Magnetic Stress-Driven Metal-Insulator Transition in Strongly Correlated Antiferromagnetic CrN.

Traditionally, the Coulomb repulsion or Peierls instability causes the metal-insulator phase transitions in strongly correlated quantum materials. In comparison, magnetic stress is predicted to drive the metal-insulator transition in materials exhibiting strong spin-lattice coupling. However, this mechanism lacks experimental validation and an in-depth understanding. Here we demonstrate the existence of the magnetic stress-driven metal-insulator transition in an archetypal material, chromium nitride. Structural, magnetic, electronic transport characterization, and first-principles modeling analysis show that the phase transition temperature in CrN is directly proportional to the strain-controlled anisotropic magnetic stress. The compressive strain increases the magnetic stress, leading to the much-coveted room-temperature transition. In contrast, tensile strain and the inclusion of nonmagnetic cations weaken the magnetic stress and reduce the transition temperature. This discovery of a new physical origin of metal-insulator phase transition that unifies spin, charge, and lattice degrees of freedom in correlated materials marks a new paradigm and could lead to novel device functionalities.

Raman Evidence of Multiple Adsorption Sites and Structural Transformation in ZIF-4.

The zeolitic imidazolate framework, ZIF-4, exhibits soft porosity and is known to show pore volume changes with temperatures, pressures, and guest adsorption. However, the mechanism and adsorption behavior of ZIF-4 are not completely understood. In this work, we report an open to narrow pore transition in ZIF-4 around T ∼ 253 K upon lowering the temperature under vacuum (10-6 Torr) conditions, facilitated by C-H···π interactions. In the gaseous environment of N2 and CO2 around the framework, characteristic Raman peaks of adsorbed gases were observed under ambient conditions of 293 K and 1 atm. A guest-induced transition at ∼153 K resulting in the opening of new adsorption sites was inferred from the Raman spectral changes in the C-H stretching modes and low-frequency modes (<200 cm-1). In contrast to a single vibrational mode generally reported for entrapped N2, we show three Raman modes of adsorbed N2 in ZIF-4. The adsorption is facilitated by dispersive and quadrupolar interactions. From our temperature-dependent Raman results and theoretical analysis based on the density functional tight-binding approach, we conclude that the C-Hs are the preferred adsorption sites on ZIF-4 in the following order: C4-H, C5-H > C2-H > center of the Im ring (interacting with C-H centers) > center of the cavity. We also show that with an increasing concentration of N2 adsorbed at low temperatures, the ZIF-4 structure undergoes shear distortion of the window formed by 4-imidazole rings and consequent volumetric expansion. Our results have immediate implications in the field of porous materials and could be vital in identifying subtle structural transformations that may favor or hinder guest adsorption.

Raman spectroscopy, an ideal tool for studying the physical properties and applications of metal-organic frameworks (MOFs).

Metal-organic frameworks (MOFs) are a unique family of materials constructed by coordinating metal ions or clusters to bridging organic ligands. Many of these materials are well known for their intricate structures, and exceptional gas adsorption properties, and have potential applications in the separation of alkanes, catalysis, energy storage, surface-enhanced Raman spectroscopy (SERS) based detections, and diagnostics. In situ or in operando Raman spectroscopic studies provide real-time information about the different processes and associated structural changes in MOFs. In the last few decades, there has been phenomenal growth in the publications on MOFs containing insights from Raman spectroscopy. Such studies have helped the research community in identifying the adsorption sites, defect sites, structural or spin transitions, reaction centers, intermediates, etc. In this review, we present the current research status of Raman spectroscopy in probing the structure, guest adsorption, catalytic activity, and reaction mechanisms of MOFs, and their application in energy storage and SERS detection. We highlight the advancements in the Raman spectroscopy technique that have facilitated in situ studies in atmosphere as well as various chemical environments. We briefly discuss the relevance of computational studies in understanding phonon modes and predicting the stability of MOFs. Although this review is particularly focussed on works related to Raman spectroscopy of MOFs, we do discuss infrared studies on MOFs, where such results or analyses are missing from the Raman studies. These discussions have been provided with the intent to develop similar analysis techniques or methods in Raman spectroscopy research.

SERS combined with PCR as a potent tool for detecting mutations: a case study of tomato plants.

Conventional methods of detecting economically essential mutations have several disadvantages. Even though fluorescence-based methods are still the best option, Surface-Enhanced Raman Spectroscopy (SERS) may soon emerge as an alternative to the current techniques for detecting these mutations, because of its ability to detect molecular vibrational signatures. We were able to identify and develop a PCR-based SERS assay that can relentlessly differentiate between different types of indels, and SNPs as demonstrated in the case of tomato genome related to tomato yellow leaf curl virus and root-knot nematodes, diseases that are economically significant to the global agriculture industry and where the selection of resistant crops is the best solution. This tri-primer assay utilizes mutation-specific forward primers and SERS probes tagged with FAM and Cy3 dyes, specific for each allele of a particular gene (Ty-3 and Mi-1). The unique Raman spectral features of these dyes enabled to perform of multiplexing, which made it possible to detect not only the indel type but also the zygosity in a single experiment. Moreover, this technique successfully differentiated between two different SNP-based alleles. Therefore, due to its efficient multiplexing capability and lack of the need for quenchers, it has the potential to become a powerful onsite and offsite screening tool in the not-too-distant future.

Insights on Aggregation of Hen Egg-White Lysozyme from Raman Spectroscopy and MD Simulations.

Protein misfolding and aggregation play a significant role in several neurodegenerative diseases. In the present work, the spontaneous aggregation of hen egg-white lysozyme (HEWL) in an alkaline pH 12.2 at an ambient temperature was studied to obtain molecular insights. The time-dependent changes in spectral peaks indicated the formation of ß sheets and their effects on the backbone and amino acids during the aggregation process. Introducing iodoacetamide revealed the crucial role of intermolecular disulphide bonds amidst monomers in the aggregation process. These findings were corroborated by Molecular Dynamics (MD) simulations and protein-docking studies. MD simulations helped establish and visualize the unfolding of the proteins when exposed to an alkaline pH. Protein docking revealed a preferential dimer formation between the HEWL monomers at pH 12.2 compared with the neutral pH. The combination of Raman spectroscopy and MD simulations is a powerful tool to study protein aggregation mechanisms.

Pressure induced topological and topological crystalline insulators.

Research on topological and topological crystalline insulators (TCIs) is one of the most intense and exciting topics due to its fascinating fundamental science and potential technological applications. Pressure (strain) is one potential pathway to induce the non-trivial topological phases in some topologically trivial (normal) insulating or semiconducting materials. In the last ten years, there have been substantial theoretical and experimental efforts from condensed-matter scientists to characterize and understand pressure-induced topological quantum phase transitions (TQPTs). In particular, a promising enhancement of the thermoelectric performance through pressure-induced TQPT has been recently realized; thus evidencing the importance of this subject in society. Since the pressure effect can be mimicked by chemical doping or substitution in many cases, these results have opened a new route to develop more efficient materials for harvesting green energy at ambient conditions. Therefore, a detailed understanding of the mechanism of pressure-induced TQPTs in various classes of materials with spin-orbit interaction is crucial to improve their properties for technological implementations. Hence, this review focuses on the emerging area of pressure-induced TQPTs to provide a comprehensive understanding of this subject from both theoretical and experimental points of view. In particular, it covers the Raman signatures of detecting the topological transitions (under pressure), some of the important pressure-induced topological and TCIs of the various classes of spin-orbit coupling materials, and provide future research directions in this interesting field.

Modulation of biliverdin dynamics and spectral properties by Sandercyanin.

Biliverdin IX-alpha (BV), a tetrapyrrole, is found ubiquitously in most living organisms. It functions as a metabolite, pigment, and signaling compound. While BV is known to bind to diverse protein families such as heme-metabolizing enzymes and phytochromes, not many BV-bound lipocalins (ubiquitous, small lipid-binding proteins) have been studied. The molecular basis of binding and conformational selectivity of BV in lipocalins remains unexplained. Sandercyanin (SFP)-BV complex is a blue lipocalin protein present in the mucus of the Canadian walleye (Stizostedion vitreum). In this study, we present the structures and binding modes of BV to SFP. Using a combination of designed site-directed mutations, X-ray crystallography, UV/VIS, and resonance Raman spectroscopy, we have identified multiple conformations of BV that are stabilized in the binding pocket of SFP. In complex with the protein, these conformers generate varied spectroscopic signatures both in their absorption and fluorescence spectra. We show that despite no covalent anchor, structural heterogeneity of the chromophore is primarily driven by the D-ring pyrrole of BV. Our work shows how conformational promiscuity of BV is correlated to the rearrangement of amino acids in the protein matrix leading to modulation of spectral properties.

Unusual CO2 Adsorption in ZIF-7: Insight from Raman Spectroscopy and Computational Studies.

Here, we use Raman spectroscopy to investigate temperature-dependent changes in the atomic-scale structure of the zeolitic imidazolate framework ZIF-7 in a CO2 atmosphere and uncover the mechanism of maximal CO2 adsorption at 206 K. At 301 K, the Raman spectra of ZIF-7 at various CO2 gas pressures reveal a narrow-pore (np) to large-pore (lp) phase transition commencing at 0.1 bar as a result of adsorption of CO2, as evident in the appearance of Fermi resonance bands of CO2 at 1272 and 1376 cm-1. Moreover, the Raman inactive bending mode of CO2 becomes active due to geometrical distortion of adsorbed CO2. It further splits into two peaks due to hydrogen bonding interactions between CO2 and the benzene ring of the benzimidazole linker ZIF-7, as supported by our computational studies. In addition, the interaction between CO2 molecules plays a key role. Upon reducing the temperature at 1 bar CO2 gas pressure, ZIF-7 exhibits softening of the imidazole puckering mode and the Fermi resonance CO2 band due to interactions between CO2 and the framework through hydrogen bonding. At 206 K, substantial modification in the lattice mode and disappearance of the Raman inactive CO2 bending mode confirm the changes in the size of the pore cavity through structural rearrangements of CO2.

Erythroid spectrin binding modulates peroxidase and catalase activity of heme proteins.

Hemoglobin oxidation due to oxidative stress and disease conditions leads to the generation of ROS (reactive oxygen species) and membrane attachment of hemoglobin in-vivo, where its redox activity leads to peroxidative damage of membrane lipids and proteins. Spectrin, the major component of the red blood cell (RBC) membrane skeleton, is known to interact with hemoglobin and, here this interaction is shown to increase hemoglobin peroxidase activity in the presence of reducing substrate ABTS (2', 2'-Azino-Bis-3-Ethylbenzothiazoline-6-Sulfonic Acid). It is also shown that in the absence of reducing substrate, spectrin forms covalently cross-linked aggregates with hemoglobin which display no peroxidase activity. This may have implications in the clearance of ROS and limiting peroxidative damage. Spectrin is found to modulate the peroxidase activity of different hemoglobin variants like A, E, and S, and of isolated globin chains from each of these variants. This may be of importance in disease states like sickle cell disease and HbE-ß-thalassemia, where increased oxidative damage and free globin subunits are present due to the defects inherent in the hemoglobin variants associated with these diseases. This hypothesis is corroborated by lipid peroxidation experiments. The modulatory role of spectrin is shown to extend to other heme proteins, namely catalase and cytochrome-c. Experiments with free heme and Raman spectroscopy of heme proteins in the presence of spectrin show that structural alterations occur in the heme moiety of the heme proteins on spectrin binding, which may be the structural basis of increased enzyme activity.

Polaronic Signatures in Doped and Undoped Cesium Lead Halide Perovskite Nanocrystals through a Photoinduced Raman Mode.

Lead halide perovskites (LHPs) are promising candidates for photovoltaic applications as they exhibit large carrier diffusion lengths and long carrier lifetimes among many other interesting properties. One of the widely accepted mechanisms for these properties is polaron formation, which is mainly driven by octahedral distortions of the inorganic framework. Since structure modifications of the framework largely affect associated distortions, we investigated Mn-doped and undoped CsPbX3 (where X = Cl, Br, Cl/Br) using a local probe via micro-Raman spectroscopy and density functional theory (DFT) calculations for polaron formation. Our results highlight a new vibrational lattice mode at 132 cm-1 due to polaronic distortion upon photoinduction. From the DFT studies, we have shown that the polaronic states are dominated by the B-site cation in the perovskite structure, but it is the strong covalent overlap of the halide which determines its stability. This elucidation to map polaronic signatures with excellent spatial resolution using traditional Raman spectroscopy can be used as a simple tool to understand the structural changes and their impacted electronic properties and thus design superior devices using its in situ applications.

Interfacial tetrazine click chemistry mediated assembly of multifunctional colloidosomes.

We demonstrate that tetrazine ligation chemistry can be employed to cross-link and assemble gold nanoparticles at the water-oil interface to create plasmonic colloidosomes. These biocompatible colloidosomes exhibit size tunability via controllable ligation kinetics and display high encapsulation efficiency, size-selective permeability, and surface-enhanced Raman scattering (SERS)-based sensing modality.

The CdTiO3/BaTiO3 superlattice interface from first principles.

The oxide interface has been studied extensively in the past decades and exhibits different physical properties from the constituent bulks. Using first-principles electronic structure calculations, we investigated the interface of CdTiO3/BaTiO3 (CTO/BTO) superlattice with ferroelectric BaTiO3. In this case, the conduction bands of CdTiO3 are composed of Cd-5s orbitals with low electron effective mass and nondegenerate dispersion, and thus expected to have high mobility. We predicted a controllable conductivity at the interface, and further analyzed how the polarization direction and strength affect the conductivity. We also explored the relationship between two components: thickness and polarization. Intriguingly, the total polarization in CTO/BTO might be even larger than that of ferroelectric bulk BaTiO3. Therefore, we found a way to maximize the superlattice polarization by increasing the fraction of the CdTiO3 layers, based on the interesting dependence of the total polarization and CTO/BTO ratio.

Divalent Ion-Induced Switch in DNA Cleavage of KpnI Endonuclease Probed through Surface-Enhanced Raman Spectroscopy.

We demonstrate the remarkable ability of surface-enhanced Raman spectroscopy (SERS) to track the allosteric changes in restriction endonuclease KpnI (R.KpnI) caused by metal ions. R.KpnI binds and promiscuously cleaves DNA upon activation by Mg2+ ions. However, the divalent ion Ca2+ induces high fidelity cleavage, which can be overcome by higher concentrations of Mg2+ ions. In the absence of any 3D crystal structure, for the first time, we have elucidated the structural underpinnings of such a differential effect of divalent ions on the endonuclease activity. A combined SERS and molecular dynamics (MD) approach showed that Ca2+ ion activates an enzymatic switch in the active site, which is responsible for the high fidelity activity of the enzyme. Thus, SERS in combination with MD simulations provides a powerful tool for probing the link between the structure and activity of enzyme molecules that play vital roles in DNA transactions.

Covalent Graphene-MOF Hybrids for High-Performance Asymmetric Supercapacitors.

In this work, the covalent attachment of an amine functionalized metal-organic framework (UiO-66-NH2  = Zr6 O4 (OH)4 (bdc-NH2 )6 ; bdc-NH2  = 2-amino-1,4-benzenedicarboxylate) (UiO-Universitetet i Oslo) to the basal-plane of carboxylate functionalized graphene (graphene acid = GA) via amide bonds is reported. The resultant GA@UiO-66-NH2 hybrid displayed a large specific surface area, hierarchical pores and an interconnected conductive network. The electrochemical characterizations demonstrated that the hybrid GA@UiO-66-NH2 acts as an effective charge storing material with a capacitance of up to 651 F g-1 , significantly higher than traditional graphene-based materials. The results suggest that the amide linkage plays a key role in the formation of a π-conjugated structure, which facilitates charge transfer and consequently offers good capacitance and cycling stability. Furthermore, to realize the practical feasibility, an asymmetric supercapacitor using a GA@UiO-66-NH2 positive electrode with Ti3 C2 TX MXene as the opposing electrode has been constructed. The cell is able to deliver a power density of up to 16 kW kg-1 and an energy density of up to 73 Wh kg-1 , which are comparable to several commercial devices such as Pb-acid and Ni/MH batteries. Under an intermediate level of loading, the device retained 88% of its initial capacitance after 10 000 cycles.

Surface-Enhanced Raman Spectroscopy as a Tool for Distinguishing Extracellular Vesicles under Autophagic Conditions: A Marker for Disease Diagnostics.

Extracellular vesicles (EVs) laden with lipids, proteins, DNA, and micro-RNAs play important biological functions in intercellular communication and have pivotal roles in pathophysiological conditions. Characterization of the EVs has always been a multistep process involving large volumes, and they are heterogeneous in size and properties. A multitude of approaches is used to distinguish the EVs. Here, we report simple citrate reduced silver nanoparticles assisted surface-enhanced Raman spectroscopy (SERS) as a tool to distinguish EVs extracted from several cell lines isolated under autophagic conditions (nitrogen starvation). This study is the first report of its kind in characterizing EVs from cells under autophagic conditions using SERS. We used two cancerous cell lines, HeLa, its corresponding autophagy-deficient cell line (Atg5-/-), and a noncancerous cell line, HEK293, to isolate EVs. Our study helps in the facile detection and differentiation of EVs isolated between two closely related human cell lines that differ by their autophagic ability. The principal component analysis (PCA) of the SERS spectra of these EVs consistently showed the presence of distinct chemical compositions of the EVs. SERS of EVs can help in probing more into the molecular level information from EVs and could become a powerful tool once coupled with improved microscopy techniques for diagnosis and therapy.

Functional Monochalcogenides: Raman Evidence Linking Properties, Structure, and Metavalent Bonding.

Pressure- and temperature-dependent Raman scattering in GeSe, SnSe, and GeTe for pressures beyond 50 GPa and for temperatures ranging from 78 to 800 K allow us to identify structural and electronic phase transitions, similarities between GeSe and SnSe, and differences with GeTe. Calculations help to deduce the propensity of GeTe for defect formation and the doping that results from it, which gives rise to strong Raman damping beyond anomalous anharmonicity. These properties are related to the underlying chemical bonding and consistent with a recent classification of bonding in several chalcogenide materials that puts GeTe in a separate class of "incipient" metals.

Deconvolution of phase-size-strain effects in metal carbide nanocrystals for enhanced hydrogen evolution.

Understanding the descriptors of electrochemical activity and ways to modulate them are of paramount importance for the efficient structural engineering of electrocatalysts. Although, many studies separately elucidated the significance of thermodynamic and kinetic descriptors, lack of integrative approaches bars the potential utilization of these engineering tools for electrocatalytic activity enhancement. Here, through a facile post-carbonization synthetic technique using templated polyoxometalate based metal organic frameworks (POMOFs), we integrate three major structural engineering tools, viz. phase, size and strain into cost-effective Mo and W carbide electrocatalysts, and demonstrate how these factors qualitatively and quantitatively affect the critical descriptors of electrochemical activity. Deconvolution of these effects through combined experimental-theoretical analyses, shines new light on structure-activity relationships in this class of HER electrocatalysts. Optimum modulation of the structural tools culminated into the design of a superior electrocatalyst, consisting of ultrasmall γ-WC nanocrystals supported on N doped graphitic carbon that exhibited multifold activity enhancement in terms of onset potential, current density and Tafel slope compared to its structural analogues reported in this work and elsewhere. The present comprehensive study showcasing the effects of the structural engineering tools on activity will have considerable influence on future designs of more efficient nano-composite electrocatalysts.

Minerals to Functional Materials: Characterization of Structural Phase Transitions and Raman Analysis of a Superionic Phase in Na6Co(SO4)4.

In search of promising Na+ ion conductors, we have detected a superionic phase in a Vantoffite mineral, Na6Co(SO4)4, at 570 °C, thus enhancing the use of minerals to produce futuristic solid state electrolytes. Na6Co(SO4)4 crystallizes concomitantly to produce di- and tetrahydrate forms from an aqueous solution. Both the crystal forms belong to a triclinic system, space group P1. The mineral transforms to a dehydrated phase as established by in situ single crystal X-ray diffraction at 217 °C and is shown to be isostructural with its Mn analogue. Even though thermal analysis indicates a single structural phase transition at 450 °C, the features associated with in situ powder X-ray diffraction as well as in situ Raman spectroscopy signify a second phase transition ≈540 °C and the behavior of ionic conductivity leads to a superionic phase (σ ≈ 10-2 S/cm at 570 °C). These observations are significant for the development and understanding of mineral based solid electrolytes.

Understanding the Mechanism of Ferroelectric Phase Transition in RbHSO4: A High-Pressure Raman Investigation.

Previous high-pressure dielectric and diffraction studies on rubidium hydrogen sulfate (RbHSO4) observed ferroelectric phase transition below 1 GPa pressure. We have performed high-pressure Raman spectroscopy studies on RbHSO4 up to a maximum pressure of 5.15 GPa and at ambient temperature to understand the microscopic origin and mechanism of ferroelectric transition. On the basis of the pressure dependence of Raman mode frequencies and their full-width at half-maxima, we observed a transition around a pressure of 0.3 GPa, similar to the ferroelectric transition discovered in dielectric measurements, followed by another transition around 2.4 GPa. These phase transitions are evident from the appearance/disappearance of Raman-active modes and the change in the slope of frequencies with pressures. From the pressure dependence of the S-O and S-OH frequencies, we deduce that HSO4- ion ordering results in ferroelectric phase transition around 0.3 GPa. Further, the transition around 2.4 GPa pressure is associated with significant changes in the stretching and bending vibrational frequencies and indicates a structural phase transition with possible lowering of the crystal symmetry. Interestingly, no significant changes are observed in the Raman spectrum around 1 GPa, at which a phase transition was noticed in earlier X-ray and dielectric studies.

Role of Explicit Solvation in the Simulation of Resonance Raman Spectra within Short-Time Dynamics Approximation.

In short-time dynamics approximation, relative resonance Raman (RR) intensity of a vibrational mode primarily depends on the magnitude of square of the excited-state gradient along the corresponding normal coordinate, ground-state normal mode eigenvector, and harmonic vibrational wavenumbers. In this study, through simulation of RR spectra of guanosine-5'-monophosphate (GMP) in two ππ* singlet excited states, we analyze how the explicitly hydrogen-bonded local solvation structure of the chromophore dictates intensities of the RR active modes in an unprecedented manner. We show that the accuracy of the structural model of solvated chromophore plays a decisive role in determining an optimal theoretical method for prediction of the Franck-Condon region of the ππ* excited states. 9-Methylguanine (9-meG) in complex with six water molecules (9-meG·6H2O) is found out to be the most accurate one for describing GMP in two different bright electronic states. We find that explicit hydrogen-bonded water molecules strongly influence computed RR intensities of GMP by modulating both the ground-state normal mode vectors and the excited-state energy gradients. We find that simultaneous inclusion of six explicit waters to describe the solute-solvent interaction near all hydration sites is essential for reliable prediction of the features of RR spectra in Lb and Bb electronic states of GMP.