Transition metal complexes have been recognized as possible therapeutic agents, attributed to their special biological actions, including anti-inflammatory, antibacterial, antifungal, and anticancer. The pharmacological perspective connected with Copper (Cu), Cobalt (Co), Nickel (Ni), Manganese (Mn), Palladium (Pd), Zinc (Zn), and Platinum (Pt) metal(II) complexes is comprehensively explored in-depth in this research. The complexes show unique coordination chemistry and modes of action that help interactions with biological targets, including DNA binding, enzyme inhibition, and the formation of reactive oxygen species. All the metal(II) complexes showed notable potential impact in their perspective activity. Conspicuously, Co(II) and Ni(II) complexes show better antibacterial and antifungal action, while Cu(II) and Zn(II) combinations show higher anti-inflammatory activity. While research is constantly investigating alternative metal-based anticancer drugs like Pd(II), which seem to have lowered side effects, Pt(II) complexes especially cisplatin continue to be the benchmark in cancer treatment. Although the possible pharmacological actions are motivating, problems with toxicity and biocompatibility still provide major difficulties, especially in relation to Cd(II) and Hg(II) complexes. Strategies like ligand modification, nanoparticle-based delivery, and prodrug methods are used to increase selectivity and reduce side effects related to metal complexes. This review compiles the most recent developments and continuous research, thereby shedding light on the potential revolutionary power of metal(II) complexes in medical therapy. Understanding their mechanisms and enhancing their safety profiles will help us open the path to creative ideas for addressing some of the most urgent medical issues of today.

To detect viruses such as hepatitis A virus (HAV) and human norovirus (HuNoV) in foods, RT-qPCR or other molecular methods are used, which cannot distinguish between infectious and non-infectious virions. Samples can be pretreated to limit detection to intact and presumably infectious virions. We compared propidium monoazide (PMA or PMAxx), platinum (IV) chloride (PtCl4), magnetic silica beads and centrifugal filter using HAV or HuNoV inactivated by heat, pulsed light, or sodium hypochlorite (NaOCl). PMAxx completely or nearly eliminated (3.96 ± 1.24 log gc) the RT-qPCR signal of HAV inactivated at 100°C for 10 min. Pretreatments could not reduce significantly RT-qPCR signal of HAV after pulsed light (0.74 ± 0.36 log gc) and NaOCl (0.24 ± 0.14 log gc) inactivation. Enzymatic treatments did not improve the results obtained with PMAxx. The exudate of raspberry, strawberry or oyster used as food matrices needed dilution by at least tenfold for PMAxx to to yield results comparable to virions without a food matrix. Overall, PMAxx shows good potential to discriminate between infectious and non-infectious despite some remaining limitations.

The development of optical sensors for metal ions has gained significant attention due to their broad applications in biology, the environment, and medicine. Colorimetric and fluorometric detection methods are particularly valued for their simplicity, cost-effectiveness, high detection limits, and analytical power. Among various chemical probes, the hydrazone functional group stands out for its extensive study and utility, owing to its ease of synthesis and adaptability. This review provides a comprehensive overview of N-acylhydrazone-based probes, serving as highly effective colorimetric and fluorometric chemosensors for a diverse range of metal ions. Probes are categorized into single-ion, dual-ion, and multi-ion chemosensors, each further classified based on the detected metal(s). Additionally, the review discusses detection modes, detection limits, association constants, and spectroscopic measurements.

Supramolecular hydrogels are three-dimensional structures composed of cross-linked macromolecules interconnected by dynamic physical bonds, which allow them to absorb and retain significant volumes of water. Their intrinsic properties, such as viscoelasticity, self-healing capabilities, and high water content, render them promising materials for cell-laden scaffolds utilized in bioinks. This review systematically summarizes the current state-of-the-art advancements in hydrogels for tissue engineering, categorizing them based on the nature of their supramolecular interactions. Particular emphasis is placed on the classification of supramolecular hydrogels and their associated properties, including kinetics, mechanical characteristics, responsiveness, and swelling behavior. The review specifically addresses the criteria that hydrogels must fulfill prior to their application in bioinks. Achieving biocompatibility and bioactivity necessitates the careful selection of hydrogel compositions with suitable properties, as well as the incorporation of external organic or inorganic bioactive molecules. Methods for measuring and enhancing biophysical and biochemical properties are discussed in detail, alongside an exploration of the unique requirements of bioinks tailored for each additive manufacturing method. This review paper serves as an instructive resource for the construction and characterization of supramolecular hydrogels, facilitating their application in bioinks for tissue engineering.

Zinc oxide (ZnO) and iron oxide (IO) nanoparticles have been identified as promising candidates for biomedical applications, based on their unique physicochemical properties. The association of these nanoparticles in a single system creates a bimodal entity, allowing the excellent luminescent properties of ZnO quantum dots to be combined with the contrast agent of IO for magnetic resonance imaging (MRI). The present study focuses on the luminescent and MRI properties of a new poly(lactic-co-glycolic acid) (PLGA) nanocarrier system formulation containing ZnO NPs and IO NPs in different nominal ratios. Microscopic analysis (TEM and SEM) reveals a circular morphology with IO and ZnO NPs. The average diameter of the particles was determined to be 220 nm, as measured by DLS. The luminescence results indicate that the PLGA system shows strong emission in the visible range, and the MRI analysis shows a high r2 relaxivity of 171 mM-1 s-1 at 7T. The optimized formulation, exhibiting a molar ratio of Fe:Zn ranging from 1:10 to 1:13 (mol:mol), demonstrates superior fluorescence and MRI performance, underscoring the significance of nanoparticle composition in bimodal imaging applications. The systems evaluated demonstrate no toxicity in the THP-1 cells for doses of up to 128 µg mL-1, with efficient labeling after 4 h of incubation, yielding images of strong luminescence and T2 contrast. The PLGA:ZnO:IO system demonstrates considerable potential as a bimodal platform for diagnostic imaging.

Super-resolution microscopy (SRM) has transformed biological imaging by overcoming the diffraction limit, offering nanoscale visualization of cellular structures and processes. However, the widespread use of organic fluorescent probes is often hindered by limitations such as photobleaching, short photostability, and inadequate performance in deep-tissue imaging. Metal complexes, with their superior photophysical properties, including exceptional photostability, tuneable luminescence, and extended excited-state lifetimes, address these challenges, enabling precise subcellular targeting and long-term imaging. Beyond imaging, their theranostic potential unlocks real-time diagnostics and treatments for diseases such as cancer and bacterial infections. This review explores recent advancements in applying metal complexes for SRM, focusing on their utility in visualizing intricate subcellular structures, capturing temporal dynamics in live cells and elucidating in vivo spatial organization. We emphasize how rational design strategies optimize biocompatibility, organelle specificity, and deep-tissue penetration, expanding their applicability in multiplexed imaging. Furthermore, we discuss the design of various metal nanoparticles (NPs) for SRM, along with emerging hybrid nanoscale probes that integrate metal complexes with gold (Au) scaffolds, offering promising avenues for overcoming current limitations. By highlighting both established successes and potential frontiers, this review provides a roadmap for leveraging metal complexes as versatile tools in advancing SRM applications.

Lead (Pb) is a non-essential toxic metal that accumulates in aquatic environments, negatively impacting fish health. This study evaluated the acute toxicity of Pb in starry flounders (Platichthys stellatus). Fish (41 ± 8.1 g, 14 ± 0.9 cm) were exposed to Pb concentrations of 0, 10, 20, 40, 80, 160, 320, and 640 mg Pb2+/L for 96 h. The lethal concentration (96 h LC50) was determined to be 227 mg Pb2+/L. Hematological analysis showed significant decreases in RBC counts, hemoglobin, and hematocrit, while MCH and MCHC increased at ≥160 mg Pb2+/L. Plasma calcium levels significantly decreased following Pb exposure, and AST activity was reduced. These findings suggest that acute waterborne Pb exposure adversely affects survival, hematological parameters, and plasma components in P. stellatus, providing insight into Pb toxicity in aquatic organisms.

Water pollution by metals and metalloids promotes toxic effects to aquatic biota especially in mining regions. Environmental legislation applied to protect aquatic life from the toxicity of metals relies on the definition of protective values (PVs) for each compound. Among methods used to define PVs, Species Sensitivity Distribution (SSD) curves enable the derivation of the Predicted No Effect concentration (PNEC). In this context, this is one of the first studies to propose the construction of acute and chronic split SSD curves built separately for three groups of freshwater organisms (algae, invertebrates and fish) to derive PNEC values for the 14 metals most commonly observed in iron ore mining tailings. Data used to construct split SSD curves were derived from the USEPA ECOTOX knowledgebase and EnviroTox databases and segregated according to the freshwater organism group and as "acute" or "chronic" toxicity. Then, split SSD curves were built using a minimum of nine species for each group to determine the hazardous concentration to 5% of species (HC5) and PNEC values for each group. Once PNEC were derived, a framework was proposed to calculate the Bioavailabity Factor (BioF) used to adjust values for local bioavailability conditions considering water quality characteristics in different regions. The lowest acute PNEC were observed for algae and invertebrates and corresponded to Silver (Ag). Nearly half of calculated PNEC were below current PVs in practice in Brazil, United States (US), United Kingdom (UK), Canada and European Union (EU). Results reinforce the pertinence of: (i) splitting SSD curves to define PVs for metals; and (ii) taking bioavailability into consideration to correct PNEC for local conditions. In addition, outcomes suggest that it is critical to rethink PVs related to metals for aquatic life protection, mainly in Brazil and Minas Gerais state, a region known for extensive mining activity. Finally, PNEC values obtained in this study may be used for ecological risk assessment studies, especially in areas affected by mining and other activities that result in pollution by metals and metalloids, such as Brazil.

Herein, five Fe(II) complexes, viz., [Fe(N,N,N)2](ClO4)2, where N,N,N = 4'-phenyl-2,2':6',2″-terpyridine (Ph-tpy, Fe1), 4'-(4 aminophenyl) 2,2':6',2″ terpyridine (NH2-Phtpy, Fe2), 4-([2,2':6',2''-terpyridin]-4'-yl)-N,N-dimethylaniline (NMe2-Phtpy, Fe3), 4'-(p-nitrophenyl)-2.2':6',2″-terpyridine (NO2-Phtpy, Fe4), and 4'-(4-trifluoromethylphenyl)-2,2':6',2''-terpyridine (CF3-Phtpy, Fe5) were developed and screened for their visible-light-triggered antibacterial activity. Fe1-Fe5 exhibited absorption at ca. 450-600 nm, beneficial for antibacterial photodynamic therapy (aPDT) under visible light exposure. The excellent photostability and ideal energy gap between T1 and S0 of the complexes made them good photosensitizers for aPDT. Fe5 had the best antibacterial activity against Escherichia coli and Bacillus subtilis upon exposure to 400-700 nm (10 J cm-2) light due to reactive oxygen species (ROS) generation. Further, Fe5 showed antibiofilm activity on different medical-grade biomaterials and devices. Biocompatibility of Fe5 was validated using in vivo and chicken embryonic models (in ovo). Moreover, in vivo studies showed that Fe5 efficiently healed infected wounds within 9 days.

Taurine is a non-proteinogenic amino acid derived from cysteine. It is involved in several phenomena such as the regulation of growth and differentiation, osmoregulation, neurohormonal modulation, and lipid metabolism. Taurine is important because of its high levels in several tissues such as the central nervous system (CNS), heart, skeletal muscles, retinal membranes, and platelets. In this report, we present the functional properties of taurine indicating that it has potential effects on various metal toxicities. Therefore, a comprehensive literature review was performed using the Scopus, PubMed, and Web of Science databases. According to the search keywords, 61 articles were included in the study. The results indicate that taurine protects tissues against metal toxicity through enhancement of enzymatic and non-enzymatic antioxidant capacity, modulation of oxidative stress, anti-inflammatory and anti-apoptotic effects, involvement in different molecular pathways, and interference with the activity of various enzymes. Taken together, taurine is a natural supplement that presents antitoxic effects against many types of compounds, especially metals, suggesting public consumption of this amino acid as a prophylactic agent against the incidence of metal toxicity.

Nozaki-Hiyama-Kishi (NHK) reactions offer a mild approach for the formation of alcohol motifs through radical-polar crossover-based pathways from various radical precursors. However, the application of multicomponent NHK-type reactions, which allow the formation of multiple bonds in a single step, has been largely restricted to bulky alkyl radical precursors, thus limiting their expanded utilization. Herein, we disclose a general three-component NHK-type reaction enabled by delayed radical-polar crossover, which efficiently tolerates a plethora of radical precursors that were previously unavailable. This method enables the modular assembly of versatile homoallylic alcohols from feedstock chemicals with excellent chemo-, regio-, diastereo-, and enantioselectivities in a single step. Experimental studies and density functional theory (DFT) calculations reveal that the kinetically favored formation of an allylchromium(III) species is paramount for enforcing the delayed radical-polar crossover over direct radical addition. Finally, straightforward transformations and applications of the homoallylic alcohol products were demonstrated, showcasing the synthetic utility of this method.

Simple aryl chlorides represent challenging substrates in iron-catalyzed borylation. A combination of Li[B(tBu)pin-Bpin] as the borylating reagent and a catalyst formed in situ from iron(II) triflate and the commercially available N-heterocyclic carbene ligand, IMes, gives significantly improved activity and a much broader scope than previously reported iron-based catalysts. Iron triflate is also a good precatalyst for the borylation of aryl triflates─a previously unreported transformation─and in these cases the IMes ligand is not required.

Catalytic regio-, diastereo- and enantioselective reductive coupling of 1,3-dienes and aldehydes through regio- and enantioselective oxidative cyclization followed by regio- and diastereoselective protonation promoted by a chiral phosphine-cobalt complex is presented. Such processes represent an unprecedented reaction pathway for cobalt catalysis that enable selective transformation of the more substituted alkene in 1,3-dienes, affording a broad scope of bishomoallylic alcohols without the need of pre-formation of stoichiometric amounts of sensitive organometallic reagents in up to 98 % yield, >98 : 2 regioselectivity, >98 : 2 dr and 98 : 2 er. Application of this method to construction of axial stereogenicity and deuterated stereogenic center provided a wide range of multifunctional chiral building blocks that are otherwise difficult to access. DFT calculations revealed the origin of regio- and stereoselectivity as well as a unique oxidative cyclization mechanism for cobalt catalysis.

The papers were searched in databases including PubMed, Scopus, Web of science, Embase, Science Direct until 21 September 2023 and meta-analysis of concentration of PTEs in honey was performed using random effects model based on country subgroups. The non-carcinogenic risk and carcinogenic risk were calculated by Target Hazard Quotient (THQ) and Cancer Risk (CR), respectively. The sort of PTEs in honey based on pooled concentration was Cu (1.10E + 02 µg/kg) > Ni (1.80E + 01 µg/kg) > Pb (2.60E + 00 µg/kg) > Hg (1.50E + 00 µg/kg) > Cd (5.10E-01 µg/kg) > As (4.80E-01 µg/kg). The concentration of PTEs in the countries of Ethiopia (As), Jordan (Cd and Pb), Thailand (Ni), Brazil (Cu and MeHg) was observed to be higher than other countries. The non-carcinogenic risk was less than 1, hence, the consumption of honey does not have non-carcinogenic risk. Except children in Nigeria, CR due to iAs in honey was acceptable for the both adults and children in the other countries, Therefore, the consumption of honey does not have carcinogenic risk.

The Goossen decarboxylative coupling reaction enables the union of thiazole-2-carboxylic acids with a 2-pyridyl triflate, leading to the formation of pyridine-thiazole clusters of the kind found in thiopeptide antibiotics. The method avoids problematic or technically challenging reaction sequences involving 2-thiazolyl organometallics, facilitating the investigation of the structure-activity relationship of the thiopeptides.

A synthetic method was developed for the generation of a quaternary carbon center in carbonyl compounds. This innovative process involved the reaction of α-thiolate lactones and cycloalkanones with two equivalents of arynes in acetonitrile to give α,α-diarylated products in 63-85% yields at 25 °C. The reaction unfolds through an unconventional domino process, encompassing sequential 1,2-elimination, 1,2-nucleophilic addition, 1,4-proton transfer, the second 1,2-nucleophilic addition, interrupted Pummerer rearrangement, intramolecular spirocyclization, and sulfonium ring-opening. The potential of this "single-flask" reaction was systematically investigated and found well-suited to generate diarylated carbonyl compounds, incorporating naphthalene, pyridine, quinoline, or isoquinoline rings adorned with various substituents.

In this contribution, we tackle the replacement of the Hg-based catalyst and fossil-derived isocyanate precursors toward the formulation of a more sustainable polyurethane thermosetting resins (PUs), emulating the performance of a fully fossil-based one employed in industrial encapsulation of optoelectronics. A mixed Bi-Zn catalyst and a 71 % bio-based isocyanate are exploited at this aim through multivariate chemometric approaches, namely Design of Experiment (DoE). DoE allows us to investigate the effect of different formulation factors on selected parameters, such as the film flexibility and transparency or the gel time. More in detail, it is found that a low amount of Zn-rich catalytic mixture leads to a ready-to-market polyurethane only when a fossil-based isocyanate is used. Differently, PUs formulated with bio-based isocyanate, albeit showing a higher bio-based content, present an insufficient optical purity, jeopardizing their market acceptability. Nevertheless, adding a negligible amount of a specific long chain fatty acid as reactivity modulator in the formulation leads to a bubbles-free and ready-to-market resin showing an impressive 65 % w/w content of circular and bio-based components.

The increasing need to understand and control the environmental impact of chemical processes has revealed the challenge in efficient evaluation of toxicity of the vast number of chemical compounds and their varying effects on biological systems. In this study, we introduce "Build-a-bio-Strip", a novel online service designed to carry out a quick initial analysis of the toxic impact of chemical processes. This platform enables users to automatically generate toxicity characteristics of chemical reactions using their own data on cytotoxicity or median lethal doses of the substances involved or computational predictions based on SMILES strings. The service calculates the toxicity metrics such as bio-Factors and cytotoxicity potentials, which can be used to identify the substances with significant contributions to the overall toxicity of a particular process. This facilitates the selection of safer synthetic routes and the optimization of chemical processes from a toxicity perspective. "Build-a-bio-Strip" represents a step toward safer and more sustainable chemical practices. It is available free-of-charge at http://app.ananikovlab.ai:8080/.

Cu-catalyzed enantioconvergent cross-coupling of alkyl halides has emerged as a powerful strategy for synthesizing enantioenriched molecules. However, this approach is intrinsically limited by the weak reducing power of copper(I) species, which restricts the scope of compatible nucleophiles and necessitates extensive ligand optimization or the use of complex chiral scaffolds. To overcome these challenges, we introduce an aryl-radical-enabled strategy that decouples the alkyl halide activation step from the chiral Cu center. We demonstrate that merging aryl-radical-enabled iodine abstraction with Cu-catalyzed asymmetric radical functionalization enables the conversion of racemic α-iodoamides to enantioenriched alkyl nitrile products with good yield and enantioselectivity. The rational design of chiral ligands identified a new class of carboxamide-containing BOX ligands. Mechanistic studies support an aryl-radical-enabled pathway and the unique hydrogen-bonding ability in the newly designed BOX ligands. This aryl-radical-enabled asymmetric substitution reaction has the potential to significantly expand the scope of Cu-catalyzed enantioconvergent cross-coupling reactions.

N-Methylation of amines is of great interest in the synthesis of pharmaceuticals and valuable compounds, and the possibility to perform this reaction with an inexpensive and non-toxic substrate like CO2 and its derivatives is quite appealing. Herein, the synthesis of four novel homoleptic Cu(II) complexes with hybrid NHC-phenolate (NHC = N-Heterocyclic Carbene) ligands is reported, and their use in the catalytic N-methylation of amines with CO2 in the presence of hydrosilanes is explored. Both bidentate or tetradentate ligands can be used in the preparation of the complexes provided that the structural requirement that the two NHC and the two phenolate donors in the metal coordination sphere are mutually in trans is fulfilled. A new reaction protocol to perform the N-methylation of secondary aromatic amines and dibenzylamine in high yield under mild reaction conditions is developed, using the ionic liquid [BMMIM][NTf2] (1-butyl-2,3-dimethylimidazolium bis(trifluoromethylsulfonyl)imide) as solvent and the catalyst precursor [Cu(L2)2]. Reactivity studies indicate that the reaction follows two different pathways with different hydrosilanes, and that the starting Cu(II) complexes are reduced under the catalytic conditions.

Organoboronic acids, some of the most common and widely used organoboron compounds, have not yet been used in the cobalt-catalyzed cross coupling reactions, despite cobalt demonstrating good reactivity with zinc reagents, Grignard reagents, and metal organoborates that are formed by n-butyl lithium or alkaline metal alkoxide salts and organoboron esters. Herein, a highly efficient and practical cobalt-catalyzed coupling reaction of aryl/alkenyl boronic acids and alkynyl chloride under mild reaction conditions is reported. The advantages of the organoboronic acids, along with a broad functional group compatibility and the reaction's tolerance to moisture and air, enable this reaction to be a synthetically useful protocol for the construction of a C(sp2)-C(sp) bond. Lastly, the synthesis of two natural products and a key intermediate of roxadustat was effectively accomplished using the methodology to construct the critical alkynyl-aryl bond.

Nanotechnology holds immense promise in revolutionising healthcare, offering unprecedented opportunities in diagnostics, drug delivery, cancer therapy, and combating infectious diseases. This review explores the multifaceted landscape of nanotechnology in healthcare while addressing the critical aspects of safety and environmental risks associated with its widespread application. Beginning with an introduction to the integration of nanotechnology in healthcare, we first delved into its categorisation and various materials employed, setting the stage for a comprehensive understanding of its potential. We then proceeded to elucidate the diverse healthcare applications of nanotechnology, spanning medical diagnostics, tissue engineering, targeted drug delivery, gene delivery, cancer therapy, and the development of antimicrobial agents. The discussion extended to the current situation surrounding the clinical translation and commercialisation of these cutting-edge technologies, focusing on the nanotechnology-based healthcare products that have been approved globally to date. We also discussed the safety considerations of nanomaterials, both in terms of human health and environmental impact. We presented the in vivo health risks associated with nanomaterial exposure, in relation with transport mechanisms, oxidative stress, and physical interactions. Moreover, we highlighted the environmental risks, acknowledging the potential implications on ecosystems and biodiversity. Lastly, we strived to offer insights into the current regulatory landscape governing nanotechnology in healthcare across different regions globally. By synthesising these diverse perspectives, we underscore the imperative of balancing innovation with safety and environmental stewardship, while charting a path forward for the responsible integration of nanotechnology in healthcare.

Toxic metal(loid)s, e.g., mercury, arsenic, lead, and cadmium are known for several environmental disturbances creating toxicity to humans if accumulated in high quantities. Although not discussed critically, the organo-forms of these inorganic metal(loid)s are considered a greater risk to humans than their elemental forms possibly due to physico-chemical modulation triggering redox alterations or by the involvement of biological metabolism. This extensive review describes the chemical and physical causes of organometals and organometal(loid)s distribution in the environment with ecotoxicity assessment and potential remediation strategies. Organo forms of various metal(loid)s, such as mercury (Hg), arsenic (As), lead (Pb), tin (Sn), antimony (Sb), selenium (Se), and cadmium (Cd) have been discussed in the context of their ecotoxicity. In addition, we elaborated on the transformation, speciation and transformation pathways of these toxic metal(loid)s in soil-water-plant-microbial systems. The present review has pointed out the status of toxic organometal(loid)s, which is required to make the scientific community aware of this pressing condition of organometal(loid)s distribution in the environment. The gradual disposal and piling of organometal(loid)s in the environment demand a thorough revision of the past-present status with possible remediation strategies prescribed as reflected in this review.

The use of deep eutectic solvents (DESs) as catalysts presents indisputable advantages, for example, their simplicity of preparation, high biodegradability, and recyclability, as well as zero toxicity and their effectiveness as environmentally friendly reaction media. However, aspects related to their reactivity and catalytic activity are still unclear. In this work, we explore the versatility of ChCl/ZnCl2 DES in the formation of C-C bonds through the Michael-type addition of pyrrole to maleimide, where ChCl/ZnCl2 DES leads to catalysis and chelation of the substrates, thus describing a recommended method for the construction of C-C bonds with high atomic economy. We describe experimental and theoretical aspects that explain the ability of ChCl/ZnCl2 DES in the presence of water to act as a catalyst in the formation of C-C bonds between pyrrole and maleimide. The potential energy surface showed that the ChCl and the zinc-zincate species 2ZnCl2·3H2O, formed by the interaction between zinc chloride and water, decrease the relative free Gibbs energy values for all the species involved in the reaction mechanism (TSs, intermediates, product), favoring the kinetics and thermodynamics of the Michael addition.

Magnesium (Mg) has attracted considerable attention as a biodegradable material for medical implants owing to its excellent biocompatibility, mitigating long-term toxicity and stress shielding. Nevertheless, challenges arise from its rapid degradation and low corrosion resistance under physiological conditions. To overcome these challenges, titanium (biocompatibility and corrosion resistance) has been integrated into Mg. The incorporation of titanium significantly improves mechanical and corrosion resistance properties, thereby enhancing performance in biological settings. Mg-Ti alloys are produced through mechanical alloying and spark plasma sintering (SPS). The SPS technique transforms powder mixtures into bulk materials while preserving structural integrity, resulting in enhanced corrosion resistance, particularly Mg80-Ti20 alloy in simulated body fluids. Moreover, Mg-Ti alloy revealed no more toxicity when assessed on pre-osteoblastic cells. Furthermore, the ability of Mg-Ti-based alloy to create composites with polymers such as PLGA (polylactic-co-glycolic acid) widen their biomedical applications by regulating degradation and ensuring pH stability. These alloys promote temporary orthopaedic implants, offering initial load-bearing capacity during the healing process of fractures without requiring a second surgery for removal. To address scalability constraints, further research is necessary to investigate additional consolidation methods beyond SPS. It is essential to evaluate the relationship between corrosion and mechanical loading to confirm their adequacy in physiological environments. This review article highlights the importance of mechanical characterization and corrosion evaluation of Mg-Ti alloys, reinforcing their applicability in fracture fixation and various biomedical implants.

Platinum single atoms anchored onto activated carbon enable highly stable Hg-free synthesis of vinyl chloride (VCM) via acetylene hydrochlorination. Compared to gold-based alternatives, platinum catalysts are in initial phases of development. Most synthetic approaches rely on chloroplatinic acid, presenting opportunities to explore other precursors and their impact on catalyst structure, reactivity, and toxicity aspects. Here, we synthesize platinum single atom catalysts (Pt SACs, 0.2-0.8 wt % Pt) employing diverse Pt2+ and Pt4+ complexes with ammine, hydroxyl, nitrate, and chloride ligands, following a scalable impregnation protocol on activated carbon extrudates. X-ray absorption spectroscopy (XAS) reveals that Pt4+ species reduce to Pt2+ upon deposition onto the support. Despite similar oxidation states, the initial activity is precursor dependent, with tetraammine-derived Pt SACs displaying 2-fold higher VCM yield than chlorinated counterparts, linked to superior hydrogen chloride binding abilities by density functional theory (DFT) simulations. Their activity gradually converges due to dynamic active site restructuring, delivering remarkable precursor-independent stability over 150 h. Operando XAS and DFT studies uncover reaction-induced ligand exchange, generating common active and stable Pt-Cl x (x = 2-3) species. Convergent active site evolution enables flexibility in metal precursor selection and thus toxicity minimization through multiparameter assessment. This study advances safe-by-design catalysts for VCM synthesis, highlighting the importance of toxicity analyses in early-stage catalyst development programs.

A novel lipoformulation was developed by encapsulating cationic (S^C)-cyclometallated gold(III) complex [Au(dppta)(N2Py-PZ-dtc)]+ (AuPyPZ) in liposomes. The liposomal form of compound AuPyPZ has a bactericidal action similar to that of the free drug without any appreciable effect on the viability of mammalian cells. Furthermore, the nanoformulation reduces metalloantibiotic-induced inhibition of hERG and the inhibition of cytochromes, significantly decreasing the potential liabilities of the metallodrug. The obtained metalloantibiotic liposomal formulation shows high stability and suitable properties for drug delivery, representing an effective strategy to fight against drug-resistant bacteria.

A Bi(III)-catalyzed synthetic strategy for regioselective construction of C-N bonds via a simple Michael addition reaction is reported. A wide range of tautomerizable heterocycles such as benzoxazolones, benzothiazolones, benzimidazolinones, indolinones, and 2-pyridones along with α,β-unsaturated carbonyls (ketones and esters) are employed to create a library of corresponding N-alkylated derivatives exclusively. High regioselectivity, high atom economy, and the participation of a range of tautomerizable heterocycles highlight the uniqueness and generality of the developed methodology.

Ionic liquids (ILs), earlier praised for their eco-friendliness, have emerged as key chemicals in advancing green chemistry, catalysis, solvent development, and more. However, the discovery of their notable toxicity has led to a controversial reputation of ILs and has shifted the research landscape towards understanding their biological impacts. The present study examines the mechanism of cytotoxicity of 32 ILs across six classes, highlighting their effects on the cell cycle of the Jurkat cell line. Focusing on five ILs with pronounced cytotoxicity, we uncover their genotoxic effects and their role in inducing apoptosis. Our findings suggest intricate interplay between the extrinsic and intrinsic apoptotic pathways at different time points after exposure to ILs. Moreover, the ILs studied displayed marked genotoxicity, likely stemming from the accumulation of double-strand DNA breaks in the Jurkat cells. This investigation offers a comprehensive view on interactions of ILs with eukaryotic cells, thereby providing new guidelines for developing safer pharmaceutical and industrial applications of these chemicals. The results not only broaden and enhance the previous perceptions but also open new avenues in research, emphasizing the dual potential of ILs in innovation and safety, and marking a significant step towards integrating chemical innovations with biological safety.

Nowadays, particularly metallic, and polymeric nanoparticles (NPs) are widely produced and used in many fields. Due to the increase in both their usage and diversity, their release and accumulation in the environment are also accelerating. Therefore, their interactions with cells, especially immune cells, and their health risks are not fully understood. The impacts of metallic alumina (Al) NPs and polystyrene (PS) NPs obtained after the polymerization of carcinogenic styrene on living organisms have not yet been elucidated. Galleria mellonella larvae can biodegrade plastics. While biodegradation and solving the waste problem have attracted much attention, the interactions of this distinctive property of G. mellonella larvae in the immune system and ecosystem are not yet completely understood. Al and PS NPs were applied to G. mellonella separately. Al NPs were purchased and PS NPs were prepared from PS by single-emulsion technique and characterized. Then LC50 values of these NPs on G. mellonella were determined. The interactions of these NPs with encapsulation, melanization, and phenoloxidase activity, which express innate immune responses in G. mellonella larvae, were revealed. NP exposure resulted in suppression of the immune response, probably because it affects the functions of hemocytes such as enzymatic activation, hemocyte division, and populations. In this context, our data suggest that Al and PS NPs induce toxic impacts and negatively alter the physiological status of G. mellonella. It is also shown that G. mellonella has the potential to be an impactful alternative model for biosafety and nanotoxicology studies.

(Z)-1,2-Disubstituted, trisubstituted, and tetrasubstituted alkenes are not only important units in medicinal chemistry, natural product synthesis, and material science but also useful intermediates in organic synthesis. Development of catalytic stereoselective transformations to access multisubstituted alkenes with various substitution patterns from easily accessible modular starting materials and readily available catalysts is a crucial goal in the field of catalysis. Water is an ideal hydrogen source for catalytic transfer hydrogenation despite of the high difficulty to activate water. Here, we report a cobalt-catalyzed protocol for regio- and stereoselective transfer semihydrogenation of 1,3-dienes to construct a broad scope of (Z)-1,2-disubstituted, (Z)-, (E)-trisubstituted, and tetrasubstituted alkenes in high stereoselectivity with H2O as the hydrogen source. Mechanistic studies revealed that the reactions proceeded through a unique Co(I)/Co(III) cycle and involved a 1,4-cobalt shift process, which is an unprecedented reaction pathway, providing a new platform for modular synthesis of multisubstituted alkenes as well as opportunities for designing novel reaction modes and pushing forward the advancement in organocobalt chemistry.

Catalytic enantioselective alkenylation of aldehydes with easily accessible alkenyl halides promoted by a chiral cobalt complex derived from a newly developed tridentate bisoxazolinephosphine is presented. Such processes represent an unprecedented reaction pathway for cobalt catalysis and a general approach that enable rapid construction of highly diversified enantioenriched allylic alcohols containing a 1,1-, 1,2-disubstituted and trisubstituted alkene as well as axial stereogenicity in up to 99 % yield and 99 : 1 er without the need of preformation of alkenyl-metal reagents. DFT calculations revealed the origin of enantioselectivity.

Although dearomative functionalizations enable the direct conversion of flat aromatics into precious three-dimensional architectures, the case for simple arenes remains largely underdeveloped owing to the high aromatic stabilization energy. We herein report a dearomative sequential addition of two nucleophiles to arene π-bonds through umpolung of chromium-arene complexes. This mode enables divergent dearomative carbonylation reactions of benzene derivatives by tolerating various nucleophiles in combination with alcohols or amines under CO-gas-free conditions, thus providing modular access to functionalized esters or amides. The tunable synthesis of 1,3- or 1,4-cyclohexadienes as well as the construction of carbon quaternary centers further highlight the versatility of this dearomatization. Diverse late-stage modifications and derivatizations towards synthetically challenging and bioactive molecules reveal the synthetic utility. A possible mechanism was proposed based on control experiments and intermediate tracking.

The selective detection of Zn2⁺ and Fe2⁺ ions is critical in environmental and biological studies. Schiff base chemosensors hold promise, but exploration of thiophene-derived variants remains limited. This work introduces a novel thiophene-derived Schiff base sensor (TBH), synthesized through the condensation reaction of thiophene-2-carboxaldehyde with benzil-bis-hydrazone, for the selective detection of Zn2⁺ and Fe2⁺ ions. TBH exhibits remarkable selectivity, with a significant 185-fold fluorescence enhancement for Zn2⁺ and complete quenching 99% for Fe2⁺, allowing for distinct detection of both ions. Notably, TBH demonstrates high binding affinity towards Zn2⁺ and Fe2⁺, even in the presence of competing cations, forming stable 1:1 complexes. This finding is supported by absorption and emission titration studies and FT-IR analysis as well. This easily synthesized, rapid and cost-effective sensor offers a promising approach for sensitive and differentiated dual detection of Zn2⁺ and Fe2⁺ in environmental and biological systems.

Iridium(III) complexes nowadays became rising stars in various health-related applications. Thus, there is a necessity to assess cytotoxicity of the synthesized molecules against cancer/normal cell lines. In this report, we present a dataset of 2694 experimental cytotoxicity values of 803 iridium complexes against 127 different cell lines. We specify the experimental conditions and provide representation of the complexes molecules in machine-readable format. The dataset provides a starting point for exploration of new iridium-based cellular probes and opens new possibilities for predictions of toxicities and data-driven generation of new organometallic anticancer agents.

Luminescent materials with aggregation-induced emission (AIE) characteristics have been recognized as highly selective and sensitive probes for the detection of toxic metal ions in recent years. In this paper, a Au-Ag cluster-based coordination polymer [Au3Ag3(L)2(CN)6(H2O)2]n [1, L = 1,3-bis((diphenylphosphanyl)methyl)-4,5-dihydro-imidazolylidene] was prepared by in situ generation of the diphosphine N-heterocyclic carbene (PCNHCP)-type ligand L in the presence of the corresponding metal salts. Compound 1 exhibited 530 nm phosphorescence under 380 nm excitation with a QY of 6.30% and a lifetime (τ) of 7.14 μs in the solid state. 1 showed good AIE behavior in the mixture of MeOH/H2O while the best aggregation state (fwater = 90%, QY = 6.79%, τ = 6.70 μs) exhibited selective and sensitive emission quenching toward Cr(VI) ions. Ultralow detection limits of 9.7 ppb (w/w) for Cr2O72- and 17.9 ppb (w/w) for CrO42- were achieved.

The global threat posed by antimicrobial resistance (AMR) to public health is an immensurable problem. The effectiveness of treating infections would be more at risk in the absence of effective antimicrobials. Researchers have shown an amplified interest in alternatives, such as developing advanced metallic nanohybrids as new therapeutic candidates for antibiotics due to their promising effectiveness against resistant microorganisms. In recent decades, the antimicrobial activity of monometallic nanoparticles has received extensive study and solid proof, providing new opportunities for developing multimetallic nanohybrid antimicrobials. Advanced metallic nanohybrids are an emerging remedy for a number of issues that develop in the field of medicine. Advanced metallic nanohybrids have shown a promising ability to combat resistant microorganisms due to their overall synergistic activity. Formulating advanced multimetallic nanohybrids falling under the umbrella of the growing field of nanoarchitectonics, which extends beyond nanotechnology. The underlying theory of nanoarchitectonics involves utilizing nanoscale units that follow the concepts of nanotechnology to architect nanomaterials. This review focuses on a comprehensive description of antimicrobial mechanisms of metallic nanohybrids and their enabling future insights on the research directions of developing the nanoarchitectonics of advanced multimetallic nanohybrids as novel antibiotics through their synergistic activity.

Metal azides are highly energetic materials that release a large amount of gas upon detonation. They also release metal particles, generating an aerosol. The most common azide is sodium azide (NaN3), which is used nowadays in car airbags. If the decomposition is not complete, harmful azide particles might be inhaled. Heavy metal azides find application as a primary explosive (primer) in ammunition. Public health officials have raised concerns about heavy metal particles released during training in shooting ranges. We identify a lack of knowledge on airborne metal particles properties released from azide detonation and on the analytical methods applied to characterize them. As a case study, we detonated milligram amounts of silver azide, copper azide, and a mixture of them in a glove box. We then analyse the airborne particles with an ensemble analytical setup, able to measure real-time their particle size distribution and chemical composition. We detected spherical metal nanoparticles in the range of 2-500 nm. These findings and the developed analytical tools may allow identifying airborne nanoparticles the passenger compartments of vehicles after airbag activation as well as in indoor shooting ranges, contributing to the evaluation of public health risks.

The use of metal catalysts to accelerate an organic transformation has proven indispensable for access to structural motifs having applications across medicinal, polymer, materials chemistry, and more. Most catalytic approaches have cast transition metals in the "leading role"; these players mediate important reactions such as C-C cross coupling and the hydrogenation of unsaturated bonds. These catalysts may require collaboration, featuring Lewis acidic or basic additives to promote a desired reaction outcome. Lewis acids can serve to accelerate reactions by way of substrate stabilization and/or activation, and as such, are valuable in optimizing catalytic transformations. A burgeoning area of chemical research which unifies these concepts has thus sought to develop transition metal complexes having ambiphilic (containing a Lewis basic and acidic unit) ligands. This approach takes advantage of metal-ligand cooperativity to increase the efficiency of a given chemical transformation, leveraging intramolecular interactions between a transition metal and an adjacent secondary ligand site. While this has shown significant potential to facilitate challenging and important transformations, there remains unexplored depth for creativity and future advancement. This Frontier highlights inter- and intramolecular combinations of transition metals and Lewis acids that together, provide a collaborative platform for chemical synthesis.

Recent global events have led to the cost of platinum group metals (PGMs) reaching unprecedented heights. Many chemical companies are therefore starting to seriously consider and evaluate if and where they can substitute PGMs for non-PGMs in their catalytic processes. This review covers recent highly relevant applications of non-PGM catalysts in the modern pharmaceutical industry. By highlighting these selected successful examples of non-PGM-catalyzed processes from the literature, we hope to emphasize the enormous potential of non-PGM catalysis and inspire further development within this field to enable this technology to progress toward manufacturing processes. We also present some historical contexts and review the perceived advantages and challenges of implementing non-PGM catalysts in the pharmaceutical manufacturing environment.

Nanozymes are nanomaterials with intrinsic enzyme-like activity with selected advantages over native enzymes such as simple synthesis, controllable activity, high stability, and low cost. These materials have been explored as surrogates to natural enzymes in biosensing, therapeutics, environmental protection, and many other fields. Among different nanozymes classes, metal- and metal oxide-based nanozymes are the most widely studied. In recent years, bi- and tri-metallic nanomaterials have emerged often showing improved nanozyme activity, some of which even possess multifunctional enzyme-like activity. Taking this concept even further, high-entropy nanomaterials, that is, complex multicomponent alloys and ceramics like oxides, may potentially enhance activity even further. However, the addition of various elements to increase catalytic activity may come at the cost of increased toxicity. Since many nanozyme compositions are currently being explored for in vivo biomedical applications, such as cancer therapeutics, toxicity considerations in relation to nanozyme application in biomedicine are of vital importance for translation. This article is categorized under: Therapeutic Approaches and Drug Discovery > Emerging Technologies Toxicology and Regulatory Issues in Nanomedicine > Toxicology of Nanomaterials Diagnostic Tools > Diagnostic Nanodevices.

Mg-based and Zn-based biodegradable materials have the potential to become the next-generation implant materials to treat bone diseases, because of their desired degradation and mechanical properties. This article reviews the status of these implant materials. The required properties of biodegradable materials such as biodegradability, mechanical properties, and biocompatibility for performance evaluation were briefly discussed. The influence of fabrication techniques, microstructure, alloying elements, and post-processing techniques on the properties of Mg and Zn-based materials was addressed. The degradation mechanism by dissolution, oxidation, and interaction with human body cells was discussed. The biocompatibility of Mg and Zn-based biodegradable materials was analyzed. The significance of in vitro and in vivo biocompatibility testing was highlighted, emphasizing the superiority of in vivo results over cell line studies. This article identifies the many Mg and Zn-based biodegradable materials and summarizes the key findings.

Most fine ambient particulate matter (PM2.5)-based epidemiological models use globalized concentration-response (CR) functions assuming that the toxicity of PM2.5 is solely mass-dependent without considering its chemical composition. Although oxidative potential (OP) has emerged as an alternate metric of PM2.5 toxicity, the association between PM2.5 mass and OP on a large spatial extent has not been investigated. In this study, we evaluate this relationship using 385 PM2.5 samples collected from 14 different sites across 4 different continents and using 5 different OP (and cytotoxicity) endpoints. Our results show that the relationship between PM2.5 mass vs. OP (and cytotoxicity) is largely non-linear due to significant differences in the intrinsic toxicity, resulting from a spatially heterogeneous chemical composition of PM2.5. These results emphasize the need to develop localized CR functions incorporating other measures of PM2.5 properties (e.g., OP) to better predict the PM2.5-attributed health burdens.

A series of four Cd(II) complexes with 5-methyl-4-imidazolecarboxaldehyde (L) with different inorganic anions within or outside the coordination sphere of general formula: [CdCl2L2] (1), [CdBr2L2] (2), [CdI2L2] (3), and [CdL4](PF6)2·3H2O (4) was synthesized through one-step and two-step reactions, respectively. All complexes were obtained as colorless crystals without the need for recrystallization and exhibited solubility in aqueous solutions. Structural analysis revealed different coordination environments for each complex, with variations in bond lengths and angles. The crystal packing of the complexes was stabilized by hydrogen bonding and π-π stacking interactions. FT-IR analysis indicated coordination of the ligand to the metal ion, and UV-Vis studies confirmed the stability of the complexes in solution. Computational analysis has revealed the polar nature of the complexes and their favorable stability constants. Affinity studies with DNA using the switchSense technique demonstrated rapid association and dissociation processes for all complexes, with temperature-dependent binding constants. Thermodynamic analysis suggested spontaneous with positive entropy change and endothermic formation processes for the complexes. Overall, the study underscores the synthesis, examination, and interaction with DNA of Cd(II) complexes, demonstrating their promise within medicinal chemistry.

Leachates from municipal landfills introduce toxic heavy metals into water, causing bioaccumulation. This study assesses metal levels and potential human health risks associated with consuming Anabas testudineus and Channa striata. Inductively coupled plasma mass spectrometry detected Cd, Cu, Cr, Ni, Pb, and Zn in both fish species. Leachate metal concentrations meet international discharge standards, Cd, Cr, and Pb in the fish exceed the international accepted values. Gastrointestinal tract+liver samples show significant variation between species, particularly in Cd and Pb. EDI, THQ/HI, and TR for the both species fall below TDIs, lower than the limit of 1, and within the acceptable range of the US-EPA permissible limit, respectively. Fish consumption appears safe regarding carcinogenic risk, but exceeding metal limits could impact heavy metals accumulation in the local food chain. Raising public awareness is crucial, and governmental agencies and environmental organizations should enhance waste treatment technologies and enact relevant health legislation.

Transition metal catalysis has contributed to the discovery of novel methodologies and the preparation of natural products, as well as new chances to increase the chemical space in drug discovery programs. In the case of marine drugs, this strategy has been used to achieve selective, sustainable and efficient transformations, which cannot be obtained otherwise. In this perspective, we aim to showcase how a variety of transition metals have provided fruitful couplings in a wide variety of marine drug-like scaffolds over the past few years, by accelerating the production of these valuable molecules.

The efficiency of a catalytic process is assessed based on conversion, yield, and time effectiveness. However, these parameters are insufficient for evaluating environmentally sustainable research. As the world is urged to shift towards green catalysis, additional factors such as reaction media, raw material availability, sustainability, waste minimization and catalyst biosafety, need to be considered to accurately determine the efficacy and sustainability of the process. By combining the high porosity and versatility of metal organic frameworks (MOFs) and the activity of gold nanoparticles (AuNPs), efficient, cyclable and biosafe composite catalysts can be achieved. Thus, a composite based on AuNPs and the nanometric flexible porous iron(III) aminoterephthalate MIL-88B-NH2 was successfully synthesized and fully characterized. This nanocomposite was tested as catalyst in the reduction of nitroarenes, which were identified as anthropogenic water pollutants, reaching cyclable high conversion rates at short times for different nitroarenes. Both synthesis and catalytic reactions were performed using green conditions, and even further tested in a time-optimizing one-pot synthesis and catalysis experiment. The sustainability and environmental impact of the catalytic conditions were assessed by green metrics. Thus, this study provides an easily implementable synthesis, and efficient catalysis, while minimizing the environmental and health impact of the process.

Free radicals produced during metabolism induce effects, such as cell damage and cancer, because of their high reactivity. Although antioxidants in food products can eliminate free radicals, they are expelled within a relatively short period of time after serving their function. In this study, we investigated the possibility of using metal-organic frameworks (MOFs) with antioxidants as their ligands. Metal-organic frameworks are crystalline polymers with repetitively coordinated ligands and metal centers. We assume that once antioxidant-based MOFs are ingested, ligands are released on a long-term basis during the process of chemical and physical disintegration. To evaluate their eligibility, we established criteria for biocompatibility, particle size, and long-term antioxidant effects. For biocompatibility, we treated cells with various concentrations of MOFs and their precursors followed by a water-soluble tetrazolium 8 (WST-8) assay. The particle size distribution was analyzed using TEM and ImageJ software, and the antioxidant release was quantified using UV-vis spectroscopy. We concluded that Fe-based FeTHQ with the antioxidant tetrahydroxy-1,4-benzoquinone (THQ) as its ligand is the most effective long-term antioxidant with its effect lasting up to 7 days. Furthermore, microwave synthesis of FeTHQ was conducted to produce more suitable particles for in vivo antioxidant applications.