Sulfur Atoms Research Articles

Synthesis, Characterization, Crystal structure determination and DFT study of a six coordinated Cu (II) complex of a phosphorous based tris-(2-pyridinylamino) phosphene sulphide ligand and its acid catalysed hydrolysis

One mono nuclear copper(II) complex (Cu-TPPS-OOCCH3 with structural formula C17H19CuN6O3PS) is synthesized using a novel tripodal tetradentate ligand, tris-(2-pyridinylamino)phosphene sulphide (TPPS), which has three pyridinylamino groups attached to a phosphorus atom connected to a sulphur atom (PS). The equatorial positions of the complex are occupied by three amino N-atoms of three aminopyridyl groups and one O-atom of the acetate group. The apical position is occupied by other O-atom of acetate group and one secondary N-atom of the tripodal ligand. The complex has been synthesized and purified as green solid and characterized by various spectroscopic techniques and the structure has been determined by X-ray single crystal diffraction study. The geometry optimizations and calculations of energies of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of the compounds are performed by using the hybrid B3LYP density functional theory (DFT) along with the def2TZVP basis set.

Thionation of conjugated porphyrin with enhanced photodynamic and photothermal effects for cancer therapy

Phototherapy has emerged as a promising modality for cancer treatment in recent years, owing to its precise temporal control and minimally invasive nature. Here, two new organic porphyrin molecules, denoted as ONP and SNP, were designed and synthesized with an acceptor–donor–acceptor (A-D-A) architecture. The donor–acceptor (D-A) pairs in molecules facilitated the intermolecular charge transfer (ICT), thereby amplifying near-infrared (NIR) absorbance and promoting nonradiative heat generation. Notably, the substitution of oxygen atoms with sulfur in naphthalimides (NI) led to significant change of their photophysical and photochemical properties. Specifically, the sulfur atoms exhibited pronounced spin–orbit coupling (SOC) effect, leading to efficient photoinduced intersystem crossing (ISC) processes, thus facilitating the generation of reactive oxygen species (ROS). Upon self-assembly, the formed nanomaterials (ONP NPs and SNP NPs) exhibited spherical morphology with average size about 150 nm. The biocompatibility and photocytotoxicity of nanoparticles against Hepa1-6 cells were evaluated using the CCK-8 assay. Additionally, the synergistic effects (photodynamic therapy and photothermal therapy) of SNP NPs were confirmed through diverse in vitro experiment under 690 nm laser irradiation. The generation of intracellular ROS by SNP NPs was confirmed with DCFH-DA as probe. This study provides an ingenious strategy for developing organic nanomaterials with high treatment efficiency through synergistic photodynamic/photothermal effects.

Role of Solvent and Noncovalent Interactions in Alkaline Reactivity of Strained and Strain-Free Macrocyclic Disulfides.

This study employs ab initiomolecular dynamics simulations to investigate the impact of solvent and non-bonded interactions on the structure-reactivity relationship of both strain-free and strained macrocyclic disulfides. Our findings reveal that interactions with water as a solvent significantly influence the minimum energy geometry structures of both conformers of the studied macrocycle. In particular, our simulations identify short contacts, specifically S···π-aromatic interactions, which suppress reactivity for the strained isomer by obstructing the reaction cone at the minimum free energy. Surprisingly, the free energy barriers for the disulfide reaction with a simple nucleophile (OH-anion) remain very similar, despite one conformer having a markedly more strained disulfide bond than the other. Enhanced molecular dynamics simulations in explicit solution elucidate this apparent contradiction by revealing different solvent exposures of the two sulfur atoms in the macrocycles.

Solar photocatalytic degradation of model naphthenic acids mixtures by Bi2WO6 and Bi2WO6/NiO/Ag: Exploring the influence of inorganic fraction of oil sands process water

This study investigates the comparative photocatalytic degradation of six model naphthenic acids, key organic constituents responsible for the toxicity of oil sands process water, using the semiconductor photocatalysts Bi2WO6 and Bi2WO6/NiO/Ag in both buffered solution and the inorganic fraction of OSPW. The heterojunction catalyst (Bi2WO6/NiO/Ag) exhibited the highest removal efficiencies for these organic pollutants with k values 0.048, 0.036, 0.019, 0.283, 0.026, and 0.075 min−1 for 1-adamantanecarboxylic acid, cyclohexanecarboxylic acid, tetrahydropyran-4-carboxylic acid, tetrahydro-2H-thiopyran-4-carboxylic acid, isonipecotic acid, and 4,5-dihydronaphtho[1,2-b]thiophene-2-carboxylic acid, respectively. Experimental analysis suggested that chloride and bicarbonate inhibited the photocatalytic degradation of the target naphthenic acids, while nitrate could accelerate the production of aminyl radicals, enhancing the degradation of isonipecotic acid. Notably, four additional nitrated and hydroxylated by-products were identified during 1-adamantanecarboxylic acid degradation in the presence of nitrate. The addition of the catalyst not only accelerated the degradation rate of 1-adamantanecarboxylic acid but also helped mitigate the formation of potentially toxic by-products. Additionally, the transformation products of 4,5-dihydronaphtho[1,2-b] thiophene-2-carboxylic acid were identified. Degradation pathways were further elucidated with the assistance of density functional theory calculations, identifying the β-carbon as the initial reactive site, with the sulfur atom also playing a significant role in reactivity. These findings contribute to the understanding of the water matrix-induced transformation process of model naphthenic acids during photocatalytic treatment, enhancing the environmental applicability of photocatalytic treatments.

The anisotropy of molybdenite planes: Analysis based on the adsorption behaviors of reagent and H2O

Multiple planes with different properties are exposed after the comminution of molybdenite because of the anisotropy of molybdenite. Study on the properties of different planes is of great significance to enhance the comprehensive utilization of molybdenite, especially in flotation. In order to explore the properties of different planes, the two main planes of molybdenite (basal plane and edge plane) are respectively taken as the research object in this paper, and the properties of planes are expressed using DFT through the adsorption behaviors of a new reagent named DTC-CTS and water molecules. The results show that edge plane has higher activity than basal plane. This is because there are exposed molybdenum atoms on the edge plane, and the sulfur atoms in DTC-CTS and oxygen atoms in water molecules are easy to react with the exposed molybdenum atoms. While the activity of basal plane is low because of the hinderance effect of sulfur atoms in the skin layer. The different adsorption behaviors of water molecules on molybdenite planes verified the hydrophobicity of different planes. In addition, the results also show that the water can affect the DTC-CTS adsorption on edge plane. Water can enhance interaction between single-bond sulfur atom and molybdenum atom, and weaken the interaction between double-bond sulfur atom and molybdenum atom on edge plane.

Investigation of acid-activated iron-based bentonite materials for the oxidation mechanism of dimethyl disulfide

Due to its low olfactory threshold and high volatility, Dimethyl disulfide (DMDS) is a well-known malodorous compound in pesticides and organic synthesis. This study utilizes sodium bentonite as catalyst support, treating it with acid activation and iron-based modification to create a catalytically active bentonite material. Following modification, the bentonite maintains its fundamental structure while integrating iron ions, resulting in an expanded interlayer spacing and increased specific surface area from 60.371 m2/g to 314.539 m2/g, thereby enhancing catalytic activity. Kinetic modeling fitting demonstrates that combining iron-based acid-activated bentonite with hydrogen peroxide (H2O2) produces the most efficient oxidative system, with the highest reaction rate constant（K = 0.08038 min−1） for DMDS degradation. The best degradation effect was achieved when the ratio of Fe-H-Bent to hydrogen peroxide was 1:5, the pH was 3, and the reaction temperature was 40 °C, and the removal rate was up to 98.9%. Electron paramagnetic resonance (EPR) spectroscopy confirms that hydroxyl radicals (·OH) are this system's primary driver of oxidation. Theoretical computations and product analyses provide insight into the oxidation pathway of DMDS, showing that initial oxidation occurs at the first sulfur atom, forming an intermediate that further oxidizes to dimethyl sulfoxide and ultimately to sulfur dioxide. This research offers a practical method for the effective removal of DMDS in pesticide plants and chemical industrial parks.

Assessment of doped graphene in the removal of atrazine from water

Atrazine is a widely used toxic herbicide that poses a threat to both the environment and human health. This study investigates the removal of Atrazine from water through armchair-hexagonal hexagonal graphene quantum dots (AHEX) simulations. The investigations are performed using density functional theory at the exchange–correlation hybrid functional B3LYP/3-21G level of theory. The activity of pristine AHEX, with a total dipole moment of 0.0 (debye), is enhanced by doping with boron (B), nitrogen (N), and sulfur atoms (S), resulting in increased total dipole moments of 8.99, 5.29, and 4.14 Debye respectively. This enhancement occurs without any structural deformation due to the doping process. Our results show significant adsorption capacity of the doped nanographene for Atrazine, evidenced by the high adsorption energies of 0.52 eV for boron, 0.62 eV for nitrogen, and 2.97 eV for sulfur. Charge distribution on the atrazine complexes further confirms effective interaction, with values of 0.03, − 0.018, and 0.032 (e). UV–vis spectroscopy reveals that the prominent absorption peaks of boron and nitrogen-doped samples, initially at ~ 658.8 and 431 nm, undergo a redshift to ~ 676 and 444.3 nm after adsorption, respectively. This redshift aligns with the dominant excitation moving to lower energies following adsorption. Conversely, the sulfurated nanographene shows a blue shift from 980.66 to 485.41 nm. These findings highlight the potential of doped nanographene as an effective treatment for atrazine-contaminated water.

Synthesis of Novel Planar-Chiral Charge-Compensated nido-Carborane-Based Amino Acid.

Amino acids with unusual types of chirality and their derivatives have recently attracted attention as precursors in the synthesis of chiral catalysts and peptide analogues with unique properties. In this study, we have synthesized a new nido-carborane-based planar-chiral amino acid, in the molecule of which the amino group is directly bonded to the B(3) atom, and the carboxyl group is attached to the B(9) atom through the CH2S+(Me) fragment. 3-Amino-9-dimethylsulfonio-nido-carborane, prepared in three steps from 3-amino-closo-carborane in a high yield, was a key intermediate in the synthesis of the target planar-chiral amino acid. The carboxymethyl group at the sulfur atom was introduced by the demethylation reaction of the dimethylsulfonio derivative, followed by S-alkylation. The structure of new 3,9-disubstituted nido-carboranes was studied for the first time using NMR spectroscopy. The resonances of all boron atoms in the 11B NMR spectrum of 3-amino-9-dimethylsulfonio-nido-carborane were assigned based on the 2D NMR correlation experiments. The nido-carborane-based planar-chiral amino acid and related compounds are of interest as a basis for peptide-like compounds and chiral ligands.

Overcoming Challenges with Biochemical Studies of Selenocysteine and Selenoproteins.

Selenocysteine (Sec) is an essential amino acid that distinguishes itself from cysteine by a selenium atom in place of a sulfur atom. This single change imparts distinct chemical properties to Sec which are crucial for selenoprotein (Sec-containing protein) function. These properties include a lower pKa, enhanced nucleophilicity, and reversible oxidation. However, studying Sec incorporation in proteins is a complex process. While we find Sec in all domains of life, each domain has distinct translation mechanisms. These mechanisms are unique to canonical translation and are composed of Sec-specific enzymes and an mRNA hairpin to drive recoding of the UGA stop codon with Sec. In this review, we highlight the obstacles that arise when investigating Sec insertion, and the role that Sec has in proteins. We discuss the strategic methods implemented in this field to address these challenges. Though the Sec translation system is complex, a remarkable amount of information has been obtained and specialized tools have been developed. Continued studies in this area will provide a deeper understanding on the role of Sec in the context of proteins, and the necessity that we have for maintaining this complex translation machinery to make selenoproteins.

Review on Thiazolo-triazole as a Promising Anticancer Agent

Thiazolo-Triazole is a fused ring heterocyclic system consisting of three nitrogen atoms and one Sulphur atom shows wide range of biological activities. Cancer is the second leading cause of death worldwide. In past few decades, there has been a crucial necessity for the design and development of innovative anticancer drugs that can diminish the serious health problems and unwanted side effects associated with presently used anticancer drugs. Many anticancer drugs are commercially accessible, but nonexistence of selectivity, target specificity, cytotoxicity, and development of resistance lead to serious side effects. Several experiments have been going on to develop compounds with negligible or no side effects. The thiazole and triazole heterocyclic are well-recognized to possess abundant pharmacological activities, including predominantly anticancer, as revealed by various investigations on anticancer compounds and the latest research findings pointed out that to study the anticancer potential of thiazolo-triazole compounds in single scaffold.

The role of spacer heteroatomic fragment in spectroscopic and luminescent behaviour of phenyl-substituted phthalocyanine complexes

Peripheral phenyl-substituted metal phthalocyanines with thio and oxa substitution in the spacer bridge fragment were obtained in the work. Spectroscopic properties were studied for the obtained complexes, and the main patterns of behavior and characteristics change depending on the solvent and the nature of the spacer atom. It is shown that the replacement of an oxygen atom in the bridge fragment of a peripheral substituent with a sulfur atom leads to a change in the values of the fluorescence quantum yields. It was revealed that the presence of a spacer fragment is one of the key factors that strongly influence both the solubility of phthalocyanine complexes and their aggregation behavior in various solvents.

Synthesis, electrochemical properties, and antioxidant activity of sterically hindered catechols with 1,3,4-oxadiazole, 1,2,4-triazole, thiazole or pyridine fragments.

A series of new RS-, RS-CH2- and R2N-CH2-functionalized сatechols with heterocyclic fragments such as 1,3,4-oxadiazole, 1,2,4-triazole, thiazole, or pyridine were synthesized by the reaction of 3,5-di-tert-butyl-o-benzoquinone or 3,5-di-tert-butyl-6-methoxymethylcatechol with different heterocyclic thiols. The S-functionalized catechols were prepared by the Michael reaction from 3,5-di-tert-butyl-o-benzoquinone and the corresponding thiols. The starting reagents such as substituted 1,3,4-oxadiazole-2-thiols and 4H-triazole-3-thiols are characterized by thiol-thione tautomerism, therefore their reactions with 3,5-di-tert-butyl-6-methoxymethylcatechol can proceed at the sulfur or nitrogen atom. In the case of mercapto-derivatives of thiazole or pyridine, this process leads to the formation of the corresponding thioethers with a methylene linker. At the same time, thiolated 1,3,4-oxadiazole or 1,2,4-triazole undergo alkylation at the nitrogen atom in the reaction with 3,5-di-tert-butyl-6-methoxymethylcatechol to form the corresponding thiones. The yield of reaction products ranges from 42 to 80%. The crystal structures of catechols with 3-nitropyridine or 1,3,4-oxadiazole-2(3H)-thione moieties were established by single-crystal X-ray analysis. The possibility of forming intra- and intermolecular hydrogen bonds has been established for these compounds. The electrochemical behavior of the studied compounds is influenced by several factors: the nature of the heterocycle and its substituents, the presence of a sulfur atom in the catechol ring, or a thione group in the heterocyclic core. The radical scavenging activity and antioxidant properties were determined using the reaction with synthetic radicals, the cupric reducing antioxidant capacity assay, the inhibition process of superoxide radical anion formation by xanthine oxidase, and the process of lipid peroxidation of rat liver (Wistar) homogenates in vitro.

Advancing Optoglycomics: Two Orthogonal Azobenzene Glycoside Antennas in One Glycocluster-Synthesis, Switching Cycles, Kinetics and Molecular Dynamics.

Carbohydrate recognition is essential for numerous biological processes and is governed by various factors within the supramolecular environment of the cell. Photoswitchable glycoconjugates have proven as valuable tools for the investigation and modulation of carbohydrate recognition as they allow to control the relative orientation of sugar ligands by light. In order to advance the possibilities of such an "optoglycomics" approach for the glycosciences, we have synthesized a biantennary glycocluster in which two glycoazobenzene antennas are conjugated to the 3- and 6-position of a scaffold glycoside. Orthogonal isomerization of the photoswitchable units was made possible by the different conjugation of the azobenzene moieties via an oxygen and a sulfur atom, respectively, and the ortho-fluorination of one of the azobenzene units. This design enabled a switching cycle comprising the EE, EZ and the ZZ isomer. This is the first example of an orthogonally photoswitchable glycocluster. The full analysis of its photochromic properties included the investigation of the isolated glycoazobenzene antennas allowing the comparison of the intra- versus the intermolecular orthogonal photoswitching. The kinetics of the thermal relaxation were analyzed in detail. A molecular dynamics study shows that indeed, the relative orientation of the glycoantennas and the distances between the terminal sugar ligands significantly vary depending on the isomeric state, as intended.

Theoretical Study of the Effects of Different Coordination Atoms (O/S/N) on Crystal Structure, Stability, and Protein/DNA Binding of Ni(II) Complexes with Pyridoxal-Semi, Thiosemi, and Isothiosemicarbazone Ligand Systems

Nickel transition metal complexes have shown various biological activities that depend on the ligands and geometry. In this contribution, six Ni(II) nitrate complexes with pyridoxal-semi, thiosemi, and isothiosemicarbazone ligands were examined using theoretical chemistry methods. The structures of three previously reported complexes ([Ni(PLSC)(H2O)3]∙2NO3−, [Ni(PLTSC)2] ∙2NO3−∙H2O, and [Ni(PLITSC)(H2O)3]∙2NO3−) were investigated based on Hirshfeld surface analysis, and the most important stabilization interactions in the crystal structures were outlined. These structures were optimized at the B3LYP/6-311++G(d,p)(H,C,N,O,(S))/LanL2DZ(Ni) level of theory, and the applicability was checked by comparing theoretical and experimental bond lengths and angles. The same level of theory was applied for the optimization of three additional structures, ([Ni(PLSC)2]2+, [Ni(PLTSC)(H2O)3]2+, and [Ni(PLITSC)2]2+). The interactions between selected ligands and Ni(II) were examined using the Natural Bond Orbital (NBO) and Quantum Theory of Atoms in Molecules (QTAIM) approaches. Particular emphasis was placed on interactions between oxygen, sulfur, and nitrogen donor atoms and Ni(II). Human Serum Albumin (HSA) and the DNA-binding properties of these complex cations were assessed using molecular docking simulations. The presence of water molecules and various substituents in the thermodynamics of the processes was demonstrated. The results showed significant effects of structural parameters on the stability and reactivity towards important biomolecules.

Synthesis of 2‐Pyridyl Based N(1)‐Substituted Thiosemicarbazonates of Nickel(II) as Bioactive Materials against MRSA, S. aureus, S. typhimurium 2, and K. pneumonia

AbstractIn this investigation, the bio‐activity and biosafe potential of thiosemicarbazonates of nickel(II) as well as that of ligands are described. Reactions of nickel(II) acetate with a series of thiosemicarbazones, {R1(py)C2=N3‐N2(H)‐C1(=S)‐NHR; R1=py, Me, H and Ph; R=H, Me, Et, Ph}, led to the loss of acidic hydrazinic N2(H) protons, and resulted in the formation of six‐coordinated complexes of stoichiometry, [Ni(N,N,S−L)2], where anionic N,N,S−L=py2tsc‐NHR, 1–4; apytsc‐NHR, 5–8; pytsc‐NHR, 9–12 and bpytsc‐NHR, 13–16. All these complexes have been characterized using analytical data, IR and UV‐visible spectroscopy and ESI‐mass spectrometry. The single crystal X‐ray crystal structure of several complexes {2(Me), 7(Et), 11(Et), 12(Ph), 13(H),14(Me) and 15(Et)} were also determined. Thio‐ligands coordinate to nickel(II) through pyridyl nitrogen‐N4, azomethine nitrogen‐N3 and thiolato sulfur atoms, resulting in the formation of homoleptic complexes with octahedral structures. Complexes 1–16 and uncoordinated thiosemicarbzones, were evaluated for their antimicrobial activity, in terms of ZOI, MIC, time kill assay and in vitro percent cell viability MTT assay, against clinical isolate methicillin‐resistant Staphylococcus aureus (MRSA), Staphylococcus aureus (MTCC740), Klebsiella pneumonia (MTCC109), Salmonella typhimurium (MTCC1251), and Candida albicans (MTCC227), a yeast. Both the ligands and their metal complexes exhibited moderate to high bioactivity, and were found to be biosafe with high cell viability, 88–92 %, in several cases.

Quantum Chemical Characterization of Rotamerism in Thio-Michael Additions for Targeted Covalent Inhibitors.

Myotonic dystrophy type I (DM1) is the most common form of adult muscular dystrophy and is a severe condition with no treatment currently available. Recently, small-molecule ligands have been developed as targeted covalent inhibitors that have some selectivity for and covalently inhibit cyclin-dependent kinase 12 (CDK12). CDK12 is involved in the transcription of elongated RNA sections that results in the DM1 condition. The covalent bond is achieved after nucleophilic addition to a Michael acceptor warhead. Previous studies of the conformational preferences of thio-Michael additions have focused on characterizing the reaction profile based on the distance between the sulfur and β-carbon atoms. Rotamerism, however, has not been investigated extensively. Here, we use high-level quantum chemistry calculations, up to coupled cluster with single, double, and perturbative triple excitations [CCSD(T)], to characterize the nucleophilic addition of an archetypal nucleophile, methanethiolate, to various nitrogen-containing Michael acceptors which are representative of the small-molecule covalent inhibitors. By investigating the structural, energetic, and electronic properties of the resulting enolates, as well as their reaction profiles, we show that synclinal additions are generally energetically favored over other additions due to the greater magnitude of attractive noncovalent interactions permitted by the conformation. The calculated transition states associated with the addition process indicate that synclinal addition proceeds via lower energetic barriers than antiperiplanar addition and is the preferred reaction pathway.

Updating Reaction Mechanistic Domains for Skin Sensitization: 1. Nucleophilic Skin Sensitizers.

It has long been recognized that skin sensitizers either are electrophilic or can be activated to electrophilic species. Several nonanimal assays for skin sensitization are based on this premise. In the course of a project to update dermal sensitization thresholds (DST), we found a substantial number of sensitizers, with no electrophilic or pro-electrophilic alerts, that could be simply explained in terms of the sensitizer acting as a nucleophile. In some cases, the nucleophilic center is a sulfur or phosphorus atom, while in others, it is an aromatic carbon atom. For carbon-centered nucleophiles, a quantitative mechanistic model based on a combination of Hammett σ+ and logP values has been derived. This has been applied to rationalize several groups of known sensitizers with no electrophilic or pro-electrophilic alerts, including anacardic acids and cardols, which are known human sensitizers associated with, inter alia, cashew nut oil, mango, and Ginkgo biloba. The possibility of nucleophilic sensitization needs to be considered when evaluating new chemicals for skin sensitization potential and potency by nonanimal assays, particularly those based on the premise that skin sensitization is dependent upon reactions of electrophiles with skin protein-based nucleophiles.

S-doped amorphous multi-metal borophosphates for efficient alkaline seawater oxidation with a high corrosion resistance

Direct seawater splitting is a promising strategy for the production of green hydrogen to address water shortage and environmental concerns. However, the primary obstacle in direct seawater splitting is directly related to the high selectivity and durability of oxygen evolution reaction (OER) electrocatalysts. In this study, we developed sulfur-doped multimetal (Ni, Fe, and Co) borophosphates (BPOs) as high-performance OER catalysts for alkalized seawater electrolytes. The incorporated sulfur atoms act as precursors to enhance the corrosion resistance, as they form negatively charged polyanionic surface layers that block the chloride ions. The best catalyst demonstrates an overpotential of 278 mV in alkaline freshwater and 292 mV in alkalized seawater electrolytes when subjected to a current density of 100 mA cm−2. The overpotential disparity between the two media was only 14 mV, suggesting that the material has substantial resistance to chloride corrosion. Furthermore, excellent electrochemical durability was attained for the sulfurized and amorphized multi-metal BPOs, highlighting their high potential as promising catalysts for seawater oxidation.

Novel copper-drugs bearing dipodal bis-mercaptobenzimidazoles: Synthesis, crystal structures, in vitro biological activities, DNA binding, DFT calculations and molecular docking

Three novel copper(II) complexes, 1–3, bearing dipodal bis-mercaptobenzimidazole derivatives based on ortho-, meta- or para-xylene (L1, L2, and L3) were successfully prepared and characterized by using various spectral techniques, including elemental analysis, FT-IR, 1H NMR, and UV–Vis spectroscopy, LC-MS spectrometry and TGA. The analysis revealed that the ligand/metal molar ratio in all copper(II) complexes is 1:1 and the ligand coordinates as a neutral N-donor onto metal center. Additionally, the crystal structures of L1, L2, L3, and copper(II) complex 2 were determined using single crystal X-ray diffraction (SC-XRD) analysis. Copper(II) complexes 1–3 displayed significant stability at pH range of 4–10. The antibacterial effect of ligands and complexes was tested against both gram-negative (Escherichia coli, E. coli ATCC 25922 PTCC 1399) and gram-positive (Staphylococcus aureus, S. aureus ATCC 6538 PTCC 1112) bacterial strains. It should be noted that the complexes showed enhanced antibacterial activity (up to 99 %) when compared to their free ligands. The in vitro studies of all synthesized compounds consisted of testing them against the human colorectal carcinoma cancer cell line (HCT-116) using the MTT assay. The findings revealed that the copper(II) complexes exhibited lower CC50 values (CC50 ranging from 0.045 mM to 0.135 mM) compared to their corresponding ligands (CC50 ranging from 0.150 mM to 0.240 mM) and carboplatin (CC50 = 0.165 mM), indicating higher anticancer activity of the complexes. Additionally, DAPI staining and fluorescence spectroscopy (at three different temperatures) were performed to further examine the impact of complexes 1–3 on inducing apoptosis and to explore their interaction with DNA, respectively. The results revealed a dynamic quenching mechanism, with hydrophobic forces playing a dominant role in the binding process. The viscosity measurements indicated that all complexes could interact in a groove binding manner with DNA. Density functional theory (DFT) calculations were employed to support the structural and vibrational studies and to predict the chemical reactivity. Docking simulations were conducted to evaluate their behavior of the synthesized compounds towards DNA (PDB: 1BNA). These results suggested that various elements, including NH groups, imidazole rings, thioetheric sulfur atom and sulfate moieties of ligands and complexes, are involved in groove binding with DNA.

Selective electrosorption of heavy metal ions from wastewater with S-doped hierarchical porous carbon derived from waste Camellia oleifera shell

Capacitive deionization (CDI) has garnered significant attention in desalination and the removal of heavy metal ions. The quest for cost-effective and high-performance electrode materials is crucial to advance CDI applications. Herein, we report a sulfur-doped hierarchical porous carbon (SPC) derived from waste camellia oleifera shells via a sustainable hydrothermal carbonization process followed by KOH/ammonium salt activation. The optimized SPC-0.2 exhibits exceptional characteristics, featuring a high specific surface area of 1875 m2 g−1 and substantial sulfur doping at 8.65 %, leading to enhanced specific capacitance (161.3 F g−1) in a 1 M NaCl solution. Under optimal operating conditions (1.2 V, 10 mL min−1, 500 mg L−1 NaCl), the SPC-0.2 electrode achieves a notable desalination capacity of 26.64 mg g−1. In particular, the electrode can selectively remove >99 % of Cr3+ and Cu2+ ions (each 10 mg L−1) in a 100 mg L−1 NaCl solution. This high selectivity is attributed to the formation of sulfides via low adsorption energies between the doped sulfur atoms and the targeted heavy metal ions. Furthermore, the SPC-0.2 electrode demonstrates robust reusability and high efficiency in the actual water body. Collectively, our findings underscore the significant potential of the synthesized SPC as an electrode material for CDI, particularly in the selective capacitive removal of heavy metal ions from wastewater. This work not only contributes to the circular economy by using waste biomass, but also offers a viable solution for environmental remediation.