Chemistry

Rapid urban and industrial sectors generate massive amounts of wastewater, creating severe ecological disruption and harming living organisms. The number of harmful pollutants such as dyes, heavy metals, antibiotics, phenolic compounds, and volatile and several organic chemicals discharged into aquatic systems varies depending on the effluent composition of various sectors. MXene-based composites with unique characteristics were spotlighted as newly developed nanomaterials specifically for environmental-related applications. Therefore, this review broadly discusses the properties, basic principles of MXene, and synthesis routes for developing different MXene-based nanomaterials. The most current strategies on the energy and environmental applications of MXene-based nanomaterials, particularly in photocatalysis, adsorption, and water splitting, were deeply explored for the remediation of different pollutants and hydrogen (H₂) evolution from wastewater. The detailed mechanism for H₂ evolution and the remediation of industrial pollutants via photocatalysis and adsorption processes was elaborated. The multi-roles of MXene-based nanomaterials with their regeneration possibilities were emphasized. Several essential aspects, including the economic, toxicity and ecological power of MXene-based nanomaterials, were also discussed regarding their opportunity for industrialization. Finally, the perspectives and challenges behind newly developed MXene and MXene-based nanomaterials for environmental pollution were reviewed. Full article

The effect of carboxyl groups on the redox activity of polyluminol-carbon nanotube composites was studied. Carboxyl groups were selected due to their known contributions toward surface wettability and pseudocapacitance while often present on naturally derived low-cost porous carbons. Density functional theory (DFT) predicted energetically favoured bonding and a significantly reduced band gap between the luminol and carboxylated graphene relative to that of bare graphene, suggesting improved charge storage for carboxylated carbon substrates. The prediction was validated using bare carbon nanotubes (CNTs) and carboxylated CNTs (COOH-CNTs) as the substrates for in situ chemical polymerized luminol (CpLum). Surface morphological studies showed a ca. 1.1 nm thick coating of CpLum on CNT (CpLum/CNT) and a ca. 1.3 nm on COOH-CNT (CpLum/COOH-CNT), while surface chemical analysis revealed ca. 10% nitrogen from CpLum on both CpLum/CNT and CpLum/COOH-CNT. However, with merely 4.4% of COOH functionalization, CpLum/COOH-CNT was able to store more charge (137.1 ± 17.1 C cm⁻³) relative to CpLum/CNT (86.1 ± 14.1 C cm⁻³) and had increased charge retention over 5000 cycles. The insights from these studies can be used to engineer the surface of carbons such as CNTs and ACs to improve the interfacial properties for redox active materials and composites. Full article

We predict the geometries, electronic properties, and aromaticity of thiophene analogues of anti-kekulene with six to nine thiophene rings 1–4, together with those of cyclobutadithiophenes (CDTs) and anti-kekulene as reference compounds, using density functional theory calculations. Investigation of the simplest reference compounds, CDTs, reveals that the local aromaticity of their thiophene rings is influenced by their fused position (b- or c-bond) to the four-membered ring (4MR). A thiophene ring fused at the b-position (b-TR) retains its aromatic character to some extent, whereas the aromatic character of one fused at the c-position is attenuated. The 4MR with two fused b-TRs retains a strong anti-aromatic character. Thiophene analogues of anti-kekulene with six to eight thiophene rings 1–3 favor bowl-shaped structures, in contrast to the planar structure of anti-kekulene, because of the shorter distances of the sulfur bridges. Compound 4, with nine thiophene rings, adopts a planar structure. The local aromaticity and anti-aromaticity of the thiophene ring and 4MR are significantly attenuated in 1–4 compared with the reference compounds, the CDTs and anti-kekulene. This can be attributed to the considerable contribution of the quinoidal electronic structure in 1–4. The present study provides new insight into the aromatic and electronic nature of systems containing cyclobutadienothiophene. Full article

The reaction of alkaline earth pentacyanocyclopentadienides with 4,4′-bipyridine in MeOH yielded undefined products of composition [M(PCC)₂(Bipy)_x(MeOH)_y(H₂O)_z] (PCC = [C₅(CN)₅]⁻). Recrystallization from MeOH, EtOH, or n-BuOH gave crystals of [Mg(H₂O)₄(4,4′-bipy)₂](PCC)₂∙2BuOH (1), [Ca(H₂O)₄(4,4′-bipy)₂](PCC)₂∙(4,4′-bipy) (2), [Sr(MeOH)₈](PCC)₂∙3(4,4′-bipy) (3), [Sr₂(H₂O)₄(BuOH)₄(PCC)₂(µ-PCC)₂ (µ-4,4′-bipy)]∙4 (4,4′-bipy)∙0.29 (BuOH) (4), [Ba₃(H₂O)₄(EtOH)₁₀ (PCC)₂(µ-PCC)₂ (µ-4,4′-bipy)₂(4,4′-bipy)](PCC)₂ ∙3(4,4′-bipy)∙2EtOH∙H₂O (5) and [Ba₄(H₂O)₈(BuOH)₆ (PCC)₂(µ-PCC)₆ (4,4′-bipy)₆]∙3(4,4′-bipy) (6). 4,4′-Bipyridine functions either as monodentate or bidentate ligand and is present in all cases except for 2 as lattice guest. While in compounds 1 and 2 only water is present as O-donor, the alcohol coordinates in the other compounds either exclusively (3) or together with water (4–6). The pentacyanocyclopentadienide does not coordinate in 1–3, but is present as mono-, bi-, or tridentate ligand in 4–6. In all compounds, a more or less complicated interplay of hydrogen bridges and π–π stacking is observed. Full article

Crystals of two new inorganic uranyl silicates, Cs[(UO₆)₂(UO₂)₉(Si₂O₇)F] (1) and Rb₂[(PtO₄)(UO₂)₅(Si₂O₇)] (2), were produced from melts in evacuated silica tubes. Their structures have been solved by direct methods: 1 is trigonal, P-31c, a = 10.2040(3), c = 17.1278(5) Å, V = 1544.45(10) ų, R₁ = 0.042; 2 is tetragonal, P4/mbm, a = 16.0400(24), c = 3.9231(6) Å, V = 1009.34(10) ų, R₁ = 0.045. 1 is the first example of cation–cation interactions between the uranyl polyhedra in uranyl silicates. Therein, U^VI adopts three coordination modes, UO₆ octahedra, UO₆F, and UO₇ pentagonal bipyramids, with the latter sharing common edges to form U₂O₁₂ dimers. Three dimers associate into six-membered rings via cation–cation interactions. The structure of 1 can be described as a complex uranyl fluoride silicate framework with channels filled by the U1 atoms and disordered Cs⁺ cations. 2 represents a new type of topology never observed before among the structures of uranyl compounds; it is also a first complex uranium platinum oxide. Therein, the UO₆ tetragonal bipyramids share edges to form chains. Five such chains are stitched into a complex ribbon via the silicon polyhedra. The ribbons are connected into a framework by the PtO₄ squares; rubidium atoms are located in the channels of the framework. Full article

Mycotoxins are toxic secondary metabolites produced by filamentous microfungi on almost every agricultural commodity worldwide. After the infection of crop plants, mycotoxins are modified by plant enzymes or other fungi and often conjugated to more polar substances, like sugars. The formed—often less toxic—metabolites are stored in the vacuole in soluble form or bound to macromolecules. As these substances are usually not detected during routine analysis and no maximum limits are in force, they are called modified mycotoxins. While, in most cases, modified mycotoxins have lower intrinsic toxicity, they might be reactivated during mammalian metabolism. In particular, the polar group might be cleaved off (e.g., by intestinal bacteria), releasing the native mycotoxin. This review aims to provide an overview of the critical issues related to modified mycotoxins. The main conclusion is that analytical aspects, toxicological evaluation, and exposure assessment merit more investigation. Full article

Ceramic-based nanofiber materials for high-performance thermal management have drawn increasing attention owing to their high-temperature resistance, efficient thermal insulation, superior mechanical flexibility, as well as excellent physical–chemical stability. We present an overview of the ceramic-based nanofiber obtained by sol–gel routes for high-performance thermal management, including the materials, the fabrication methods of the sol–gel route, and their application for thermal management. We first provide a brief introduction to the ceramic-based nanofibers. The materials and fabrication methods of the sol–gel route are further discussed in the second part, including the kinds of nanofibers such as oxide, carbide, and nitride, and the methods such as centrifugal spinning, electrospinning, solution blow spinning, and self-assembly. Finally, their application for thermal management is further illustrated. This review will provide some necessary suggestions to researchers for the investigation of ceramic-based nanofibers produced with the sol–gel route for thermal management. Full article

Toxicity and pharmacological activity scales of molecules, in particular toxicants, xenobiotics, drugs, nutraceuticals, etc., are described by multiples indicators, and the most popular is the median lethal dose (LD₅₀). At the molecular level, reversible inhibition or binding constants provide unique information on the potential activity of molecules. The important problem concerning the meaningfulness of IC₅₀ for irreversible ligands/inhibitors is emphasized. Definitions and principles for determination of these quantitative parameters are briefly introduced in this article. Special attention is devoted to the relationships between these indicators. Finally, different approaches making it possible to link pharmacological and toxicological properties of molecules in terms of molecular interactions (or chemical reactions) with their biological targets are briefly examined. Experimental trends for future high-throughput screening of active molecules are pointed out. Full article

Multi-emissive compounds have attracted significant attention from the research community owing to the wide array of potential application areas. However, to move towards application, such systems should be readily immobilized by solution-based methods to form soft materials such as gels and films. Herein we report the use of Langmuir–Blodgett (LB) deposition to easily immobilize luminescent lanthanide-based amphiphilic solids into multi-emissive ultrathin LB films, by multilayering different luminescent amphiphiles. Utilizing this technique, we have reliably fabricated dual- and triple-emissive films where the overall emission from the film is tuned. Furthermore, we have demonstrated that these multi-emissive films are temperature-dependent, with emission profiles significantly altering from 294 to 340 K, resulting in colour changes and potential application as ultrathin, contactless ratiometric thermometer coatings. Full article

The design of new metallocage polyhedra towards pre-determined structures can offer both practical as well as intellectual challenges. In this mini-review we discuss a selection of recent examples in which the use of the metalloligand approach has been employed to overcome such challenges. An attractive feature of this approach is its stepwise nature that lends itself to the design and rational synthesis of heterometallic metal–organic cages, with the latter often associated with enhanced functionality. Full article

The calcium- and strontium- alumo-germanides Sr_xCa_1–xAl₂Ge₂ (x ≈ 0.4) and SrAl₂Ge₂ have been synthesized and structurally characterized. Additionally, a binary calcium germanide CaGe has also been identified as a byproduct. All three crystal structures have been established from single-crystal X-ray diffraction methods and refined with high accuracy and precision. The binary CaGe crystallizes with a CrB-type structure in the orthorhombic space group Cmcm (no. 63; Z = 4; Pearson symbol oC8), where the germanium atoms are interconnected into infinite zigzag chains, formally [Ge]²⁻. The calcium atoms are arranged in monocapped trigonal prisms, centered by Ge atoms. Sr_xCa_1−xAl₂Ge₂ (x ≈ 0.4) and SrAl₂Ge₂ have been confirmed to crystallize with a CaAl₂Si₂-type structure in the trigonal space group P$\overline{3}$m1 (no. 164; Z = 1; Pearson symbol hP5), where the germanium and aluminum atoms form puckered double-layers, formally [Al₂Ge₂]²⁻. The calcium atoms are located between the layers and reside inside distorted octahedra of Ge atoms. All presented structures have a valence electron count satisfying the octet rules (e.g., Ca²⁺Ge²⁻ and Ca²⁺[Al₂Ge₂]²⁻) and can be regarded as Zintl phases. Full article

Dipeptides have emerged as attractive building blocks for supramolecular materials thanks to their low-cost, inherent biocompatibility, ease of preparation, and environmental friendliness as they do not persist in the environment. In particular, hydrophobic amino acids are ideal candidates for self-assembly in polar and green solvents, as a certain level of hydrophobicity is required to favor their aggregation and reduce the peptide solubility. In this work, we analyzed the ability to self-assemble and the gel of dipeptides based on the amino acids norvaline (Nva) and phenylalanine (Phe), studying all their combinations and not yielding to enantiomers, which display the same physicochemical properties, and hence the same self-assembly behavior in achiral environments as those studied herein. A single-crystal X-ray diffraction of all the compounds revealed fine details over their molecular packing and non-covalent interactions. Full article

A simple and cost-effective optical sensing system based on quinizarin fluorescent dye (QZ) for the selective and reversible sensing of CH₃COO⁻ anions is reported. The anion binding affinity of QZ towards different anions was monitored using electronic absorption and fluorescence emission titration studies in DMSO. The UV-visible absorption spectrum of QZ showed a decrease in the intensity of the characteristic absorption peaks at λ = 280, 323, and 475 nm, while a new peak appeared at λ = 586 nm after the addition of CH₃COO⁻ anions. Similarly, the initial strong emission intensity of QZ was attenuated following titration with CH₃COO⁻ anions. Notably, similar titration using other anions, such as F⁻, Cl⁻, I⁻, NO₃⁻, NO₂^−, and H₂PO₄^-, caused no observable changes in both absorption and emission spectra. The selective sensing of CH₃COO⁻ anions was also reflected by a sharp visual color change from bright green to faint green under room light. Further, the binding was found to be reversible, and this makes QZ a potential optical and colorimetric sensor for selective, reversible, and ppb-level detection of CH₃COO⁻ anions in a DMSO medium. Full article

β-carboline consists of a pyridine ring fused to an indole skeleton; it possesses numerous pharmacological activities, including anticancer. Previously, we reported a satisfactory 2D and 3D QSAR study on β-carboline derivatives. Based on QSAR studies, we designed, synthesized, characterized, and screened fourteen β-carboline derivatives for anticancer activity. Eleven of them demonstrated potent anticancer activity against both liver (HepG2) and adenocarcinoma (A549) cell lines. Compound 1-(N, N-dimethylbenzenamine)-3-(4-(p-tolylmethanimine)-5-thio-1, 2, 4-triazol-3-yl) β-carboline (9) was found to be most potent against both cancer cell lines and equipotent towards standard drug Adriamycin. Compounds 1-(p-tolyl)-3-(4-(p-(iminomethyl)-N, N-dimethylbenzenamine) -5-thio-1, 2, 4-triazol-3-yl) β-carboline (4) and 1-(N, N-dimethylbenzenamine)-3-(4-(m-tolylmethanimine)-5-thio-1, 2, 4-triazol-3-yl) β-carboline (10) were found to be 7 to 10 times less potent as compared to Adriamycin against the HepG2 cell line. Molecular docking was also performed with the Glide docking program to explore the binding mode between the synthesized β-carboline derivatives and the receptor CDK2 [1AQ1] protein. Full article

The simultaneous determination of heregulin-α and HER 1–4 plays an important role in brain cancer diagnosis and treatment. To date, only enzyme-linked immunosorbent assay (ELISA) or a semiquantitative colorimetric method have been used for the assay of these biomarkers; these methods are quite expensive and can only determine one biomarker in a run. Four 3D stochastic microsensors based on multi-walled carbon nanotubes enriched with gold nanoparticles and modified with inulin were designed for the simultaneous determination of heregulin-α and HER 1–4 in tumor brain tissue and whole blood samples. For the simultaneous measurement of HRG-α and HER 1–4, all sensors demonstrated low limits of determination (as fg mL⁻¹ magnitude order), high sensitivities, and wide concentration ranges. From biological samples, high recovery values of more than 96% of analytes were obtained. The proposed sensor can detect HER 1–4 and heregulin-α in whole blood and tumor tissue samples at the same time. Full article

Researchers have been focusing increasingly on preparing innovative packaging films made from renewable and biodegradable materials in recent years. This research set out to fabricate and analyze pH-sensitive edible films based on salep mucilage combined with anthocyanin from saffron (Crocus sativus L.) (SA_As). A casting technique was developed with varying concentrations of SA_As (0, 2.5, 5, 7.5, and 10%v/v) pH-sensitive edible films. The surface morphology, physicochemical, barrier, and mechanical properties, as well as the pH sensitivity of films, were investigated. The results showed SA_As increased thickness, water solubility, moisture content, and oxygen permeability (O₂P) up to 199.03 µm, 63.71%, 14.13%, and 47.73 (cm³ µm m⁻² day⁻¹ kPa⁻¹), respectively, of the pH-sensitive salep mucilage edible indicator films. As expected, the SA_As concentration from 0% to 10%v/v decreased tensile strength, transparency, and contact angle to 11.94 MPa, 14.27%, and 54.02°, respectively. Although achieving the highest elongation at the break (108%) and the lowest water vapor permeability (WVP) (1.39 g s⁻¹ m⁻¹ Pa⁻¹ × 10⁻¹¹), the pH-sensitive edible indicator film containing 5 %v/v of SA_As showed the best results. An investigation of pH sensitivity revealed that the solution’s pH variation altered the SA_As color. When the pH was raised from 3 to 11, the SA_As’ color shifted from pink to brown. The SA_As-halochromic salep mucilage edible indicator film was employed as a label in an experiment to track the degradation of fish fillets stored at 4 °C, revealing that the halochromic indicator changed color from yellow to brown as the fish was stored. Our findings show that SA_As-loaded salep mucilage indicator films help monitor real-time food deterioration. Full article

Evolving technology has posed a constantly increasing need for materials that can work well under harsh conditions such as elevated temperatures. Aromatic polyimides have a great potential for this purpose, having excellent thermal, mechanical, dielectric, and optical properties, along with good chemical resistance and high dimensional stability. In spite of their general difficulty in processing and high cost, polyimides are intensively studied for applications in many areas due to their high-end value. This article reviews the progress made on polyimide materials in the “Petru Poni” Institute of Macromolecular Chemistry (ICMPP) of the Romanian Academy during the last decade, with focus on their performance as films, matrices for nanocomposites, coatings for microelectronics and opto-electronic devices, or dielectrics for thin film capacitors. Full article

A significant interest was granted lately to enzymes, which are versatile catalysts characterized by natural origin, with high specificity and selectivity for particular substrates. Additionally, some enzymes are involved in the production of high-valuable products, such as antibiotics, while others are known for their ability to transform emerging contaminates, such as dyes and pesticides, to simpler molecules with a lower environmental impact. Nevertheless, the use of enzymes in industrial applications is limited by their reduced stability in extreme conditions and by their difficult recovery and reusability. Rationally, enzyme immobilization on organic or inorganic matrices proved to be one of the most successful innovative approaches to increase the stability of enzymatic catalysts. By the immobilization of enzymes on support materials, composite biocatalysts are obtained that pose an improved stability, preserving the enzymatic activity and some of the support material’s properties. Of high interest are the polymer/enzyme composites, which are obtained by the chemical or physical attachment of enzymes on polymer matrices. This review highlights some of the latest findings in the field of polymer/enzyme composites, classified according to the morphology of the resulting materials, following their most important applications. Full article

In the present work, ab initio calculations and Monte Carlo simulations were combined to investigate the effect of linker functionalization on nitric oxide (NO)’s storage ability of metal–organic frameworks (MOFs). The binding energy (BE) of nitric oxide with a set of forty-two strategically selected, functionalized benzenes was investigated using Density Functional Theory calculations at the RI-DSD-BLYP/def2-TZVPP level of theory. It was found that most of the functional groups (FGs) increased the interaction strength compared to benzene. Phenyl hydrogen sulfate (–OSO₃H) was the most promising among the set of ligands, with an enhancement of 150%. The organic linker of IRMOF-8 was modified with the three top-performing functional groups (–OSO₃H, –OPO₃H₂, –SO₃H). Their ability for NO adsorption was investigated using Grand Canonical Monte Carlo (GCMC) simulations at an ambient temperature and a wide pressure range. The results showed great enhancement in NO uptake constituting the above-mentioned FGs, suggesting them to be promising modification candidates in a plethora of porous materials. Full article