Superconducting Cavity-Based Sensing of Band Gaps in 2D Materials.

The superconducting coplanar waveguide (SCPW) cavity plays an essential role in various areas like superconducting qubits, parametric amplifiers, radiation detectors, and studying magnon-photon and photon-phonon coupling. Despite its wide-ranging applications, the use of SCPW cavities to study various van der Waals 2D materials has been relatively unexplored. The resonant modes of the SCPW cavity exquisitely sense the dielectric environment. In this work, we measure the charge compressibility of bilayer graphene coupled to a half-wavelength SCPW cavity. Our approach provides a means to detect subtle changes in the capacitance of the bilayer graphene heterostructure, which depends on the compressibility of bilayer graphene, manifesting as shifts in the resonant frequency of the cavity. This method holds promise for exploring a wide class of van der Waals 2D materials, including transition metal dichalcogenides (TMDs) and their moiré, where DC transport measurement is challenging.

Three-Fold Coordination of Copper in Sulfides: A Blockade for Hole Carrier Delocalization but a Driving Force for Ultralow Thermal Conductivity.

Copper-rich sulfides are very promising for energy conversion applications due to their environmental compatibility, cost effectiveness, and earth abundance. Based on a comparative analysis of the structural and transport properties of Cu3BiS3 with those of tetrahedrite (Cu12Sb4S13) and other Cu-rich sulfides, we highlight the role of the cationic coordination types and networks on the electrical and thermal properties. By precession-assisted 3D electron diffraction analysis, we find very high anisotropic thermal vibration of copper attributed to its 3-fold coordination, with an anisotropic atomic displacement parameter up to 0.09 Å2. Density functional theory calculations reveal that these Cu atoms are weakly bonded and give rise to low-energy Einstein-like vibrational modes that strongly scatter heat-carrying acoustic phonons, leading to ultralow thermal conductivity. Importantly, we demonstrate that the 3-fold coordination of copper in Cu3BiS3 and in other copper-rich sulfides constituted of interconnected CuS3 networks causes a hole blockade. This phenomenon hinders the possibility of optimizing the carrier concentration and electronic properties through mixed valency Cu+/Cu2+, differently from tetrahedrite and most other copper-rich chalcogenides, where the main interconnected Cu-S network is built of CuS4 tetrahedra. The comparison with various copper-rich sulfides demonstrates that seeking for frameworks characterized by the coexistence of tetrahedral and 3-fold coordinated copper is very attractive for the discovery of efficient thermoelectric copper-rich sulfides. Considering that lattice vibrations and carrier concentration are key factors for engineering transport phenomena (electronic, phonon, ionic, etc.) in copper-rich chalcogenides for various types of applications, our findings improve the guidelines for the design of materials enabling sustainable energy solutions with wide-ranging applications.

Strong Antibonding I (p)-Cu (d) States Lead to Intrinsically Low Thermal Conductivity in CuBiI4.

Chemical bonding present in crystalline solids has a significant impact on how heat moves through a lattice, and with the right chemical tuning, one can achieve extremely low thermal conductivity. The desire for intrinsically low lattice thermal conductivity (κlat) has gained widespread attention in thermoelectrics, in refractories, and nowadays in photovoltaics and optoelectronics. Here we have synthesized a high-quality crystalline ingot of cubic metal halide CuBiI4 and explored its chemical bonding and thermal transport properties. It exhibits an intrinsically ultralow κlat of ∼0.34-0.28 W m-1 K-1 in the temperature range 4-423 K with an Umklapp crystalline peak of 1.82 W m-1 K-1 at 20 K, which is surprisingly lower than other copper-based halide or chalcogenide materials. The crystal orbital Hamilton population analysis shows that antibonding states generated just below the Fermi level (Ef), which arise from robust copper 3d and iodine 5p interactions, cause copper-iodide bond weakening, which leads to reduction of the elastic moduli and softens the lattice, finally to produce extremely low κlat in CuBiI4. The chemical bonding hierarchy with mixed covalent and ionic interactions present in the complex crystal structure generates significant lattice anharmonicity and a low participation ratio in low-lying optical phonon modes originating mostly from localized copper-iodide bond vibrations. We have obtained experimental evidence of these low-lying modes by low-temperature specific heat capacity measurement as well as Raman spectroscopy. The presence of strong p-d antibonding interactions between copper and iodine leads to anharmonic soft crystal lattice which gives rise to low-energy localized optical phonon bands, suppressing the heat-carrying acoustic phonons to steer intrinsically ultralow κlat in CuBiI4.

Lone Pair Rotation and Bond Heterogeneity Leading to Ultralow Thermal Conductivity in Aikinite.

Understanding the relationship between the crystal structure, chemical bonding, and lattice dynamics is crucial for the design of materials with low thermal conductivities, which are essential in fields as diverse as thermoelectrics, thermal barrier coatings, and optoelectronics. The bismuthinite-aikinite series, Cu1-x□xPb1-xBi1+xS3 (0 ≤ x ≤ 1, where □ represents a vacancy), has recently emerged as a family of n-type semiconductors with exceptionally low lattice thermal conductivities. We present a detailed investigation of the structure, electronic properties, and the vibrational spectrum of aikinite, CuPbBiS3 (x = 0), in order to elucidate the origin of its ultralow thermal conductivity (0.48 W m-1 K-1 at 573 K), which is close to the calculated minimum for amorphous and disordered materials, despite its polycrystalline nature. Inelastic neutron scattering data reveal an anharmonic optical phonon mode at ca. 30 cm-1, attributed mainly to the motion of Pb2+ cations. Analysis of neutron diffraction data, together with ab-initio molecular dynamics simulations, shows that the Pb2+ lone pairs are rotating and that, with increasing temperature, Cu+ and Pb2+ cations, which are separated at distances of ca. 3.3 Å, exhibit significantly larger displacements from their equilibrium positions than Bi3+ cations. In addition to bond heterogeneity, a temperature-dependent interaction between Cu+ and the rotating Pb2+ lone pair is a key contributor to the scattering effects that lower the thermal conductivity in aikinite. This work demonstrates that coupling of rotating lone pairs and the vibrational motion is an effective mechanism to achieve ultralow thermal conductivity in crystalline materials.

A Tunable Structural Family with Ultralow Thermal Conductivity: Copper-Deficient Cu1-x□xPb1-xBi1+xS3.

Understanding the mechanism that connects heat transport with crystal structures and order/disorder phenomena is crucial to develop materials with ultralow thermal conductivity (κ), for thermoelectric and thermal barrier applications, and requires the study of highly pure materials. We synthesized the n-type sulfide CuPbBi5S9 with an ultralow κ value of 0.6-0.4 W m-1 K-1 in the temperature range 300-700 K. In contrast to prior studies, we show that this synthetic sulfide does not exhibit the ordered gladite mineral structure but instead forms a copper-deficient disordered aikinite structure with partial Pb replacement by Bi, according to the chemical formula Cu1/3□2/3Pb1/3Bi5/3S3. By combining experiments and lattice dynamics calculations, we elucidated that the ultralow κ value of this compound is due to very low energy optical modes associated with Pb and Bi ions and, to a smaller extent, Cu. This vibrational complexity at low energy hints at substantial anharmonic effects that contribute to enhance phonon scattering. Importantly, we show that this aikinite-type sulfide, despite being a poor semiconductor, is a potential matrix for designing novel, efficient n-type thermoelectric compounds with ultralow κ values. A drastic improvement in the carrier concentration and thermoelectric figure of merit have been obtained upon Cl for S and Bi for Pb substitution. The Cu1-x□xPb1-xBi1+xS3 series provides a new, interesting structural prototype for engineering n-type thermoelectric sulfides by controlling disorder and optimizing doping.

Nature-Inspired Coral-like Layered [Co0.79Al0.21(OH)2(CO3)0.11]·mH2O for Fast Selective ppb Level Capture of Cr(VI) from Contaminated Water.

Rapid industrialization has led to the release of hexavalent chromium (Cr(VI)), a "Class A" human carcinogen, mutagen, and teratogen in biological systems. Current adsorbents like anionic exchange resins and metal-organic frameworks can remove harmful heavy metal oxyanions from water but are not stable in a broad pH range, suffer from selectivity, and cannot capture them from trace values below the tolerance limits given by the U.S. EPA (100 ppb) and WHO (50 ppb). Herein, we have synthesized nature-inspired coral-like three-dimensional hierarchical structures of [Co0.79Al0.21(OH)2(CO3)0.11]·mH2O (CoAl-LDH) that sets a new benchmark for sequestering oxyanions of Cr(VI). CoAl-LDH shows a broad pH working range (1.93-12.22), high selectivity toward saturated water samples containing monovalent (Cl-, F-, Br-, and NO3-) and divalent (SO42-) anions with fast kinetics (reaches equilibrium within a minute), high capacity (93.4 ± 7.8 mg g-1), and high distribution coefficient of 1.09 × 106 mL g-1. Unlike other materials, it can decrease Cr(VI) concentration up to 0.012 ppb. This high selectivity for Cr(VI) is linked to the weak bonding interaction between Cr2O72- and brucite-like layers, as revealed from thermogravimetric and infrared spectroscopy. With these remarkable features coupled with low cost and an environmentally friendly nature, we have also designed an anion exchange column that can remove >99% Cr(VI) with just 1 wt % of CoAl-LDH and 99 wt % of sand and is a prominent candidate for the elimination of Cr(VI) from industrial effluents.

Synthesis and Localized Photoluminescence Blinking of Lead-Free 2D Nanostructures of Cs3 Bi2 I6 Cl3 Perovskite.

Two-dimensional (2D) lead-free halide perovskites have generated enormous perception in the field of optoelectronics due to their fascinating optical properties. However, an in-depth understanding on their shape-controlled charge-carrier recombination dynamics is still lacking, which could be resolved by exploring the photoluminescence (PL) blinking behaviour at the single-particle level. Herein, we demonstrate, for the first time, the synthesis of nanocrystals (NCs) and 2D nanosheets (NSs) of layered mixed halide, Cs3 Bi2 I6 Cl3 , by solution-based method. We applied fluorescence microscopy and super-resolution optical imaging at single-particle level to investigate their morphology-dependent PL properties. Narrow emission line widths and passivation of non-radiative defects were evidenced for 2D layered nanostructures, whereas the activation of shallow trap states was recognized at 77 K. Interestingly, individual NCs were found to display temporal intermittency (blinking) in PL emission. On the other hand, NS showed temporal PL intensity fluctuations within localized domains of the crystal. In addition, super-resolution optical image of the NS from localization-based method showed spatial inhomogeneity of the PL intensity within perovskite crystal.

BODIPY-Based Molecules for Biomedical Applications.

BODIPY (4,4-difluoro-4-bora-3a,4a-diaza-s-indacene) derivatives have attracted attention as probes in applications like imaging and sensing due to their unique properties like (1) strong absorption and emission in the visible and near-infrared regions of the electromagnetic spectrum, (2) strong fluorescence and (3) supreme photostability. They have also been employed in areas like photodynamic therapy. Over the last decade, BODIPY-based molecules have even emerged as candidates for cancer treatments. Cancer remains a significant health issue world-wide, necessitating a continuing search for novel therapeutic options. BODIPY is a flexible fluorophore with distinct photophysical characteristics and is a fascinating drug development platform. This review provides a comprehensive overview of the most recent breakthroughs in BODIPY-based small molecules for cancer or disease detection and therapy, including their functional potential.

Controlling the Thermoelectric Properties of Nb-Doped TiO2 Ceramics through Engineering Defect Structures.

Donor-doped TiO2 ceramics are promising high-temperature oxide thermoelectrics. Highly dense (1 - x)TiO2-xNb2O5 (0.005 ≤ x ≤ 0.06) ceramics were prepared by a single-step, mixed-oxide route under reducing conditions. The microstructures contained polygonal-shaped grains with uniform grain size distributions. Subgrain structures were formed in samples with low Nb contents by the interlacing of rutile and higher-order Magnéli phases, reflecting the high density of shear planes and oxygen vacancies. Samples prepared with a higher Nb content showed no subgrain structures but high densities of planar defects and lower concentrations of oxygen vacancies. Through optimizing the concentration of point defects and line defects, the carrier concentration and electrical conductivity were enhanced, yielding a much improved power factor of 5.3 × 10-4 W m-1 K-2 at 823 K; lattice thermal conductivity was significantly reduced by enhanced phonon scattering. A low, temperature-stable thermal conductivity of 2.6 W m-1 K-1 was achieved, leading to a ZT value of 0.17 at 873 K for compositions with x = 0.06, the highest ZT value reported for single Nb-doped TiO2 ceramics without the use of spark plasma sintering (SPS). We demonstrate the control of the thermoelectric properties of Nb-doped TiO2 ceramics through the development of balanced defect structures, which could guide the development of future oxide thermoelectric materials.

Charge Transfer in the Heterostructure of CsPbBr3 Nanocrystals with Nitrogen-Doped Carbon Dots.

Heterostructures of inorganic halide perovskites with mixed-dimensional inorganic nanomaterials have shown great potential not only in the field of optoelectronic energy devices and photocatalysis but also for improving our fundamental understanding of the charge transfer across the heterostructure interface. Herein, we present for the first time the heterostructure integration of the CsPbBr3 nanocrystal with an N-doped carbon dot. We explore the photoluminescence (PL) and photoconductivity of the heterostructure of CsPbBr3 nanocrystals and N-doped carbon dots. PL quenching of CsPbBr3 nanocrystals with the addition of N-doped carbon dots was observed. The photoexcited electrons from the conduction band of CsPbBr3 are trapped in the N-acceptor state of N-doped carbon dots, and the charge transfer occurs via quasi type II-like electronic band alignment. The charge transfer in the halide perovskite-based heterostructure should motivate further research into the new heterostructure synthesis with perovskites and the fundamental understanding of the mechanism of charge/energy transfer across the heterostructure interface.

Correction: An efficient one pot ipso-nitration: structural transformation of a dipeptide by N-terminus modification.

[This corrects the article DOI: 10.1039/C5RA09789D.].

Mechanochemical Synthesis and Temperature-Dependent Optical Properties of Thermochromic (Ag1-x Cux )2 HgI4.

Thermochromic materials are generally synthesized via high-temperature melting reaction or solution-based synthesis. Herein, all-inorganic thermochromic compounds of (Ag1-x Cux )2 HgI4 were synthesized by solvent-free simple and scalable mechanochemical grinding at room temperature. Temperature-dependent electronic absorption spectroscopy along with DSC analysis confirmed the thermochromic events within these materials, and the phase transition temperature varied with solid solution compositions. The photoluminescence (PL) spectra is red-shifted with the increase in the Cu content in (Ag1-x Cux )2 HgI4 (x=0-1).

Self-Healing Hydrogel from a Dipeptide and HCl Sensing.

Ordered self-assembly of small organic molecules may induce novel properties in a supramolecular arrangement and can act as advance functional materials. This paper discusses the development of a new stimuli-responsive dipeptide hydrogelator containing l-phenylalanine and α-aminoisobutyric acid (Aib). The dipeptide Boc-Phe-Aib-OH, on addition with three equivalent of sodium hydroxide and water, transformed into a robust hydrogel. The transparent hydrogel is self-healing in nature. The instant gelation is highly selective toward sodium hydroxide and does not need any sonication or heating-cooling cycle. The thixotropic nature of the gel has been confirmed by rheological step-strain experiments at room temperature. Moreover, in the oil-water mixture, the compound exhibits phase-selective gelation. When the gel cylinder is cut into pieces, it does not conduct electricity, but once self-healing occurs, it conducts electricity. The diffusion of rhodamine 6G through the hydrogel indicates the dynamic nature. The hydrogel is highly sensitive toward HCl, that is, in the presence of HCl vapor, the gel becomes deformed.

1-(2-aminophenyl)-1H-1,2,3-triazole-4-carboxylic acid: activity against Gram-positive and Gram-negative pathogens including Vibrio cholerae.

We report a new synthetic aromatic ε-amino acid containing a triazole moiety with antimicrobial potential against Gram-positive, Gram-negative and pathogenic bacteria including Vibrio cholerae. Structure-property relationship studies revealed that all the functional groups are essential to enhance the antimicrobial activity. The 1-(2-aminophenyl)-1H-1,2,3-triazole-4-carboxylic acid was synthesized by click chemistry. From X-ray crystallography, the amino acid adopts a kink-like structure where the phenyl and triazole rings are perpendicular to each other and the amine and acid groups maintain an angle of 60°. The agar diffusion test shows that the amino acid has significant antibacterial activity. The liquid culture test exhibits that the minimum inhibitory concentration (MIC) value for Bacillus subtilis and Vibrio cholerae is 59.5 µg ml-1. FE-SEM experiments were performed to study the morphological changes of bacterial shape after treatment with compound 1. The antimicrobial activity of the amino acid was further studied by DNA binding and degradation study, protein binding, dye-binding assay and morphological analysis. Moreover, the amino acid does not have any harmful effect on eukaryotes.

POSS-Appended Diphenylalanine: Self-Cleaning, Pollution-Protective, and Fire-Retardant Hybrid Molecular Material.

Ordered self-assemblies of hybrid molecules have potential as protective umbrellas against environmental pollution and corrosion. This article describes the design and fabrication of a new self-cleaning hybrid molecular material containing polyhedral oligomeric silsesquioxane (POSS) and diphenylalanine as hydrophobic and pollution-protective coating. The colorless organic-inorganic hybrid materials, in which the diphenylalanine motif controls the self-assembly, exhibit unique water resistance property and enhance mechanical strength of paper 1.5-fold. The hybrid building blocks self-assemble in antiparallel sheet manner through noncovalent interactions to form a supramolecular layerlike surface with enhanced roughness. The hybrid material is soluble in organic solvents at room temperature that makes it easy to coat on paper, wood, or metal surfaces. The coating is effective against rusting, corrosion, environmental pollution, and bacterial attack. The coating has been used as fire retardant and enhances fire safety. The sustainable molecular material is promising for the packaging industry and metal industry and artifact preservation.

A small molecule peptidomimetic of spider silk and webs.

A peptidomimetic compound containing leucine, tyrosine and malonic acid self-assembles through various noncovalent interactions to form spider silk-like fibers at ambient temperature. From the high-density liquid, a liquid-solid phase transition is initiated at 20 °C and solidification occurs upon contact with air. The fiber has comprehensive mechanical strength and optical properties similar to spider silk, and can be used to mimic a natural spider web.