Influence of acid-base equilibrium on interactions of some monofunctional coumarin Pd(II) complexes with biologically relevant nucleophiles-comprehensive kinetic study.

This aimed to develop a comprehensive theoretical protocol for examining substitution reaction processes. The researchers used a theoretical quantum-mechanical protocol based on the QM-ORSA approach, which estimates the kinetic parameters of thermodynamically favourable reaction pathways. This theoretical protocol was validated by experimentally investigating substitution mechanisms in two previously synthesised Pd(II) complexes: chlorido-[(3-(1-(2-hydroxypropylamino)ethylidene)chroman-2,4-dione)]palladium(II) (C1) and chlorido-[(3-(1-(2-mercaptoethylamino)-ethylidene)-chroman-2,4dione)]palladium(II) (C2), along with biologically relevant nucleophiles, namely L-cysteine (l-Cys), L-methionine (l-Met), and guanosine-5'-monophosphate (5'-GMP). Reactions were investigated under pseudo-first-order conditions, monitoring nucleophile concentration and temperature changes using stopped-flow UV-vis spectrophotometry. All reactions were conducted under physiological conditions (pH = 7.2) at 37 °C. The reactivity of the studied nucleophiles follows the order: l-Cys > l-Met > 5'-GMP, and the reaction mechanism is associative based on the activation parameters. The experimental and theoretical data showed that C2 is more reactive than C1, confirming that the complexes' structural and electronic properties greatly affect their reactivity with selected nucleophiles. The study's findings have confirmed that the primary interaction occurs with the acid-base species L-Cys, mostly through the involvement of the partially negative sulfur atom (87.2%). On the other hand, C2 has a higher propensity for reacting with L-Cys-, primarily through the partially negative oxygen atom (92.6%). The implementation of this theoretical framework will significantly restrict the utilization of chemical substances, hence facilitating cost reduction and environmental protection.

Novel triphenyltin(IV) compounds with carboxylato N-functionalized 2-quinolones as promising potential anticancer drug candidates: in vitro and in vivo evaluation.

Three newly synthesized triphenyltin(IV) compounds, Ph3SnL1 (L1- = 3-(4-methyl-2-oxoquinolin-1(2H)-yl)propanoato), Ph3SnL2 (L2- = 2-(4-methyl-2-oxoquinolin-1(2H)-yl)ethanoato), and Ph3SnL3 (L3- = 2-(4-hydroxy-2-oxoquinolin-1(2H)-yl)ethanoato), were characterized by elemental microanalysis, FT-IR spectroscopy and multinuclear (1H, 13C and 119Sn) NMR spectroscopy. A single X-ray diffraction study indicates that compounds Ph3SnL1 and Ph3SnL2 exhibit a 1D zig-zag chain polymeric structure, which in the case of Ph3SnL2 is additionally stabilized by π-interactions. In addition, the synthesized compounds were further examined using density functional theory and natural bond orbital analysis. The compounds have been evaluated for their in vitro anticancer activity against three human cell lines: MCF-7 (breast adenocarcinoma), A375 (melanoma), HCT116 (colorectal carcinoma), and three murine cell lines: 4T1 (breast carcinoma), B16 (melanoma), CT26 (colon carcinoma) using MTT and CV assays. The IC50 values fall in the nanomolar range, indicating that these compounds possess better anticancer activity than cisplatin. The study of the effect of the newly developed drug Ph3SnL1 showed its plasticity in achieving an antitumor effect in vitro, which depends on the specificity of the phenotype and the redox status of the malignant cell line and ranges from the initiation of apoptotic cell death to the induction of differentiation to a more mature cell form. In the syngeneic model of murine melanoma, Ph3SnL1 showed the potential to reduce the tumor volume similar to cisplatin, but in a well-tolerated form and with low systemic toxicity, representing a significant advantage over the conventional drug.

Reduction in Pathogenic Biofilms by the Photoactive Composite of Bacterial Cellulose and Nanochitosan Dots under Blue and Green Light.

In this study, nanochitosan dots (ChiDs) were synthesized using gamma rays and encapsulated in bacterial cellulose (BC) polymer matrix for antibiofilm potential in photodynamic therapy. The composites were analyzed for structural changes using SEM, AFM, FTIR, XRD, EPR, and porosity measurements. Additionally, ChiD release was assessed. The results showed that the chemical composition remained unaltered, but ChiD agglomerates embedded in BC changed shape (1.5-2.5 µm). Bacterial cellulose fibers became deformed and interconnected, with increased surface roughness and porosity and decreased crystallinity. No singlet oxygen formation was observed, and the total amount of released ChiD was up to 16.10%. Antibiofilm activity was higher under green light, with reductions ranging from 48 to 57% under blue light and 78 to 85% under green light. Methicillin-resistant Staphylococcus aureus was the most sensitive strain. The new photoactive composite hydrogels show promising potential for combating biofilm-related infections.

Antibacterial and Antibiofouling Activities of Carbon Polymerized Dots/Polyurethane and C60/Polyurethane Composite Films.

The cost of treatment of antibiotic-resistant pathogens is on the level of tens of billions of dollars at the moment. It is of special interest to reduce or solve this problem using antimicrobial coatings, especially in hospitals or other healthcare facilities. The bacteria can transfer from medical staff or contaminated surfaces to patients. In this paper, we focused our attention on the antibacterial and antibiofouling activities of two types of photodynamic polyurethane composite films doped with carbon polymerized dots (CPDs) and fullerene C60. Detailed atomic force, electrostatic force and viscoelastic microscopy revealed topology, nanoelectrical and nanomechanical properties of used fillers and composites. A relationship between the electronic structure of the nanocarbon fillers and the antibacterial and antibiofouling activities of the composites was established. Thorough spectroscopic analysis of reactive oxygen species (ROS) generation was conducted for both composite films, and it was found that both of them were potent antibacterial agents against nosocomial bacteria (Klebsiela pneumoniae, Proteus mirabilis, Salmonela enterica, Enterococcus faecalis, Enterococcus epidermis and Pseudomonas aeruginosa). Antibiofouling testing of composite films indicated that the CPDs/PU composite films eradicated almost completely the biofilms of Pseudomonas aeruginosa and Staphylococcus aureus and about 50% of Escherichia coli biofilms.

Mechanism of Antiradical Activity of Coumarin-Trihydroxybenzohydrazide Derivatives: A Comprehensive Kinetic DFT Study.

As part of this study, the mechanisms of the antioxidant activity of previously synthesized coumarin-trihydrobenzohydrazine derivatives were investigated: (E)-2,4-dioxo-3-(1-(2-(2″,3″,4″-trihydroxybenzoyl)hydrazineyl)ethylidene)chroman-7-yl acetate (1) and (E)-2,4-dioxo-3-(1-(2-(3″,4″,5″-trihydroxybenzoyl)hydrazineyl)ethylidene)chroman-7-yl acetate (2). The capacity of the compounds to neutralize HO• was assessed by EPR spectroscopy. The standard mechanisms of antioxidant action, Hydrogen Atom Transfer (HAT), Sequential Proton Loss followed by Electron Transfer (SPLET), Single-Electron Transfer followed by Proton Transfer (SET-PT), and Radical Adduct/Coupling Formation (RAF/RCF) were examined using the QM-ORSA methodology. It was estimated that the newly synthesized compounds, under physiological conditions, exhibited antiradical activity via SPLET and RCF mechanisms. Based on the estimated overall rate constants (koverall), it can be concluded that 2 exhibited a greater antiradical capacity. The obtained values indicated a good correlation with the EPR spectroscopy results. Both compounds exhibit approximately 1.5 times more activity in comparison to the precursor compound used in the synthesis (gallic acid).

Biosynthesis and characterization of silver nanoparticles synthesized using extracts of Agrimonia eupatoria L. and in vitro and in vivo studies of potential medicinal applications.

This research explores the synthesis, characterization, and biological activities of silver nanoparticles (AgNPs) derived from acetone (AgNPs-acetone) and aqueous (AgNPs-H2O) extracts of Agrimonia eupatoria. The nanoparticles exhibit isometric morphology and uniform size distribution, as elucidated through Transmission Electron Microscopy (TEM) and high-resolution TEM (HRTEM) analyses. The utilization of Scanning Transmission Microscopy (STEM) with High-Angle Annular Dark-Field (HAADF) imaging and energy dispersive spectrometry (EDS) confirms the crystalline nature of AgNPs. Fourier Transform Infrared (FTIR) analysis reveals identical functional groups in the plant extracts and their corresponding AgNPs, suggesting the involvement of phytochemicals in the reduction of silver ions. Spectrophotometric monitoring of the synthesis process, influenced by various parameters, provides insights into the kinetics and optimal conditions for AgNP formation. The antioxidant activities of the plant extracts and synthesized AgNPs are evaluated through DPPH and ABTS methods, highlighting AgNPs-acetone as a potent antioxidant. Third-instar larvae exposed to the extracts have differential effects on DNA damage, with the acetone extract demonstrating antigenotoxic properties. Similarly, biosynthesized AgNPs-acetone displays antigenotoxic effects against EMS-induced DNA damage. The genotoxic effect of water extract and AgNPs-acetone was dose-dependent. Hemolytic potential is assessed on rat erythrocytes, revealing that low concentrations of AgNPs-acetone and AgNPs-H2O had a nontoxic effect on erythrocytes. Cytotoxicity assays demonstrate time-dependent and dose-dependent effects, with AgNPs-acetone exhibiting superior cytotoxicity. Proapoptotic activity is confirmed through apoptosis induction, emphasizing the potential therapeutic applications of AgNPs. The antimicrobial activity of AgNPs reveals concentration-dependent effects. AgNPs-H2O display better antibacterial activity, while antifungal activities are comparable between the two nanoparticle types.

Investigation of novel radical scavenging mechanisms in the alkaline environment: Green, sustainable and environmentally friendly antioxidative agent(s).

Pharmaceutical and industrial utilization of synthetic chemicals has an immerse impact on the environment. In that sense, novel chemicals with potential for industrial application should be investigated for their behaviour in reactions with hydroxyl radical, simulating AOPs (Advanced Oxidation Processes). AOPs are known for being highly effective in wastewater management and natural water remediation. In this paper, exhaustive research on the radical scavenging activity of a newly synthesized coumarin derivative (4HCBH), as a representative of the series of coumarin-benzohydrazides with high antioxidative potential was conducted. This study took into consideration the pH value range significant for practically all living organisms (pH = 7.0-8.5). According to the experimentally obtained results, the 4HCBH showed an increase in radical scavenging activity, following the slight increase in pH values, which suggested that the formation of anionic form of 4HCBH is responsible for its antiradical activity. Further investigations led to the postulation of a novel mechanistic approach called Sequential Proton Loss Electron Transfer - Radical-Radical Coupling (SPLET-RRC), in which, by a series of steps, a new, stable compound was formed. Furthermore, it was demonstrated that the product generated through SPLET-RRC showed lower toxicity than the parent molecule.

An Effective, Green Synthesis Procedure for Obtaining Coumarin-Hydroxybenzohydrazide Derivatives and Assessment of Their Antioxidant Activity and Redox Status.

In this study, green synthesis of two derivatives of coumarin-hydroxybenzohydrazide, (E)-2,4-dioxo-3-(1-(2-(2,3,4-trihydroxybenzoyl)hydrazyl)ethylidene)-chroman-7-yl acetate (C-HB1), and (E)-2,4-dioxo-3-(1-(2-(3,4,5-trihydroxybenzoyl)hydrazyl)ethylidene)chroman-7-yl acetate (C-HB2) is reported. Using vinegar and ethanol as a catalyst and solvent, the reactions were carried out between 3-acetyl-4-hydroxy-coumarin acetate and corresponding trihydroxybenzoyl hydrazide. The antioxidant potential of these compounds was investigated using the DPPH and ABTS assays, as well as the FRAP test. The obtained results reveal that even at very low concentrations, these compounds show excellent radical scavenging potential. The IC50 values for C-HB1 and C-HB2 in relation to the DPPH radical are 6.4 and 2.5 µM, respectively, while they are 4.5 and 2.0 µM in relation to the ABTS radical. These compounds have antioxidant activity that is comparable to well-known antioxidants such as gallic acid, NDGA, and trolox. These results are in good correlation with theoretical parameters describing these reactions. Moreover, it was found that inhibition of DPPH● follows HAT, while inactivation of ABTS+● follows SET-PT and HAT mechanisms. Additionally, coumarin-hydroxybenzohydrazide derivatives induced moderate cytotoxic activity and show significant potential to modulate redox status in HCT-116 colorectal cancer cells. The cytotoxicity was achieved via their prooxidative activity and ability to induce oxidative stress in cancer cells by increasing O2˙- concentrations, indicated by increased MDA and GSH levels. Thus, ROS manipulation can be a potential target for cancer therapies by coumarins, as cancer cells possess an altered redox balance in comparison to normal cells. According to the ADMET analysis, the compounds investigated show good pharmacokinetic and toxicological profiles similar to vitamin C and gallic acid, which makes them good candidates for application in various fields of industry and medicine.

Synthesis, Structural Characterization, Cytotoxicity, and Protein/DNA Binding Properties of Pyridoxylidene-Aminoguanidine-Metal (Fe, Co, Zn, Cu) Complexes.

Pyridoxylidene-aminoguanidine (PLAG) and its transition metal complexes are biologically active compounds with interesting properties. In this contribution, three new metal-PLAG complexes, Zn(PLAG)(SO4)(H2O)].∙H2O (Zn-PLAG), [Co(PLAG)2]SO4∙2H2O (Co-PLAG), and [Fe(PLAG)2]SO4∙2H2O) (Fe-PLAG), were synthetized and characterized by the X-ray crystallography. The intermolecular interactions governing the stability of crystal structure were compared to those of Cu(PLAG)(NCS)2 (Cu-PLAG) within Hirshfeld surface analysis. The structures were optimized at B3LYP/6-31+G(d,p)(H,C,N,O,S)/LanL2DZ (Fe,Co,Zn,Cu), and stability was assessed through Natural Bond Orbital Theory and Quantum Theory of Atoms in Molecules. Special emphasis was put on investigating the ligand's stability and reactivity. The binding of these compounds to Bovine and Human serum albumin was investigated by spectrofluorometric titration. The importance of complex geometry and various ligands for protein binding was shown. These results were complemented by the molecular docking study to elucidate the most important interactions. The thermodynamic parameters of the binding process were determined. The binding to DNA, as one of the main pathways in the cell death cycle, was analyzed by molecular docking. The cytotoxicity was determined towards HCT116, A375, MCF-7, and A2780 cell lines. The most active compound was Cu-PLAG due to the presence of PLAG and two thiocyanate ligands.

Coumarin N-Acylhydrazone Derivatives: Green Synthesis and Antioxidant Potential-Experimental and Theoretical Study.

Coumarin N-acylhydrazone derivatives were synthesized in the reaction of 3-acetylcoumarin and different benzohydrazides in the presence of molecular iodine as catalyst and at room temperature. All reactions were rapidly completed, and products were obtained in good to excellent yields. It is important to emphasize that four products were reported for the first time in this study. The obtained compounds were subjected to evaluation of their in vitro antioxidative activity using DPPH, ABTS, and FRAP methods. It was shown that products with a catechol moiety in their structure are the most potent antioxidant agents. The thermodynamic parameters and Gibbs free energies of reactions were used to determine the most probable mechanism of action. The results of in silico examination emphasize the need to take solvent polarity and free radical species into account when examining antiradical action. It was discovered by using computational approaches that HAT and SPLET are competitive molecular pathways for the radical scavenging activity of all compounds in polar mediums, while the HAT is the dominant mechanism in non-polar environments.

Synthesis, characterization, biomolecular interactions, molecular docking, and in vitro and in vivo anticancer activities of novel ruthenium(III) Schiff base complexes.

In order to discover new anticancer drugs, novel ruthenium(III) complexes [Ru(L)Cl(H2O)], where L is tetradentate Schiff base bis(acetylacetone)ethylendiimine (acacen, 1), bis(benzoylacetone)ethylendiimine (bzacen, 2), (acetylacetone)(benzoylaceton)ethylendiimine (acacbzacen, 3), bis(acetylacetone)propylendiimine (acacpn, 4), bis(benzoylacetone)propylendiimine (bzacpn, 5) or (acetylacetone)(benzoylaceton)propylendiimine (acacbzacpn, 6), were synthesized. The complexes 1 - 6 were characterized by elemental analysis, molar conductometry, and by various spectroscopic techniques, such as UV-Vis, IR, EPR, and ESI-MS. Based on in vitro DNA/BSA experiments, complexes 2 (bzacen) and 5 (bzacpn) with two aromatic rings showed the highest DNA/BSA-activity, suggesting that the presence of the aromatic ring on the tetradentate Schiff base ligand contributes to increased activity. Moreover, these two compounds showed the highest cytotoxic effects toward human, A549 and murine LLC1 lung cancer cells. These complexes altered the ratio of anti- and pro-apoptotic molecules and induced apoptosis of A549 cells. Further, complexes 2 and 5 reduced the percentage of Mcl1 and Bcl2 expressing LLC1 cells, induced their apoptotic death and exerted an antiproliferative effect against LLC1. Finally, complex 5 reduced the volume of mouse primary heterotopic Lewis lung cancer, while complex 2 reduced the incidence and mean number of metastases per lung. Additionally, molecular docking with DNA revealed that the reduced number of aromatic rings or their absence causes lower intercalative properties of the complexes in order: 2 > 5 > 6 > 3 > 4 > 1. It was observed that conventional hydrogen bonds and hydrophobic interactions contribute to the stabilization of the structures of complex-DNA. A molecular docking study with BSA revealed a predominance of 1 - 6 in binding affinity to the active site III, a third D-shaped hydrophobic pocket within subdomain IB.

The Effect of Metal Ions (Fe, Co, Ni, and Cu) on the Molecular-Structural, Protein Binding, and Cytotoxic Properties of Metal Pyridoxal-Thiosemicarbazone Complexes.

Thiosemicarbazones and their transition metal complexes are biologically active compounds and anticancer agents with versatile structural properties. In this contribution, the structural features and stability of four pyridoxal-thiosemicarbazone (PLTSC) complexes with Fe, Co, Ni, and Cu were investigated using the density functional theory and natural bond orbital approach. Special emphasis was placed on the analysis of the donor atom-metal interactions. The geometry of compounds and crystallographic structures were further examined by Hirshfeld surface analysis, and the main intermolecular interactions were outlined. It has been shown that the geometry and the number of PLTSC units in the structure determine the type and contribution of the specific interactions. The binding of all four complexes to bovine and human serum albumin was investigated through spectrofluorometric titration. The dependency of the thermodynamic parameters on the present metal ion and geometry was explained by the possible interactions through molecular docking simulations. The binding of complexes to DNA, as one of the possible ways the compounds could induce cell death, was examined by molecular docking. The cytotoxicity was measured towards HCT116, A375, MCF-7, A2780, and MCF5 cell lines, with Cu-PLTSC being the most active, as it had the highest affinity towards DNA and proteins.

In silico evaluation of pharmacokinetic parameters, delivery, distribution and anticoagulative effects of new 4,7-dihydroxycoumarin derivative.

In this study, pharmacological profiling and investigation of the anticoagulant activity of the newly synthesized coumarin derivative: (E)-3-(1-((4-hydroxy-3-methoxyphenyl)amino)ethylidene)-2,4-dioxochroman-7-yl acetate (L) were performed. The obtained results were compared with the parameters obtained for Warfarin (WF), which is a standard good oral anticoagulant. The estimated high binding affinity of L toward plasma proteins (PPS% value is > 90%) justifies the investigation of binding affinity and comparative analysis of L and WF to Human Serum Albumin (HSA) using the spectrofluorimetric method (296, 303 and 310 K) as well as molecular docking and molecular dynamics simulations. Compound L shows a very good binding affinity especially to the active site of WF (the active site I -subdomain IIA), quenching HSA fluorescence by a static process. Also, the finite element smeared model (Kojic Transport Model, KTM), which includes blood vessels and tissue, was implemented to compute the convective-diffusion transport of L and WF within the liver. Finally, compound L shows a high degree of inhibitory activity toward the VKOR receptor comparable to the inhibitory activity of WF. Stabilization and limited flexibility of amino acid residues in the active site of the VKOR after binding of L and WF indicates a very good inhibitory potential of compound L. The high affinity of the L for the VKOR enzyme (Vitamin K antagonist), as well as the structural similarity to commercial anticoagulants (WF), provide a basis for further studies and potential application in the treatment of venous thrombosis, pulmonary embolism and ischemic heart disease.Communicated by Ramaswamy H. Sarma.

The Electronic Effects of 3-Methoxycarbonylcoumarin Substituents on Spectral, Antioxidant, and Protein Binding Properties.

Coumarin derivatives are a class of compounds with pronounced biological activities that depend primarily on the present substituents. Four 3-methoxycarbonylcoumarin derivatives with substituents of different electron-donating/electron-withdrawing abilities (Br, NO2, OH, and OMe) were investigated structurally by NMR, IR, and UV-VIS spectroscopies and density functional theory methods. The appropriate level of theory (B3LYP-D3BJ/6-311++G(d,p) was selected after comparing similar compounds' experimental and theoretical structural parameters. The natural bond orbital and quantum theory of atoms in molecules were employed to investigate the intramolecular interactions governing stability. The electronic effects of substituents mostly affected the aromatic ring that the substituents are directly attached to. The antioxidant properties were investigated by electron paramagnetic resonance spectroscopy towards HO•, and the percentages of reduction were between 13% (6-Br) and 23% (6-OMe). The protein binding properties towards transport proteins were assessed by spectrofluorimetry, molecular docking, and molecular dynamics (MD). The experimentally determined binding energies were well reproduced by molecular docking, showing that the spontaneity of ibuprofen binding was comparable to the investigated compounds. The flexibility of HSA in MD simulations depended on the substituents. These results proved the importance of electronic effects for the protein binding affinities and antioxidant properties of coumarin derivatives.

Employing Gamma-Ray-Modified Carbon Quantum Dots to Combat a Wide Range of Bacteria.

Nowadays, it is a great challenge to develop new medicines for treating various infectious diseases. The treatment of these diseases is of utmost interest to further prevent the development of multi-drug resistance in different pathogens. Carbon quantum dots, as a new member of the carbon nanomaterials family, can potentially be used as a highly promising visible-light-triggered antibacterial agent. In this work, the results of antibacterial and cytotoxic activities of gamma-ray-irradiated carbon quantum dots are presented. Carbon quantum dots (CQDs) were synthesized from citric acid by a pyrolysis procedure and irradiated by gamma rays at different doses (25, 50, 100 and 200 kGy). Structure, chemical composition and optical properties were investigated by atomic force microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, Raman spectroscopy, UV-Vis spectrometry and photoluminescence. Structural analysis showed that CQDs have a spherical-like shape and dose-dependent average diameters and heights. Antibacterial tests showed that all irradiated dots had antibacterial activity but CQDs irradiated with dose of 100 kGy had antibacterial activity against all seven pathogen-reference bacterial strains. Gamma-ray-modified CQDs did not show any cytotoxicity toward human fetal-originated MRC-5 cells. Moreover, fluorescence microscopy showed excellent cellular uptake of CQDs irradiated with doses of 25 and 200 kGy into MRC-5 cells.

Investigation of the radical scavenging potential of vanillin-based pyrido-dipyrimidines: experimental and in silico approach.

Antioxidants have a significant contribution in the cell protection against free radicals which may induce oxidative stress, and permanently damage the cells causing different disorders such as tumors, degenerative diseases, and accelerated aging. Nowadays, a multi-functionalized heterocyclic framework plays an important role in drug development, and it is of great importance in organic synthesis and medicinal chemistry. Encouraged by the bioactivity of the pyrido-dipyrimidine scaffold and vanillin core, herein, we made an effort to thoroughly investigate the antioxidant potential of the vanillin-based pyrido-dipyrimidines A-E to reveal novel promising free radical inhibitors. The structural analysis and the antioxidant action of the investigated molecules were performed in silico by DFT calculations. Studied compounds were screened for their antioxidant capacity using in vitro ABTS and DPPH assays. All the investigated compounds showed remarkable antioxidant activity, especially derivative A exhibiting inhibition of free radicals at the IC50 value (ABTS and DPPH assay 0.1 mg ml-1 and 0.081 mg ml-1, respectively). Compound A has higher TEAC values implying its stronger antioxidant activity compared to a trolox standard. The applied calculation method and in vitro tests confirmed that compound A has a strong potential against free radicals and may be a novel candidate for application in antioxidant therapy.

Lights and Dots toward Therapy-Carbon-Based Quantum Dots as New Agents for Photodynamic Therapy.

The large number of deaths induced by carcinoma and infections indicates that the need for new, better, targeted therapy is higher than ever. Apart from classical treatments and medication, photodynamic therapy (PDT) is one of the possible approaches to cure these clinical conditions. This strategy offers several advantages, such as lower toxicity, selective treatment, faster recovery time, avoidance of systemic toxic effects, and others. Unfortunately, there is a small number of agents that are approved for usage in clinical PDT. Novel, efficient, biocompatible PDT agents are, thus, highly desired. One of the most promising candidates is represented by the broad family of carbon-based quantum dots, such as graphene quantum dots (GQDs), carbon quantum dots (CQDs), carbon nanodots (CNDs), and carbonized polymer dots (CPDs). In this review paper, these new smart nanomaterials are discussed as potential PDT agents, detailing their toxicity in the dark, and when they are exposed to light, as well as their effects on carcinoma and bacterial cells. The photoinduced effects of carbon-based quantum dots on bacteria and viruses are particularly interesting, since dots usually generate several highly toxic reactive oxygen species under blue light. These species are acting as bombs on pathogen cells, causing various devastating and toxic effects on those targets.

Risk Evaluation of Pollutants Emission from Coal and Coal Waste Combustion Plants and Environmental Impact of Fly Ash Landfilling.

Emission factors (EFs) of gaseous pollutants, particulate matter, certain harmful trace elements, and polycyclic aromatic hydrocarbons (PAHs) from three thermal power plants (TPPs) and semi-industrial fluidized bed boiler (FBB) were compared. EFs of particulate matter, trace elements (except Cd and Pb), benzo[a]pyrene, and benzo[b]fluoranthene exceed the upper limits specified in the EMEP inventory guidebook for all combustion facilities. The comparison of trace elements and PAHs content in fly ashes (FAs) from lignite and coal waste combustion in TPPs and FBB, respectively, as well as the potential environmental impact of FAs disposal, was performed by employing a set of ecological indicators such as crustal enrichment factor, risk assessment code, risk indices for trace elements, and benzo[a]pyrene equivalent concentration for PAHs. Sequential analysis shows that the trace elements portion is the lowest for water-soluble and exchangeable fractions. The highest enrichment levels in FAs are noticed for As and Hg. Based on toxic trace elements content, FAs from TPPs represent a very high ecological risk, whereas fly ash from FBB poses a moderate ecological risk but has the highest benzo[a]pyrene equivalent concentration, indicating its increased carcinogenic potential. Lead isotope ratios for Serbian coals and FAs can contribute to a lead pollution global database.

UHPLC-MS Phytochemical Profiling and Insight into Bioactivity of Rabelera holostea (Greater Stitchwort) Extract.

Rabelera holostea (L.) M. T. Sharples & E. A. Tripp (Greater Stitchwort), formerly known as Stellaria holostea L., is widespread in the warm temperate areas of Europe and Western Asia, the Caucasus region, as well as in some countries of North Africa. Nowadays it is considered as a weed, but earlier it was often used raw in salads or for the treatment of various inflammatory disorders. The goal of this study was to determine the constituents of the methanol extract of R. holostea aerial parts and its biological potential in terms of antioxidant, antimicrobial, and anti-inflammatory properties. Until now, the constituents and biological activities of this plant were not reported in detail. A comprehensive phytochemical profiling of the extract has shown that phenolic acids, such as ferulic, chlorogenic, and p-coumaric acid, flavonoids and flavonoid glucosides, such as chrysoeriol, rutin, and naringin, are the most abundant compounds. The antioxidant activity of R. holostea extract towards DPPH and ABTS radicals, but also the total antioxidant capacity and the inhibition of lipid peroxidation were moderate. The antimicrobial potential was pronounced mostly towards some fungi such as F. oxysporum (MIC 1.25 mg/mL), whereas the capacity of R. holostea to affect the growth of bacteria was much less pronounced. R. holostea extract was most inclined to anti-inflammatory activity. At a concentration of 50 µg/mL, it significantly inhibited both cyclooxygenase enzymes (COX-1 and COX-2) by 71.24% and 72.83%, respectively. Molecular docking studies indicated that chlorogenic acid and chrysoeriol are the main contributors to COX-1 and COX-2 inhibitory activity.

Degradation Mechanisms of 4,7-Dihydroxycoumarin Derivatives in Advanced Oxidation Processes: Experimental and Kinetic DFT Study.

Coumarins represent a broad class of compounds with pronounced pharmacological properties and therapeutic potential. The pursuit of the commercialization of these compounds requires the establishment of controlled and highly efficient degradation processes, such as advanced oxidation processes (AOPs). Application of this methodology necessitates a comprehensive understanding of the degradation mechanisms of these compounds. For this reason, possible reaction routes between HO• and recently synthesized aminophenol 4,7-dihydroxycoumarin derivatives, as model systems, were examined using electron paramagnetic resonance (EPR) spectroscopy and a quantum mechanical approach (a QM-ORSA methodology) based on density functional theory (DFT). The EPR results indicated that all compounds had significantly reduced amounts of HO• radicals present in the reaction system under physiological conditions. The kinetic DFT study showed that all investigated compounds reacted with HO• via HAT/PCET and SPLET mechanisms. The estimated overall rate constants (koverall) correlated with the EPR results satisfactorily. Unlike HO• radicals, the newly formed radicals did not show (or showed negligible) activity towards biomolecule models representing biological targets. Inactivation of the formed radical species through the synergistic action of O2/NOx or the subsequent reaction with HO• was thermodynamically favored. The ecotoxicity assessment of the starting compounds and oxidation products, formed in multistage reactions with O2/NOx and HO•, indicated that the formed products showed lower acute and chronic toxicity effects on aquatic organisms than the starting compounds, which is a prerequisite for the application of AOPs procedures in the degradation of compounds.