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Kaolin, a naturally occurring clay mineral renowned for its distinctive properties, holds significant importance across various industries. The integration of dimethyl sulfoxide (DMSO) into kaolin matrices, both in the presence and absence of water, has been extensively explored for its potential to enhance material characteristics. Addressing debates surrounding the proposed adsorption mechanism for the type I structure of DMSO, this study undertook a comprehensive physicochemical characterization of DMSO-kaolin complexes (DMSO-KCs) derived from untreated (UnK) and HCl-treated (HK) Egyptian ore, with a focus on elucidating the loading mechanism facilitated by water. Key insights gleaned from electrical conductivity, dielectric constant, and Fine Testing Technology - Fourier-transform infrared (FTT-FTIR) measurements, shedding light on the bonding nature of DMSO-KCs. FTT-FTIR analysis revealed two stages of water departure at 180 °C, with the final stage coinciding with the release of pyrolysis gases, confirming the catalytic degradation of DMSO. Through X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), and thermogravimetric analysis (TGA), two distinct bonding types of DMSO molecules with kaolinite were identified: amorphous adsorbed (type I) and lattice-oriented intercalated (type II). Electrical characteristic evaluations within the temperature range of room temperature (RT) to 260 °C and frequency range of 42 Hz-1 MHz revealed that DMSO intercalation enhances the electrical properties of kaolin. Hydrated DMSO-KCs exhibited higher values of σac and ɛ' compared to non-hydrated samples. The activation energy (Ea) values for HCl-treated samples were smaller than those of untreated ones. Alternating current (AC) conductivity analysis indicated predominantly ionic behavior with frequency and temperature dependency in both HCl-treated and untreated kaolin. Our findings substantiate the adsorption mechanism of Type I DMSO, highlighting its amorphous nature, instability, and catalytic degradation over time, in contrast to the intercalated type II. This elucidation is pivotal for understanding the behavior of DMSO-KCs across diverse applications, including electronics, ceramics, and materialsscience.

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Dissolved black carbon (DBC) plays a crucial role in the migration and bioavailability of iron in water. However, the properties of DBC releasing under diverse pyrolysis conditions and dissolving processes have not been systematically studied. Here, the compositions of DBC released from biochar through redox processes dominated by bacteria and light were thoroughly studied. It was found that the DBC released from straw biochar possess more oxygen-containing functional groups and aromatic substances. The content of phenolic and carboxylic groups in DBC was increased under influence of microorganisms and light, respectively. The concentration of phenolic hydroxyl groups increased from 10.0∼57.5 mmol/gC to 6.6 ∼65.2 mmol/gC, and the concentration of carboxyl groups increased from 49.7∼97.5 mmol/gC to 62.1 ∼113.3 mmol/gC. Then the impacts of DBC on pyrite dissolution and microalgae growth were also investigated. The complexing Fe3+ was proved to play a predominant role in the dissolution of ferrous mineral in DBC solution. Due to complexing between iron ion and DBC, the amount of dissolved Fe in aquatic water may rise as a result of elevated number of aromatic components with oxygen containing groups and low molecular weight generated under light conditions. Fe-DBC complexations in solution significantly promoted microalga growth, which might be attributed to the stimulating effect of dissolved Fe on the chlorophyll synthesis. The results of study will deepen our understanding of the behavior and ultimate destiny of DBC released into an iron-rich environment under redox conditions.

Asunto(s)

Carbono , Carbón Orgánico , Hierro , Oxidación-Reducción , Hierro/química , Carbón Orgánico/química , Carbono/química , Contaminantes Químicos del Agua/química

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The Structural Maintenance of Chromosomes (SMC) protein complexes are DNA-binding molecular machines required to shape chromosomes into functional units and to safeguard the genome through cell division. These ring-shaped multi-subunit protein complexes, which are present in all kingdoms of life, achieve this by organizing chromosomes in three-dimensional space. Mechanistically, the SMC complexes hydrolyze ATP to either stably entrap DNA molecules within their lumen, or rapidly reel DNA into large loops, which allow them to link two stretches of DNA in cis or trans. In this chapter, the canonical structure of the SMC complexes is first introduced, followed by a description of the composition and general functions of the main types of eukaryotic and prokaryotic SMC complexes. Thereafter, the current model for how SMC complexes perform in vitro DNA loop extrusion is presented. Lastly, chromosome loop formation by SMC complexes is introduced, and how the DNA loop extrusion mechanism contributes to chromosome looping by SMC complexes in cells is discussed.

Asunto(s)

Cromosomas , Cromosomas/química , Complejos Multiproteicos/metabolismo , Complejos Multiproteicos/química , Proteínas de Ciclo Celular/metabolismo , Proteínas de Ciclo Celular/genética , ADN/química , ADN/metabolismo , ADN/genética , Proteínas Cromosómicas no Histona/metabolismo , Proteínas Cromosómicas no Histona/química , Adenosina Trifosfato/metabolismo , Proteínas de Unión al ADN/metabolismo , Proteínas de Unión al ADN/química

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Introduction: Equipped with a photosynthetic apparatus that uses the energy of solar radiation to fuel biosynthesis of organic compounds, chloroplasts are the metabolic factories of mature leaf cells. The first steps of energy conversion are catalyzed by a collection of protein complexes, which can dynamically interact with each other for optimizing metabolic efficiency under changing environmental conditions. Materials and methods: For a deeper insight into the organization of protein assemblies and their roles in chloroplast adaption to changing environmental conditions, an improved complexome profiling protocol employing a MS-cleavable cross-linker is used to stabilize labile protein assemblies during the organelle isolation procedure. Results and discussion: Changes in protein:protein interaction patterns of chloroplast proteins in response to four different light intensities are reported. High molecular mass assemblies of central chloroplast electron transfer chain components as well as the PSII repair machinery react to different light intensities. In addition, the chloroplast encoded RNA-polymerase complex was found to migrate at a molecular mass of ~8 MDa, well above its previously reported molecular mass. Complexome profiling data produced during the course of this study can be interrogated by interested readers via a web-based online resource (https://complexomemap.de/projectsinteraction-chloroplasts).

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The study focused on the extraction of free erythromycin from commercially manufactured tablets and the use of metal salts to synthesize erythromycin-metal complexes, specifically involving silver (Ag), nickel (Ni), cobalt (Co), and copper (Cu). The synthesis was confirmed through various methods, including elemental analysis, thermogravimetric analysis, Fourier-transform infrared (FTIR), and UV-visible spectroscopy. The microbiological investigation involved Salmonella typhi, Escherichia coli, Staphylococcus aureus, Bacillus cereus, Candida albicans, and Microsporum canis as test organisms. The NCCLS broth microdilution reference method was used to determine the minimum fungicidal concentration and minimum inhibitory concentration of the complexes. The synthesized complexes were highly effective against a variety of fungi and bacteria, with compound Ery-Cu having MIC as low as 1.56 mg/mL, Ery-Cu and Ery-Ni with MBCs of 6.25 mg/mL and Ery-Cu having MFC of 6.25 mg/mL. Dose-dependent inhibitory effects were found upon examination of the antimicrobial susceptibility of specific complexes (Cu, Ni, Co and Ag) at varying concentrations of 100, 50, 25 and 12.5 mm/mL. Antibiotic susceptibility testing revealed efficacy against the tested pathogens. The study suggests that the synthesis of erythromycin-metal complexes, coupled with their antibacterial effectiveness against a diverse spectrum of bacteria and fungi, as they showed promising inhibitory properties when tested against a range of test species (Bacillus cereus, Staphylococcus aureus, Escherichia coli, Salmonella typhi, Candida albicans, and Microsporum canis), could lead to the development of innovative antibacterial agents. Molecular docking simulations were used to examine the interactions between metal complexes with proteins filamentous temperature-sensitive protein Z and lanosterol 14α-demethylase. The study highlights the need for further exploration in pharmaceutical research.

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There is a great deal of research interest in the design of alternative metallodrugs to Pt(II)-derivatives for cancer treatment. The low solubility of such drugs in biological mediums leading to poor bioavailability is the major hurdle of several metal-based anticancer agents. These issues have recently been addressed by designing bio-active ligands based on metal-containing anticancer agents. Conjugating with bioactive ligands has significantly improved the bioavailability of the metallodrugs and their cancer cell targeting ability. One such naturally available bioactive ligand is curcumin. Until recently, several curcumin-based anticancer metallodrugs have been developed and successfully demonstrated for their anticancer studies. In this article, we aim to highlight, the synthesis, structure, and anticancer properties of various Zn(II)-curcumin-based coordination complexes. The effect of introducing different functional groups, targeting ligands, and photo-active ligands on the anticancer potential of such complexes has been mentioned in detail. The current status and future perspective on curcumin-based metallodrugs for cancer treatment have also been stated.

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Three novel polypyridyl-Co(III)-vitamin B6 complexes viz., [Co(CF3-phtpy)(SBVB6)]Cl (Co1), [Co(anthracene-tpy)(SBVB6)]Cl (Co2), [Co(NMe2-phtpy)(SBVB6)]Cl (Co3), where 4'-(4-(trifluoromethyl)phenyl)-2,2':6',2''-terpyridine = CF3-phtpy, 4'-(anthracen-9-yl)-2,2':6',2''-terpyridine = anthracene-tpy;, 4-([2,2':6',2''-terpyridin]-4'-yl)-N,N-dimethylaniline = NMe2-phtpy, (E)-5-(hydroxymethyl)-4-(((2-hydroxyphenyl)imino)methyl)-2-methylpyridin-3-ol = H2SBVB6 was successfully developed for aPDT (antibacterial photodynamic therapy) applications. Co1-Co3 exhibited an intense absorption band at ca. 435-485 nm, which is attributed to ligand-to-metal charge transfer and was beneficial for antibacterial photodynamic therapy. The distorted octahedral geometry of the complexes with CoIIIN4O2 core was evident from the DFT study. The visible light absorption ability and good photo-stability of Co1-Co3 made them good photosensitizers for aPDT. Co1-Co3 displayed significant antibacterial responses against gram-positive (S. aureus) and gram-negative (E. coli) bacteria upon light exposure (10 J cm-2, 400-700 nm) and showed MIC values between 0.01-0.005 µg mL-1. The aPDT activities of these complexes were due to their ability to damage bacterial cell membranes via ROS generation. Overall, this study shows the photo-triggered ROS-mediated bacteria-killing potential of Co(III) complexes.

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Two-coordinate coinage metal complexes have been exploited for various applications. Herein, a new donor-metal-acceptor (D-M-A) complex PZI-Au-TOT, using bulky pyrazine-fused N-heterocyclic carbene (PZI) and trioxytriphenylamine (TOT) ligands, was synthesized. PZI-Au-TOT displays decent thermally activated delayed fluorescence (TADF) with a quantum yield of 93% in doped film. The crystals of PZI-Au-TOT show simultaneous TADF, polymorphism, and linearly polarized luminescence (LPL). The polymorph-dependent emission properties with widely varied peaks from 560 to 655 nm are attributed to different packing modes in terms of isolated monomers, discrete π-π stacked dimers or dimer PLUS. Two well-defined microcrystals of PZI-Au-TOT exhibit linearly polarized thermally activated delayed fluorescence with a degree of polarization up to 0.64. This work demonstrates that the molecular rotational flexibility of D-M-A type complexes endows an integration of multiple functions into one complex through manipulation of supramolecular aggregation. This type of complexes is expected to serve as a versatile platform for the fabrication of crystal materialsfor advanced photonic applications.

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Manganese catalysts that activate hydrogen peroxide have seen increased use in organic transformations, such as olefin epoxidation and alkane C-H bond oxidation. Proposed mechanisms for these catalysts involve the formation and activation of MnIII-hydroperoxo intermediates. Examples of well-defined MnIII-hydroperoxo complexes are rare, and the properties of these species are often inferred from MnIIIalkylperoxo analogues. In this study, we show that the reaction of the MnIII-hydroxo complex [MnIII(OH)(6Medpaq)]+ (1) with hydrogen peroxide and acid results in the formation of a dark-green MnIII-hydroperoxo species [MnIII(OOH)(6Medpaq)]+ (2). The formulation of 2 is based on electronic absorption, 1H NMR, IR, and ESI-MS data. The thermal decay of 2 follows a first order process, and variable-temperature kinetic studies of the decay of 2 yielded activation parameters that could be compared with those of a MnIII-alkylperoxo analogue. Complex 2 reacts with the hydrogen-atom donor TEMPOH two-fold faster than the MnIII-hydroxo complex 1. Complex 2 also oxidizes PPh3, and this MnIII-hydroperoxo species is 600-fold more reactive with this substrate than its MnIII-alkylperoxo analogue [MnIII(OOtBu)(6Medpaq)]+. DFT and time-dependent (TD) DFT computations are used to compare the electronic structure of 2 with similar MnIII-hydroperoxo and MnIII-alkylperoxo complexes.

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Understanding the functions of metal ions in biological systems is crucial for many aspects of research, including deciphering their roles in diseases and potential therapeutic use. Structural information about the molecular or atomic details of these interactions, generated by methods like X-ray crystallography, cryo-electron microscopy, or nucleic magnetic resonance, frequently provides details that no other method can. As with any experimental method, they have inherent limitations that sometimes lead to an erroneous interpretation. This manuscript highlights different aspects of structural data available for metal-protein complexes. We examine the quality of modeling metal ion binding sites across different structure determination methods, where different kinds of errors stem from, and how they can impact correct interpretations and conclusions.

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Understanding the behavior of cyanide in rivers is of utmost importance as it has a direct impact on the health of people who depend on these water sources. Cyanide contamination from gold mining activities poses a significant environmental threat to river ecosystems, particularly in southern Ecuador. This study aimed to investigate the behavior of cyanide when it enters contact with other metals in these rivers. Simulations were conducted to determine the speciation of cyanide, mercury, arsenic, lead, and manganese in a study area, taking into account the water temperature and pH at four locations. The findings revealed that CN-and HCN(aq) species were present in the research area. Additionally, mercury-cyanide (Hg(CN)2(aq), Hg(CN)3-), and manganese-cyanide (MnCN+) complexes were identified 3 km downriver from the site where the mining activity is higher. These metal-cyanide complexes tend to dissociate quickly under weak acidic conditions, making them hazardous to the environment. This research is crucial, not only for the environment but also for human health, as it allows to predict toxicity risks for people supplied with this water source, emphasizing the potential harm to human health. This study highlights the importance of stringent regulations and effective monitoring practices to mitigate cyanide contamination and safeguard environmental and occupational health.

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The dynamic interplay between intramammary IgG, formation of antigen-IgG complexes and effector immune cell function is essential for immune homeostasis within the bovine mammary gland. We explore how changes in the recognition and binding of anti-LPS IgG to the glycolipid "functional" core in milk from healthy or clinically diagnosed Escherichia coli (E. coli) mastitis cows' controls endotoxin function. In colostrum, we found a varied anti-LPS IgG repertoire and novel soluble LPS/IgG complexes with direct IgG binding to the LPS glycolipid core. These soluble complexes, absent in milk from healthy lactating cows, were evident in cows diagnosed with E. coli mastitis and correlated with endotoxin-driven inflammation. E. coli mastitis milk displayed a proportional reduction in anti-LPS glycolipid core IgG compared to colostrum. Milk IgG extracts showed that only colostrum IgG attenuated LPS induced endotoxin activity. Furthermore, LPS-stimulated reactive oxygen species (ROS) in milk granulocytes was only suppressed by colostrum IgG, while IgG extracts of neither colostrum nor E. coli mastitis milk influenced N-formylmethionine-leucyl-phenylalanine (fMLP)-stimulated ROS in LPS primed granulocytes. Our findings support bovine intramammary IgG diversity in health and in response to E. coli infection generate milk anti-LPS IgG repertoires that coordinate appropriate LPS innate-adaptive immune responses essential for animal health.

Asunto(s)

Calostro , Infecciones por Escherichia coli , Escherichia coli , Glucolípidos , Inmunoglobulina G , Lipopolisacáridos , Mastitis Bovina , Leche , Animales , Bovinos , Femenino , Calostro/inmunología , Calostro/metabolismo , Inmunoglobulina G/inmunología , Inmunoglobulina G/metabolismo , Mastitis Bovina/inmunología , Mastitis Bovina/microbiología , Escherichia coli/inmunología , Lipopolisacáridos/inmunología , Leche/inmunología , Glucolípidos/metabolismo , Glucolípidos/inmunología , Infecciones por Escherichia coli/inmunología , Endotoxinas/inmunología , Endotoxinas/metabolismo , Especies Reactivas de Oxígeno/metabolismo , Granulocitos/inmunología , Granulocitos/metabolismo , Unión Proteica , Glándulas Mamarias Animales/inmunología , Glándulas Mamarias Animales/metabolismo

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Starch is a fundamental material in the food industry. However, the inherent structural constraints of starch impose limitations on its physicochemical properties, including thermal instability, viscosity, and retrogradation. To address these obstacles, polyphenols are extensively employed for starch modification owing to their distinctive structural characteristics and potent antioxidant capabilities. Interaction between the hydroxyl groups of polyphenols and starch results in the formation of inclusion or non-inclusion complexes, thereby inducing alterations in the multiscale structure of starch. These modifications lead to changes in the physicochemical properties of starch, while simultaneously enhancing its nutritional value. Recent studies have demonstrated that both thermal and non-thermal processing exert a significant influence on the formation of starch-polyphenol complexes. This review meticulously analyzes the techniques facilitating complex formation, elucidating the critical factors that dictate this process. Of noteworthy importance is the observation that thermal processing significantly boosts these interactions, whereas non-thermal processing enables more precise modifications. Thus, a profound comprehension and precise regulation of the production of starch-polyphenol complexes are imperative for optimizing their application in various starch-based food products. This in-depth study is dedicated to providing a valuable pathway for enhancing the quality of starchy foods through the strategic integration of suitable processing technologies.

RESUMEN

X-ray absorption spectroscopy (XAS) is a powerful tool for examining changes of the electronic and molecular structure following light-induced excitation of a molecule. Specifically, this method can be applied to investigate the ground (GS, RuNO) and metastable states (MS1, RuON and MS2, Ruη2(NO)) of the nitrosyl ligand (NO), which differ in their coordination mode to the metal. In this work, we report for the first time experimental and theoretical (DFT) Ru L3,2-edge XA spectra for the octahedral complex trans-[RuNOPy4F](ClO4)2 (1, Py = pyridine) in both ground and metastable states. The transition from GS to MS1 using 420 nm light excitation leads to a significant downshift of the 2p â†’ LUMO(+1) peaks by about 0.5-0.8 eV, attributed to the destabilisation of 2p orbitals and stabilization of LUMO(+1). Subsequent irradiation of MS1 at 920 nm produces isomer MS2, for which even greater stabilization of LUMO occurs, though without a significant change in 2p energy. The change in 2p energy is attributed to a variation in the charge on the Ru atom after NO isomerization, while LUMO(+1) stabilization is related to changes in the Ru(NO) bond length and the composition of this orbital.

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This study investigated the effectiveness and safety of a hybrid thiosemicarbazone ligand (HL) and its metal complexes (MnII-L, FeIII-L, NiII-HL, and ZnII-HL) against epidermoid carcinoma (A-431). The results indicated that FeIII-L is the most effective, with a high selectivity index of 8.01 and an IC50 of 17.49 ± 2.12 µM for FeIII-L. The study also revealed that the synthesized complexes effectively inhibited gene expression of the Phosphoinositide 3-kinases (PI3K), alpha serine/threonine-protein kinase (AKT1), epidermal growth factor receptor (EGFR2) axis mechanism (P < 0.0001). Additionally, these complexes trigger a chain of events that include the inhibition of proliferating cell nuclear antigen (PCNA), transforming growth factor ß1 (TGF ß1), and topoisomerase II, and leading to a decrease in epidermoid cell proliferation. Furthermore, the inhibitory activity also resulted in the upregulation of caspases 3 and 9, indicating the acceleration of apoptotic markers, and the down regulation of miRNA221, suggesting a decrease in epidermoid proliferation. Molecular modeling of FeIII-L revealed that it had the best binding energy -8.02 kcal/mol and interacted with five hydrophobic π-interactions with Val270, Gln79, Leu210, and Trp80 against AKT1. Furthermore, the binding orientation of FeIII-L with Topoisomerase II was found to be the most stable, with a binding energy -8.25 kcal/mol. This stability was attributed to the presence of five hydrophobic π-interactions with His759, Guanin13, Cytosin8, and Ala465, and numerous ionic interactions, which were more favorable than those of doxorubicin and etoposide for new regimens of chemotherapeutic activities against skin cancer.

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High-pressure homogenization and pH-shifting can be used to modify soybean lipophilic protein (SLP), and to enhance its ability to deliver vitamin B12. The structural changes of SLP were analyzed by multispectral techniques and the results showed that secondary and tertiary structures of SLP were altered by modification. The modification unfolded the SLP structure, released more free hydrogen ions, and increased positive charge density on the protein surface. Also, the solubility of modified SLP increased by maximum of 34.75 %. Furthermore, molecular docking showed that complexes were formed between SLP and vitamin B12 mainly through hydrogen bonding and hydrophobic interactions, and the encapsulation rate of modified SLP was maximally increased by 2.3 %. In vitro digestion showed that modified SLP enhanced stability and bioaccessibility of vitamin B12. This study provides theoretical basis for modification of SLP and effective delivery of bioactive substances.

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We investigated the binary Cm-citrate system using time-resolved laser fluorescence spectroscopy (TRLFS), parallel factor analysis (PARAFAC), and quantum chemical calculations. Evidence collectively suggests the stepwise coordination and deprotonation of citrate alcohol groups in Cm-cit complexes with two bound citrate moieties upon increasing pH, which is supported by a bathochromic shift in emission spectra, an observed increase in lifetime measurements, and lower energy minima for citrate alcohol involvement versus hydrolysis of the Cm-citrate species. Our PARAFAC results agree with a 3-component model for the Cm-citrate system and offer pure component decompositions, yielding fraction species across the studied pH range that have a correlated slope = 1 as a function of pH. For the first time, evidence of ternary Ca-Cm-citrate complexes was revealed by TRLFS with increasing calcium concentration at fixed pHm. The formation of these ternary complexes was substantiated with density functional theory (DFT) calculations on simple model systems of the complexes. Shared citrate carboxylate groups between calcium and curium were proposed for all three ternary Ca-Cm-cit complexes based on DFT-determined Ca-O and Cm-O distances. Moreover, we found that the ternary complex with both alcohol groups deprotonated is most stable when it shares both two carboxylate and two alcohol groups between Ca and Cm. The presence of shared functional groups highlights the enhanced stability of these ternary complexes. Additional work is warranted to further constrain the stoichiometry, stability constants and dependence on ionic strength of these complexes for purposes of thermodynamic modeling of repository settings.

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Cyclin-dependent kinase 2 (CDK2) has been recognized as one of the crucial factors in cell cycle regulation and has been proposed as a potential target for cancer therapies, particularly for colorectal cancer (CRC). Due to the increased incidence rate of CRC and challenges associated with existing treatment options, there is a need for efficient and selective anti-cancer compounds. The current work aims to explore the ability of novel kaempferol derivatives as CDK2 inhibitors by performing conceptual pharmacophore modeling, molecular docking, and molecular dynamic analysis. Kaempferol and its derivatives were obtained from PubChem, and the optimized 3D structures of the compounds were generated using Maestro Ligprep. Subsequently, a pharmacophore model was developed to identify compounds with high fitness values, resulting in the selection of several kaempferol derivatives for further study. We evaluated the ADMET properties of these compounds to assess their therapeutic potential. Molecular docking was conducted using Maestro and BIOVIA Discovery Studio version 4.0 to predict the binding affinities of the compounds to CDK2. The top candidates were subjected to MM-GBSA analysis to predict their binding free energies. Molecular dynamics simulations using GROMACS were performed to assess the thermodynamic stability of the ligand-protein complexes. The results revealed several kaempferol derivatives with high predicted binding affinities to CDK2 and favorable ADMET properties. Specifically, compounds 5281642, 5318980, and 14427423 demonstrated binding free energies of -30.26, -38.66, and -34.2 kcal/mol, respectively. Molecular dynamics simulations indicated that these ligand-protein complexes remained stable throughout the simulation period, with RMSD values remaining below 2 Å. In conclusion, the identified kaempferol derivatives show potential as CDK2 inhibitors based on computational predictions and demonstrate stability in molecular dynamics simulations, suggesting their future application in CRC treatment by targeting CDK2. These computational findings encourage further experimental validation and development of kaempferol derivatives as anti-cancer agents.

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New solvated Mo(VI) complexes were isolated from the reaction of [MoO2(acac)2] with asymmetric isatin bisthiocarbohydrazone ligands. The ligands were obtained from the reaction of isatin monothiocarbohydrazone with 3,5-dibromo salicylaldehyde (L1), 3,5-dichloro salicylaldehyde (L2) and 3-chloro-5-bromo salicylaldehyde (L3), respectively. In the complexes, the ligands serve as ONS donors and coordinate to the [MoO2]2+ nucleus. The bonding sites are azomethine nitrogen atom, phenolic oxygen atom and thiol sulfur atom. The sixth coordination site is completed by an oxygen atom from an ethanol solvent. The ethanol-coordinated Mo(VI) complexes, C1-C3, [MoO2L(EtOH)] (L: L1-L3), were characterized using elemental analysis, IR and 1H NMR spectroscopies, and conductivity measurements. By crystallizing ethanol-solvated solid complexes from an EtOH/DMSO mixture, DMSO-solvated complexes (C4-C6) suitable for X-ray crystallography were obtained. Crystal structure analysis supports the proposed complex structures and geometries, but the ethanol in the sixth coordination site has been replaced by DMSO. When the anticarcinogenic effects of the ligands and complexes (C1-C3) on the C6 cell line were examined, it was found that the complexes showed higher activity than the ligands. The C3 complex appears to have the best anti-cancer activity compared to doxorubicin. Additionally, all compounds were determined to have high total antioxidant capacity. Data obtained from theoretical studies (DFT and docking) support experimental studies.

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The brain is an energy demanding organ, constituting about 20 % of the body's resting metabolic rate. An efficient energy metabolism is critical to neuronal functions. Glucose serves as the primary essential energy source for the adult brain and plays a critical role in supporting neural growth and development. Endocrine disrupting chemicals (EDCs) such as phthalates has been shown to have a negative impact on neurological functions. The impact of diisononyl phthalate (DiNP) on neural energy transduction using cellular energy metabolizing enzymes as indicators was examined. Over the course of 14 days, eighteen (18) albino rats divided into three groups (1,2 and 3) of six albino rats were given Tween-80/saline, 20 and 200 mg/kg body weight respectively. In the brain, we assessed histological changes as well as activities of selected enzymes of energy metabolism such as the glycolytic pathway, citric acid cycle and mitochondrial electron transport-linked complexes. Activities of the glycolytic and TCA cycle enzymes assayed were significantly decreased except citrate synthase activity with no statistically significant change following the administration of DiNP. Also, respiratory chain complexes (Complex I-IV) activities were significantly reduced when compared to control. DiNP exposure altered the histological integrity of various brain sections. These include degenerated Purkinje neurons, distortion of the granular layer and Purkinje cell layer. Data from this study indicated impaired brain energy metabolism via down-regulation of enzymes of cellular respiration of the glycolytic and oxidative phosphorylation pathways and altered brain histoarchitecture orchestrated by DiNP exposure.