Hasil untuk "Inorganic chemistry"

Petya Marinova, Denica Blazheva, Stoyanka Nikolova

<b>Background:</b> Gold (Au) complexes have emerged as promising anticancer candidates due to their distinct coordination chemistry and ability to modulate thiol-dependent and redox-regulated cellular pathways, particularly thioredoxin reductase (TrxR). In recent years, structurally diverse Au(I) and Au(III) complexes have been reported with potent in vitro anticancer activity; however, cross-study comparability and design principles remain unclear. <b>Aim:</b> This systematic review critically evaluates anticancer Au(I/III) complexes reported since 2016, with the specific aim of identifying how oxidation state, coordination geometry, and ligand class influence <i>in vitro</i> potency, selectivity, and translational potential. <b>Methods:</b> A PRISMA-guided literature search was performed in Scopus, Web of Science, PubMed, and ScienceDirect for studies published between January 2016 and March 2025. Two independent reviewers screened titles/abstracts and full texts according to predefined inclusion criteria. Only original studies reporting anticancer activity of structurally characterized Au(I/III) complexes in human cancer models were included. After the removal of duplicates, 1100 records were screened at the title and abstract level. Of these, 240 articles were assessed in full text for eligibility. Ultimately, 128 studies reporting anticancer activity of structurally characterized Au(I/III) complexes met the inclusion criteria and were included in the qualitative synthesis. Biological potency data were harmonized to μM units where applicable, and results were synthesized qualitatively due to heterogeneity in experimental design. <b>Results:</b> A total of 128 studies met the inclusion criteria. Au(I) complexes—particularly phosphine- and N-heterocyclic carbene (NHC)-based compounds—consistently showed sub-micromolar cytotoxicity in TrxR-dependent cancer cell lines, whereas Au(III) complexes displayed greater structural diversity but variable stability and redox behavior. In vivo efficacy was reported for a limited subset of compounds and was frequently constrained by solubility, systemic toxicity, or metabolic instability. <b>Conclusions:</b> The available evidence indicates that anticancer activity of gold complexes is strongly dependent on oxidation state, ligand environment, and redox stability. While Au(I) scaffolds show more reproducible in vitro potency, successful translation to in vivo models remains limited. This review defines structure–activity and structure–liability relationships that can guide the rational design of next-generation gold-based anticancer agents.

Anna A. Vorfolomeeva, Alena A. Zaguzina, Evgeny A. Maksimovskiy et al.

Lithium- and sodium-ion batteries (LIBs and SIBs) suffer from the significant degradation of electrochemical performance at low temperatures. This work presents promising hybrid anodes synthesized by the rapid thermolysis of ammonium tetrathiomolybdate and graphene oxide (GO) at 600 and 700 °C. Transmission electron microscopy revealed the formation of MoS₂ crystallites oriented along or perpendicular to the surface of reduced GO (rGO) layers. X-ray photoelectron spectroscopy found the covalent C–S bonds connecting components in the MoS₂/rGO hybrids. The MoS₂/rGO_600 hybrid showed higher specific capacities in LIBs of 1370 mAh/g, 835 mAh/g, and 711 mAh/g at a current density of 0.1 A/g and temperatures of 25 °C, 0 °C, and −20 °C, respectively, due to the presence of excess sulfur in the sample. Increasing the current density to 2 A/g retained 78 and 34% of the capacity at 25 °C and −20 °C. In SIBs, the MoS₂/rGO_700 hybrid showed more promising results, achieving 550 mAh/g at 0.1 A/g and 400 mAh/g at 2 A/g, while lowering the temperature to −20 °C retained 48 and 17% of the capacity. Such good SIB performance is attributed to the enrichment of the sample with vertically oriented MoS₂ layers covalently bonded to the rGO surface.

Melina Witt, Martin A. Lange, Wolfgang G. Zeier

Solid‐state batteries represent a new approach to energy storage, offering superior safety, higher energy density, and extended cycle life compared to conventional liquid electrolyte‐based lithium‐ion batteries. However, the practical application of solid‐state batteries is hindered by degradation phenomena, particularly on interfaces between components, compromising their long‐term performance. In this work, the kinetics of the state‐of‐charge‐dependent electrolyte degradation at the LiNi0.83Co0.11Mn0.06O2│Li6PS5Cl interface, as well as its influence on cycling performance, are systematically studied electrochemically in solid‐state battery half cells. Combining cycling and C‐rate experiments with electrochemical impedance spectroscopy reveals that half cells charged to higher cutoff potentials (≥3.8 V versus In/InLi; ≥4.4 V versus Li+/Li) exhibit significantly faster degradation kinetics. These influence the cycling performance leading to a plateau in the charge capacity at ≥3.8 V versus In/InLi, while the electrolyte degradation does not affect the bulk electrode transport. Overall, this work emphasizes the importance to investigate state‐of‐charge‐dependent decomposition kinetics in composite electrodes to better understand cycling behavior.

Evan W. Muller, Aleksey Ruditskiy, Jie Jiang et al.

Hybrid organic-inorganic perovskites with chiral organic cations are very interesting for optoelectronic applications because of their intrinsically chiral light-matter interactions. Chiral distortions in these materials lead to circular dichroism, circular birefringence, and circularly polarized luminescence in the band transitions of the inorganic sublattice. Raman-active vibrational modes in these crystals are governed by crystal symmetry and therefore are also strongly impacted by the nature and magnitude of the chiral distortions. Here, we report low-frequency Raman modes that are sensitive to circularly polarized excitation in chiral hybrid organic-inorganic perovskites (CHOIPs) across a wide range of structures and compositions. The circularly polarized Raman spectra from enantiomers of CHOIP single crystals exhibit sharp modes below 150 cm-1, corresponding to vibrations of the lead iodide octahedra. These modes exhibit strong differences in intensities (Raman optical activity, ROA) depending on the handedness of the excitation, with high degree of polarization for several modes. Calculations reveal the presence of several chiral phonon modes with opposite phonon angular momenta. The strong ROA and the chiral phonon modes are a direct consequence of chirality transfer from the chiral organic linker to the lead iodide octahedra in the CHOIP structure, resulting in a strong chiroptical response in the phonon modes.

Mijie Pang, Jianbing Jin, Arjo Segers et al.

Atmospheric chemistry encapsulates the emission of various pollutants, the complex chemistry reactions, and the meteorology dominant transport, which form a dynamic system that governs air quality. While deep learning (DL) models have shown promise in capturing intricate patterns for forecasting individual atmospheric component - such as PM2.5 and ozone - the critical interactions among multiple pollutants and the combined influence of emissions and meteorology are often overlook. This study introduces an advanced DL-based atmospheric chemistry transport model Zeeman for multi-component atmospheric chemistry simulation. Leveraging an attention mechanism, our model effectively captures the nuanced relationships among these constituents. Performance metrics demonstrate that our approach rivals numerical models, offering an efficient solution for atmospheric chemistry. In the future, this model could be further integrated with data assimilation techniques to facilitate efficient and accurate atmospheric emission estimation and concentration forecast.

Hans Gundlach, Keeper Sharkey, Jayson Lynch et al.

For decades, computational chemistry has been posited as one of the areas in which quantum computing would revolutionize. However, the algorithmic advantages that fault-tolerant quantum computers have for chemistry can be overwhelmed by other disadvantages, such as error correction, processor speed, etc. To assess when quantum computing will be disruptive to computational chemistry, we compare a wide range of classical methods to quantum computational methods by extending the framework proposed by Choi, Moses, and Thompson. Our approach accounts for the characteristics of classical and quantum algorithms, and hardware, both today and as they improve. We find that in many cases, classical computational chemistry methods will likely remain superior to quantum algorithms for at least the next couple of decades. Nevertheless, quantum computers are likely to make important contributions in two important areas. First, for simulations with tens or hundreds of atoms, highly accurate methods such as Full Configuration Interaction are likely to be surpassed by quantum phase estimation in the coming decade. Secondly, in cases where quantum phase estimation is most efficient less accurate methods like Couple Cluster and Moller-Plesset, could be surpassed in fifteen to twenty years if the technical advancements for quantum computers are favorable. Overall, we find that in the next decade or so, quantum computing will be most impactful for highly accurate computations with small to medium-sized molecules, whereas classical computers will likely remain the typical choice for calculations of larger molecules.

Stefania-Claudia Jitaru, Andra-Cristina Enache, Corneliu Cojocaru et al.

Currently, ultrashort oligopeptides consisting of fewer than eight amino acids represent a cutting-edge frontier in materials science, particularly in the realm of hydrogel formation. By employing solid-phase synthesis with the Fmoc/tBu approach, a novel pentapeptide, FEYNF-NH₂, was designed, inspired by a previously studied sequence chosen from hen egg-white lysozyme (FESNF-NH₂). Qualitative peptide analysis was based on reverse-phase high performance liquid chromatography (RP-HPLC), while further purification was accomplished using solid-phase extraction (SPE). Exact molecular ion confirmation was achieved by matrix-assisted laser desorption–ionization mass spectrometry (MALDI-ToF MS) using two different matrices (HCCA and DHB). Additionally, the molecular ion of interest was subjected to tandem mass spectrometry (MS/MS) employing collision-induced dissociation (CID) to confirm the synthesized peptide structure. A combination of research techniques, including Fourier-transform infrared spectroscopy (FTIR), fluorescence analysis, transmission electron microscopy, polarized light microscopy, and Congo red staining assay, were carefully employed to glean valuable insights into the self-assembly phenomena and gelation process of the modified FEYNF-NH₂ peptide. Furthermore, molecular docking simulations were conducted to deepen our understanding of the mechanisms underlying the pentapeptide’s supramolecular assembly formation and intermolecular interactions. Our study provides potential insights into amyloid research and proposes a novel peptide for advancements in materials science. In this regard, in silico studies were performed to explore the FEYNF peptide’s ability to form polyplexes.

Xiaoman Yu, Zimo Ren, Paolo Coghi et al.

Tea is a daily drink for most people, and one of its major ingredients, epigallocatechin-3-gallate (EGCG), has been widely recognized as a potent antioxidant with diverse biological activities. However, its low stability and bioavailability hinder its further clinical applications. In this study, we designed and synthesized a novel EGCG-valine derivative <b>4</b> by replacing the gallic acid with a valine moiety in four steps. The structural elucidation of derivative <b>4</b> was performed using NMR, IR, mass, and UV spectroscopies. Additionally, the physicochemical properties of <b>4</b> were predicted by SwissADME, showing improved drug-like parameters and intestinal absorption compared to the parent compound EGCG.

José A. C. Oliveira, Jonatas M. Negreiro, Fátima M. Nunes et al.

Hiroki Sayama

Hash Chemistry, a minimalistic artificial chemistry model of open-ended evolution, has recently been extended to non-spatial and cellular versions. The non-spatial version successfully demonstrated continuous adaptation and unbounded growth of complexity of self-replicating entities, but it did not simulate multiscale ecological interactions among the entities. On the contrary, the cellular version explicitly represented multiscale spatial ecological interactions among evolving patterns, yet it failed to show meaningful adaptive evolution or complexity growth. It remains an open question whether it is possible to create a similar minimalistic evolutionary system that can exhibit all of those desired properties at once within a computationally efficient framework. Here we propose an improved version called Structural Cellular Hash Chemistry (SCHC). In SCHC, individual identities of evolving patterns are explicitly represented and processed as the connected components of the nearest neighbor graph of active cells. The neighborhood connections are established by connecting active cells with other active cells in their Moore neighborhoods in a 2D cellular grid. Evolutionary dynamics in SCHC are simulated via pairwise competitions of two randomly selected patterns, following the approach used in the non-spatial Hash Chemistry. SCHC's computational cost was significantly less than the original and non-spatial versions. Numerical simulations showed that these model modifications achieved spontaneous movement, self-replication and unbounded growth of complexity of spatial evolving patterns, which were clearly visible in space in a highly intuitive manner. Detailed analysis of simulation results showed that there were spatial ecological interactions among self-replicating patterns and their diversity was also substantially promoted in SCHC, neither of which was present in the non-spatial version.

He Cao, Yanjun Shao, Zhiyuan Liu et al.

Multimodal Large Language Models (MLLMs) have seen growing adoption across various scientific disciplines. These advancements encourage the investigation of molecule-text modeling within synthetic chemistry, a field dedicated to designing and conducting chemical reactions to synthesize new compounds with desired properties and applications. Current approaches, however, often neglect the critical role of multiple molecule graph interaction in understanding chemical reactions, leading to suboptimal performance in synthetic chemistry tasks. This study introduces PRESTO(Progressive Pretraining Enhances Synthetic Chemistry Outcomes), a new framework that bridges the molecule-text modality gap by integrating a comprehensive benchmark of pretraining strategies and dataset configurations. It progressively improves multimodal LLMs through cross-modal alignment and multi-graph understanding. Our extensive experiments demonstrate that PRESTO offers competitive results in downstream synthetic chemistry tasks. The code can be found at https://github.com/IDEA-XL/PRESTO.

Ondřej Jankovský, Anna-Marie Lauermannová, Filip Antončík et al.

The excellent technical parameters of magnesium oxychloride cement (MOC) and its ability to sequester CO2 from the environment predestine its use as an alternative to Portland cement. However, its main shortcomings, low water resistance, and excessive water absorption need to be addressed to enable its wider application in construction. For this reason, the improvement of the water resistance of MOC-based composites through the use of nanosized molybdenum disulfide (MoS2) is the subject of this case study. The MOC-based composites were subjected to experimental testing of their chemical, structural and physical parameters using a wide range of advanced laboratory techniques. The composites enriched by MoS2 nanoadditive exhibited a densified and compact structure with improved mechanical parameters and stiffness. Water transport and storage were significantly decelerated and reduced by the incorporation of MoS2 nanoparticles, resulting in an improvement of water resistance, characterized by the softening coefficient, which was 66.1 % after 24 h of immersion in water, which is about 13.8 % higher than that of the reference MOC-based composite.

Efraín Albor-Ramírez, Miguel Reyes-Alberto, Luis M. Vidal-Flores et al.

Synthetic phantoms that recreate the characteristics of biological tissues are valuable tools for systematically studying and comprehending physiologies, pathologies, and biological processes related to tissues. The reproduction of mechanical and optical properties allows for the development and evaluation of novel systems and applications in areas such as imaging, optics, ultrasound, or dosimetry, among others. This paper proposes a methodology for manufacturing agarose-based phantoms that mimics the optical properties of healthy brain tissue within the wavelength infrared range of 800 to 820 nm. The fabrication of such phantoms enables the possibility of testing and experimentation in controlled and safe environments toward the design of new near-infrared multispectral imaging systems in neurosurgery. The results of an experimental optical characterization study indicate the validity and reliability of the proposed method for fabricating brain tissue phantoms in a cost-effective and straightforward fashion.

Josué M. Galindo, Carlos Tardío, Basanta Saikia et al.

This review article provides an in-depth exploration of the role of gels in the fields of organic electronics and photonics, focusing on their unique properties and applications. Despite their remarkable potential, gel-based innovations remain relatively uncharted in these domains. This brief review aims to bridge the knowledge gap by shedding light on the diverse roles that gels can fulfil in the enhancement of organic electronic and photonic devices. From flexible electronics to light-emitting materials, we delve into specific examples of gel applications, highlighting their versatility and promising outcomes. This work serves as an indispensable resource for researchers interested in harnessing the transformative power of gels within these cutting-edge fields. The objective of this review is to raise awareness about the overlooked research potential of gels in optoelectronic materials, which have somewhat diminished in recent years.

Erik Fransson, Julia Wiktor, Paul Erhart

The atomic scale dynamics of halide perovskites have a direct impact not only on their thermal stability but their optoelectronic properties. Progress in machine learned potentials has only recently enabled modeling the finite temperature behavior of these material using fully atomistic methods with near first-principles accuracy. Here, we systematically analyze the impact of heating and cooling rate, simulation size, model uncertainty, and the role of the underlying exchange-correlation functional on the phase behavior of CsPbX3 with X=Cl, Br, and I, including both the perovskite and the delta-phases. We show that rates below approximately 30 K/ns and system sizes of at least a few ten thousand atoms are indicated to achieve convergence with regard to these parameters. By controlling these factors and constructing models that are specific for different exchange-correlation functionals we then show that the semi-local functionals considered in this work (SCAN, vdW-DF-cx, PBEsol, and PBE) systematically underestimate the transition temperatures separating the perovskite phases while overestimating the lattice parameters. Among the considered functionals the vdW-DF-cx functional yields the closest agreement with experiment, followed by SCAN, PBEsol, and PBE. Our work provides guidelines for the systematic analysis of dynamics and phase transitions in inorganic halide perovskites and similar systems. It also serves as a benchmark for the further development of machine-learned potentials as well as exchange-correlation functionals.

R. Campana, C. Evola, C. Labanti et al.

A characteristic of every inorganic scintillator crystal is its light yield, i.e., the amount of emitted scintillation photons per unit of energy deposited in the crystal. Light yield is known to be usually non-linear with energy, which impacts the spectroscopic properties of the scintillator. Cerium-doped gadolinium-aluminium-gallium garnet (GAGG:Ce) is a recently developed scintillator with several interesting properties, which make it very promising for space-based gamma-ray detectors, such as in the HERMES nanosatellite mission. In this paper we report an accurate measurement of the GAGG:Ce non-linearity in the 20-662 keV gamma-ray energy interval, using a setup composed of three samples of GAGG:Ce crystals read out by Silicon Drift Detectors (SDDs).

Elena Gazzarrini, Rose K. Cersonsky, Marnik Bercx et al.

Why are materials with specific characteristics more abundant than others? This is a fundamental question in materials science and one that is traditionally difficult to tackle, given the vastness of compositional and configurational space. We highlight here the anomalous abundance of inorganic compounds whose primitive unit cell contains a number of atoms that is a multiple of four. This occurrence - named here the 'rule of four' - has to our knowledge not previously been reported or studied. Here, we first highlight the rule's existence, especially notable when restricting oneself to experimentally known compounds, and explore its possible relationship with established descriptors of crystal structures, from symmetries to energies. We then investigate this relative abundance by looking at structural descriptors, both of global (packing configurations) and local (the smooth overlap of atomic positions) nature. Contrary to intuition, the overabundance does not correlate with low-energy or high-symmetry structures; in fact, structures which obey the 'rule of four' are characterized by low symmetries and loosely packed arrangements maximizing the free volume. We are able to correlate this abundance with local structural symmetries, and visualize the results using a hybrid supervised-unsupervised machine learning method.

Houchao Xu, Anne Wochele, Minghe Luo et al.

An improved synthesis for tryptophan-dehydrobutyrine diketopiperazine (TDD), a co-metabolite of the hybrid polyketide/non-ribosomal peptide hangtaimycin, starting from ʟ-tryptophan is presented. Comparison to TDD isolated from the hangtaimycin producer Streptomyces spectabilis confirmed its S configuration. The X-ray structure of the racemate shows an interesting dimerisation through hydrogen bridges. The results from bioactivity testings of hangtaimycin, TDD and the hangtaimycin degradation product HTM222 are given.

Ying Zhang, Xuhuan Zhao, Hao Wang et al.

The aim of this research was to study the effect of temperature on the adhesion and disinfection activities of an Ag⁺-doped BiVO₄ (Ag⁺/BiVO₄) coating. Ag⁺/BiVO₄ was prepared by a sol–gel method, and spraying was used as the deposition method of coating. X-ray diffraction patterns showed that the monoclinic scheelite phase of the samples was unchanged by annealing at 450–650 °C. Scanning electron microscopy results showed that, at high temperatures, the particles melted and formed a dense coating, and the roughness of the coating decreased after initially increasing. The adhesion and disinfection activities were evaluated by ASTM D3359-08 and disinfection experiments. The results showed that the samples modified by silver had a good disinfection activity when annealed in the range of 450–650 °C. The adhesion increased upon increasing the annealing temperature. The sample annealed at 650 °C showed the best coating adhesion and completely killed <i>Escherichia coli</i>, <i>Staphylococcus aureus</i>, <i>Shigella</i>, and <i>Salmonella</i> after 2 h of visible-light irradiation.

Kira E. Vostrikova

This review is devoted to an analysis of currently known heterometallic molecular magnets based on an orbitally degenerate 5<i>d</i> metalloligand, [Re^IV(CN)₇]³⁻. Heptacyanidometallates with a pentagonal bipyramidal structure of the coordination site and degenerate ground spin state are the source of anisotropic magnetic exchange interactions upon the formation of cyanide-bonded assemblies involving the paramagnetic complexes of the first transition series. Therefore, the development of methods for chemical design using such molecular magnetic modules is extremely important. If for the 4d congener, isoelectronic [Mo^III(CN)₇]³⁻, a family of approximately 40 heterometallic compounds, was obtained, whereas for heptacyanorhenate(IV), no more than 20 are known. However, as a result of recent studies, heterobimetallic magnetic assemblies of all dimensionalities have been synthesized, from 0D to 1D, demonstrating slow magnetization relaxation, to 2D networks and 3D frameworks possessing large magnetic hysteresis. The most anisotropic is a 2D network, PPN[{Mn^III(acacen)}₂Re^IV(CN)₇]·Solv, with a critical temperature of 20 K and magnetic hysteresis with a record coercivity for cyanide-bridged molecular materials.