polarization-dependent third-harmonic generation (THG). Unprecedentedly, the divergence between the experimental results and the theoretical prediction of the perpendicular component of polarization-dependent THG indicates a fine structural distortion, namely, a <1.4° rotation of the oxygen square in the tetragonal (Bi2 O2 ) layers. This rotation breaks the intrinsic mirror symmetry of 2D Bi2 O2 Se, eventually reducing the symmetry from the D4h to the C4h point group. The results demonstrate that THG is highly sensitive to even fine symmetry variations, thereby showing its potential to uncover hidden phase transitions and interacting polarized sublattices in novel 2D material systems.

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Unknown changes in the crystalline order of regular TiO2 result in the formation of black titania, which has garnered significant interest as a photocatalytic material due to the accompanying electronic changes. Herein, the nature of the lattice distortion caused by an oxygen vacancy was determined that in turn results in the formation of mid-band-gap states found in previous studies of black titania. An innovative technique is introduced using a state-of-the-art silicon drift detector, which can be used in conjunction with extended X-ray absorption fine structure (EXAFS) to measure bulk interatomic distances. Also discussed is how the energy dispersive nature of such a detector can allow for an unimpeded signal, indefinitely in energy space, thereby sidestepping the hurdles of more conventional EXAFS, which is often impeded by other absorption edges.

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Exploring and manipulating domain configurations in ferroelectric thin films are of critical importance for the design and fabrication of ferroelectric heterostructures with a novel functional performance. In this study, BiFeO3 (BFO) ultrathin films with various Bi/Fe ratios from excess Bi to deficient Bi have been grown on (La0.7Sr0.3)MnO3 (LSMO)-covered SrTiO3 substrates by a laser molecular beam epitaxy system. Atomic force microscopy and piezoresponse force microscopy measurements show that both the surface morphology and ferroelectric polarization of the films are relevant to Bi nonstoichiometry. More significantly, a Bi-excess thin film shows an upward (from substrate to film surface) uniform ferroelectric polarization, whereas a Bi-deficient thin film exhibits a downward uniform polarization, which means the as-grown polarization of BFO thin films can be controlled by changing the Bi contents. Atomic-scale structural and chemical characterizations and second-harmonic generation measurements reveal that two different kinds of structural distortions and interface atomic configurations in the BFO/LSMO heterostructures can be induced by the change of Bi nonstoichiometry, leading to the two opposite as-grown ferroelectric polarizations. It has also been revealed that the band gap of BFO thin films can be modulated via Bi nonstoichiometry. These results demonstrate that Bi nonstoichiometry plays a key role on the ferroelectric domain states and physical properties of BFO thin films and also open a new avenue to manipulate the structure and ferroelectric domain states in BFO thin films.

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Single- and few-layer metal chalcogenide compounds are of significant interest due to structural changes and emergent electronic properties on reducing dimensionality from three to two dimensions. To explore dimensionality effects in SnSe, a series of [(SnSe)1+δ]mTiSe2 intergrowth structures with increasing SnSe layer thickness (m = 1-4) were prepared from designed thin-film precursors. In-plane diffraction patterns indicated that significant structural changes occurred in the basal plane of the SnSe constituent as m is increased. Scanning transmission electron microscopy cross-sectional images of the m = 1 compound indicate long-range coherence between layers, whereas the m ≥ 2 compounds show extensive rotational disorder between the constituent layers. For m ≥ 2, the images of the SnSe constituent contain a variety of stacking sequences of SnSe bilayers. Density functional theory calculations suggest that the formation energy is similar for several different SnSe stacking sequences. The compounds show unexpected transport properties as m is increased, including the first p-type behavior observed in (MSe)m(TiSe2)n compounds. The resistivity of the m ≥ 2 compounds is larger than for m = 1, with m = 2 being the largest. At room temperature, the Hall coefficient is positive for m = 1 and negative for m = 2-4. The Hall coefficient of the m = 2 compound changes sign as temperature is decreased. The room-temperature Seebeck coefficient, however, switches from negative to positive at m = 3. These properties are incompatible with single band transport indicating that the compounds are not simple composites.

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Two-dimensional materials offer a remarkably rich materials platform to study the origin of different material behaviors at the atomic level, and doping provides a key means of tailoring such materials' functional properties. The local atomic structure around such dopants can be critically important in determining the material's behavior as it could modulate scattering, catalytic activity, electronic and magnetic properties, and so forth. Here, using aberration-corrected scanning transmission electron microscopy (STEM) with sub-Ångstrom resolution in conjunction with density functional theory calculations, we demonstrate a strong coupling between Mo dopants and two types of defects in WS2 monolayers: sulfur monovacancies and grain boundaries. Although Mo does occupy a transition metal lattice site, it is not an ideal substitutional dopant: ∼80% of the S vacancies identified by STEM colocalize with Mo dopants, an affinity that appears to be enhanced by symmetry breaking of a partially occupied midgap defect state. Although a Mo dopant by itself does not considerably distort the WS2 lattice, it induces substantial lattice deformation by apparently facilitating the charging of a sulfur monovacancy paired with it, which is consistent with the results of first-principles calculations. This coupling of foreign substitutional dopants with vacancies could potentially be exploited to control the distribution and location of chalcogenide vacancies within transition metal dichalcogenides (TMD), by segregating vacancies into regions of high Mo concentration that are purposely placed away from active regions of TMD-based devices.

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The corrugated layer structure bismuth has been successfully tailored into negative thermal expansion along c axis by size effect. Pair distribution function and extended X-ray absorption fine structure are combined to reveal the local structural distortion for nanosized bismuth. The comprehensive method to identify the local structure of nanomaterials can benefit the regulating and controlling of thermal expansion in nanodivices.

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The relations between the spin-Hamiltonian (SH) parameters and the structural parameters of the Fe(3+) ions in Fe(3+): ZnAl2O4 crystals have been established by means of the microscopic spin Hamiltonian theory and the superposition model (SPM). On the basis of this, the local structure distortion, the second-order zero-field splitting (ZFS) parameter D, the fourth-order ZFS parameter (a-F), and the Zeeman g-factors g factors: g//, g⊥, and Δg(=g//-g⊥) for Fe(3+) ions in Fe(3+): ZnAl2O4 crystals, for the first time taking into account the electronic magnetic interactions, i.e. the spin-spin (SS), the spin-other-orbit (SOO), and the orbit-orbit (OO) interactions, besides the well-known spin-orbit (SO) interaction, are theoretically investigated using complete diagonalization method (CDM). This investigation reveals that the local structure distortion effect plays an important role in explaining the spectroscopic properties of Fe(3+) ions in Fe(3+): ZnAl2O4 crystals. The theoretical second-order ZFS parameter D, the fourth-order ZFS parameter (a-F), and the Zeeman g-factors: g//, g⊥, and Δg of the ground state for Fe(3+) ion in Fe(3+): ZnAl2O4 crystals yield a good agreement with experiment findings by taking into account the lattice distortions: ΔR=0.0191nm and Δθ=0.076°. In conclusion, our research shows that there is a slight local structure distortion for Fe(3+) ions in Fe(3+): ZnAl2O4 crystals, but the site of Fe(3+) still retains D3d symmetry. On the other hand, it is found for Fe(3+) ions in Fe(3+): ZnAl2O4 crystals that the SO mechanism is the most important one, whereas the contributions to the SH parameters from other four mechanisms, including the SS, SOO, OO, and SO∼SS∼SOO∼OO mechanisms are not appreciable, especially for the ZFS parameter D.

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To clarify the contrasting impurity effects of Mn and Zn dopants on the critical temperature of optimally doped Ba0.5K0.5Fe2As2 superconductors, extended X-ray absorption fine-structure spectroscopy was implemented at the Fe and As K-edge. In Mn-doped compounds a gradual deviation of the symmetric FeAs4 tetrahedron and weakening of the Fe-As bond was observed. Conversely, in Zn-doped compounds the perfect FeAs4 tetrahedron is maintained and the Fe-As bond is rigid. The local structural details are consistent with the development of superconductivity in these two systems, suggesting a significant role played by the topology of the FeAs4 tetrahedron and rigidness of the Fe-As bond in Mn/Zn-doped Ba0.5K0.5Fe2As2 superconductors.

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