Exploratory synthesis in new chemical spaces is the essence of solid-state chemistry. However, uncharted chemical spaces can be difficult to navigate, especially when materials synthesis is challenging. Nitrides represent one such space, where stringent synthesis constraints have limited the exploration of this important class of functional materials. Here, we employ a suite of computational materials discovery and informatics tools to construct a large stability map of the inorganic ternary metal nitrides. Our map clusters the ternary nitrides into chemical families with distinct stability and metastability, and highlights hundreds of promising new ternary nitride spaces for experimental investigation—from which we experimentally realized seven new Zn- and Mg-based ternary nitrides. By extracting the mixed metallicity, ionicity and covalency of solid-state bonding from the density functional theory (DFT)-computed electron density, we reveal the complex interplay between chemistry, composition and electronic structure in governing large-scale stability trends in ternary nitride materials.High-throughput computation is especially useful for materials screening where synthesis is challenging. Here, it is used to construct a stability map of ternary nitrides, allowing discovery of stable compounds and providing insight into principles that govern nitride stability.
Amorphous forms serve as thermodynamic upper bounds on the free energy scale for synthesis of metastable crystalline polymorphs. Realizing the growing number of possible or hypothesized metastable crystalline materials is extremely challenging. There is no rigorous metric to identify which compounds can or cannot be synthesized. We present a thermodynamic upper limit on the energy scale, above which the laboratory synthesis of a polymorph is highly unlikely. The limit is defined on the basis of the amorphous state, and we validate its utility by effectively classifying more than 700 polymorphs in 41 common inorganic material systems in the Materials Project for synthesizability. The amorphous limit is highly chemistry-dependent and is found to be in complete agreement with our knowledge of existing polymorphs in these 41 systems, whether made by the nature or in a laboratory. Quantifying the limits of metastability for realizable compounds, the approach is expected to find major applications in materials discovery.
Sergey Kh. Batygov, Liudmila V. Moiseeva, Valeria V. Vinokurova
et al.
Ce3+ luminescence was studied in a flurozirconate glass in the ZrF4–BaF2–LaF3–AlF3–NaF (ZBLAN) and in a fluorohafnate HfF4-BaF2-LaF3-AlF3-NaF (HBLAN) glass systems under X-ray and UV excitation. Ce3+ luminescence temperature quenching in glasses in the temperature range 77–300 K was observed. The Ce3+ luminescence quenching in ZBLAN glass host is conditioned by two mechanisms: via the electrons ionization from the excited 5d-level of Ce3+ into the conduction band (CB); and quenching as a result of the intersection of the Ce3+ ground state and excited state potential curves. In HBLAN glass host the luminescence quenching is caused by the intersection of the Ce3+ ground state and excited state potential curves in the temperature range 77–300 K. The activation energies of Ce3+ luminescence quenching in ZBLAN and HBLAN have been determined.
Diabetic wounds are characterized by a refractory healing cycle resulting from the synergistic effects of hyperglycemic microenvironment, oxidative stress, bacterial infection, and impaired angiogenesis. Conventional hydrogel dressings, with limited functionality, struggle to address the complexities of chronic diabetic ulcers. Smart hydrogels, possessing biocompatibility, porous architectures mimicking extracellular matrix, and environmental responsiveness, have emerged as promising biomaterials for diabetic wound management. This review systematically elucidates the specific response mechanisms of smart hydrogels to wound microenvironmental stimuli, including pH, matrix metalloproteinase-9 (MMP-9), reactive oxygen species (ROS), and glucose levels, enabling on-demand release of antimicrobial agents and growth factors through dynamic bond modulation or structural transformations. Subsequently, the review highlights recent advances in novel hydrogel-based sensors fabricated via optical (photonic crystal, fluorescence) and electrochemical principles for real-time monitoring of glucose levels and wound pH. Finally, critical challenges in material development and scalable manufacturing of multifunctional hydrogel components are discussed, alongside prospects for precision diagnostics and therapeutics in diabetic wound care.
Anna Borisovna Karabanova, Sergey Olegovich Ilyin, Anna Vladimirovna Vlasova
et al.
Despite extensive use of polyvinylpyrrolidone (PVP)–polyethylene glycol (PEG) hydrogels in biomedical adhesives, a systematic understanding of how water content governs their rheological and adhesive performance remains lacking—particularly under variable humidity. This work addresses this gap by introducing 3–12 wt% hydroxypropyl cellulose (HPC) as a non-covalent crosslinker into a PVP/PEG gel (2/1 wt/wt) to tune its moisture uptake and stabilize viscoelasticity, thereby enabling robust, humidity-adaptive adhesion. Analysis of water content in hydrogels across a relative humidity range of 3% to 100% revealed that HPC restricts their water absorption capacity, thereby enhancing their tolerance to high-humidity conditions. The adhesive and rheological properties of the hydrogels were investigated as functions of HPC and water concentrations. With an increase in the HPC content, the adhesive properties of the initial low-water hydrogels decreased. However, high humidity strongly affected the hydrogels’ adhesive and rheological properties. The water content for hydrogels to maintain their adhesive properties was about 7–16%, depending on the hydrogel composition. This range corresponds to relative air humidity of 45–80%, tending to shift towards more moisture conditions under the effect of HPC. Thus, HPC enables PVP/PEG adhesives to operate over a broader range of relative humidities and in contact with wet skin when used in medicine as matrices for transdermal therapeutic systems, wound dressings, and flexible electrodes.
Maciej Combrzyński, Jakub Soja, Michał Staniak
et al.
Functional foods represent a new and thriving area of research. A significant direction of these studies is based on new products containing edible house cricket-derived additives. The aim of the presented studies was to determine the effect of using cricket powder (at 10% and 30% content) on the extrusion cooking parameters and the nutritional value, antioxidant activity, and selected physical properties of extruded potato-based snack pellets. The results suggest that house cricket powder is a promising functional ingredient. The processing efficiency and the physical and functional properties of the extrudates, including SME, WAI, WSI, bulk density, and mechanical durability, were affected by the addition of cricket powder, screw speed, and moisture content. Generally, higher levels of cricket powder reduced processing efficiency and altered structural properties due to changes in composition, particularly the balance between protein, fiber, and starch. The addition of cricket powder significantly improved antioxidant activity (>94% of DPPH scavenging for 30% content of additive) and increased the total polyphenol content in the assessed samples in comparison to potato bases (212.3 and 21.7 μg GAE/g dry weight, respectively). These innovative snack pellets containing cricket powder could be an appealing option due to their potential health benefits.
In the last 30 years we have assisted to a massive advance of nanomaterials in material science. Nanomaterials and structures, in addition to their small size, have properties that differ from those of larger bulk materials, making them ideal for a host of novel applications. The spread of nanotechnology in the last years has been due to the improvement of synthesis and characterization methods on the nanoscale, a field rich in new physical phenomena and synthetic opportunities. In fact, the development of functional nanoparticles has progressed exponentially over the past two decades. This work aims to extensively review 30 years of different strategies of surface modification and functionalization of noble metal (gold) nanoparticles, magnetic nanocrystals and semiconductor nanoparticles, such as quantum dots. The aim of this review is not only to provide in-depth insights into the different biofunctionalization and characterization methods, but also to give an overview of possibilities and limitations of the available nanoparticles.
Research on chemically stable inorganic perovskites has achieved rapid progress in terms of high efficiency exceeding 19% and high thermal stabilities, making it one of the most promising candidates for thermodynamically stable and high‐efficiency perovskite solar cells. Among those inorganic perovskites, CsPbI3 with good chemical components stability possesses the suitable bandgap (≈1.7 eV) for single‐junction and tandem solar cells. Comparing to the anisotropic organic cations, the isotropic cesium cation without hydrogen bond and cation orientation renders CsPbI3 exhibit unique optoelectronic properties. However, the unideal tolerance factor of CsPbI3 induces the challenges of different crystal phase competition and room temperature phase stability. Herein, the latest important developments regarding understanding of the crystal structure and phase of CsPbI3 perovskite are presented. The development of various solution chemistry approaches for depositing high‐quality phase‐pure CsPbI3 perovskite is summarized. Furthermore, some important phase stabilization strategies for black phase CsPbI3 are discussed. The latest experimental and theoretical studies on the fundamental physical properties of photoactive phase CsPbI3 have deepened the understanding of inorganic perovskites. The future development and research directions toward achieving highly stable CsPbI3 materials will further advance inorganic perovskite for highly stable and efficient photovoltaics.
ABSTRACT With the rapid development of conductive polymers, they have shown great potential in room-temperature chemical gas detection, as their electrical conductivity can be changed upon exposure to oxidative or reductive gas molecules at room temperature. However, due to their relatively low conductivity and high affinity toward volatile organic compounds and water molecules, they always exhibit low sensitivity, poor stability, and gas selectivity, which hinder their practical gas sensor applications. In addition, inorganic sensitive materials show totally different advantages in gas sensors, such as high sensitivity, fast response to low concentration analytes, high surface area, and versatile surface chemistry, which could complement the conducting polymers in terms of the sensing characteristics. It seems to be a win-win choice to combine inorganic sensitive materials with polymers for gas detection due to their synergistic effects, which has attracted extensive interests in gas-sensing applications. In this review, we summarize the recent development in polymer-inorganic nanocomposite based gas sensors. The roles of inorganic nanomaterials in improving the gas-sensing performances of conducting polymers are introduced and the progress of conducting polymer-inorganic nanocomposites including metal oxides, metal, carbon (carbon nanotube, graphene), and ternary composites are presented. Finally, a conclusion and a perspective in the field of gas sensors incorporating conducting polymer-inorganic nanocomposite are summarized. Graphical Abstract
Christina Stamou, Zoi G. Lada, Sophia Paschalidou
et al.
Metal complexes of benzotriazole-type ligands continue to attract the intense interest of many inorganic chemistry groups around the world for a variety of reasons, including their aesthetically beautiful structures, physical properties and applications. 1-methylbenzotriazole (Mebta) is the <i>N</i>-substituted archetype of the parent 1<i>H</i>-benzotriazole. The first attempt to build a “periodic table” of Mebta, which includes its complexes with several metal ions, is described in this work. This, at first glance, trivial ligand has led to interesting results in terms of the chemistry, structures and properties of its metal complexes. This work reviews the to-date published coordination chemistry of Mebta with Mn(II), Fe(II), Fe(III), Co(II), Ni(II), Cu(I), Cu(II), Zn(II), Pd(II), Au(I) and {U<sup>VI</sup>O<sub>2</sub>}<sup>2+</sup>, with emphasis on their preparations, reactivity, structures and properties. Unpublished results from our group comprising other Co(II), Ni(II), Cu(II) and Zn(II) complexes, as well as Cd(II), Hg(II), Ag(I), In(III) and Sn(IV) ones are briefly reported. Mebta can also provide access to 1D and 3D heterometallic thiocyanato-bridged Co(II)/Hg(II) and Ni(II)/Hg(II) compounds. In almost all cases, Mebta behaves as a monodentate ligand with the nitrogen of position 3 of the azole ring as the donor atom. However, there are two copper complexes in which this molecule adopts a bidentate bridging coordination behavior. Our efforts to complete the “periodic table” of Mebta are continued.
Acid-driven multiphase chemistry of isoprene epoxydiols (IEPOX), key isoprene oxidation products, with inorganic sulfate aerosol yields substantial amounts of secondary organic aerosol (SOA) through the formation of organosulfur compounds. The extent and implications of inorganic-to-organic sulfate conversion, however, are unknown. In this article, we demonstrate that extensive consumption of inorganic sulfate occurs, which increases with the IEPOX-to-inorganic sulfate concentration ratio (IEPOX/Sulfinorg), as determined by laboratory measurements. Characterization of the total sulfur aerosol observed at Look Rock, Tennessee, from 2007 to 2016 shows that organosulfur mass fractions will likely continue to increase with ongoing declines in anthropogenic Sulfinorg, consistent with our laboratory findings. We further demonstrate that organosulfur compounds greatly modify critical aerosol properties, such as acidity, morphology, viscosity, and phase state. These new mechanistic insights demonstrate that changes in SO2 emissions, especially in isoprene-dominated environments, will significantly alter biogenic SOA physicochemical properties. Consequently, IEPOX/Sulfinorg will play an important role in understanding the historical climate and determining future impacts of biogenic SOA on the global climate and air quality.