Complex Potentials Research Articles

Evaluation of DNA and BSA-Binding, Nuclease Activity, and Anticancer Properties of New Cu(II) and Ni(II) Complexes with Quinoline-Derived Sulfonamides

Four complexes of essential metal ions, Cu(II) and Ni(II), with the new sulfonamide ligand N-(pyridin-2-ylmethyl)quinoline-8-sulfonamide (HQSMP) were synthesized and physicochemically and structurally characterized. Complex [Cu(QSMP)Cl]n (2) consists of a polymeric chain formed by distorted square pyramidal units. In 2, the sulfonamide ligand acts as a bridge coordinating to one Cu(II) through its three N atoms and to another metal ion via one O atom in the sulfonamido group, while the pentacoordinate complex [Cu(QSMP)(C6H5COO)] (3) presents a highly distorted square pyramidal geometry. Complex [Ni(QSMP)(C6H5COO)(CH3OH)][Ni(QSMP)(CH3COO)(CH3OH)] (4) consists of two mononuclear entities containing different anion coligands, either a benzoate or an acetate group. Both units exhibit a distorted octahedral geometry. The interaction of the complexes with CT-DNA was studied by means of UV-Vis and fluorescence spectroscopy, interestingly revealing that the Ni(II) complex presents the highest affinity towards the nucleic acid. Complexes 1 and 2 are able to cleave DNA. Both compounds show promising nuclease activity at relatively low concentrations by mediating the production of a reactive oxygen species (ROS). The interaction of the four complexes with bovine serum albumin (BSA) was also investigated, showing that the compounds can bind to serum proteins. The antitumor potential of complexes 1 and 2 was evaluated against the A549 lung adenocarcinoma cell line, revealing cytotoxic properties that were both dose- and time-dependent.

PROSPECTS OF FUNCTIONAL ADAPTATION OF THE CASTLE COMPLEX IN VILLAGE PODZAMOCHOK OF TERNOPOL REGION

The historical castle complex in the village Podzamochok of the Ternopol region has significant resource potential for adaptation to modern functions. However, the architectural monument of national importance is increasingly destroy due to adverse anthropogenic and natural factors. In order to preserve this unique object of cultural heritage of Ukraine, it is necessary to form a program of functional adjustment of the castle complex. In the course of the research, the author analyzed examples of global scientific and project experience, projects of adapting historical castle complexes to new functions, and the resource potential of the historical castle complex in the village Podzamochok. Based on the obtained results, a corresponding program of functional adaptation of the complex formed. The most important points of this program are the following: • carry out emergency and restoration works for the planning and spatial structure of the castle complex; • create of a tourist water route along the Strypa River. The route will pass through the village Podzamochok, Buchach, village Zhiznomir, village Rusyliv, village Skomorokhy, village Sokilets and village Berem'yany. A mooring for watercraft must should be arrang 400 m from the castle fortifications in the village Podzamochok; • organize of museum expositions of objects of art and daily life of the ancient inhabitants of Opil'a. Exhibitions will be place in the restored rooms of the pentagonal corner and the palace (northern corner of the castle fortifications); • create of a "sports and tourist center of hang gliding (paragliding) and extreme tourism". Place the instructor's room and the first aid station on the first floor of the pentagonal corner (southern corner of the fortifications of the castle complex). Place a hang-gliding and paragliding area on the western side of the castle complex. Therefore, the most promising functional purpose for the historical castle complex in the village of Podzamochok is a tourist attraction. Such a function will contribute to the most complete disclosure of the resource potential of the complex.

Terpyridine complexes as superior catalysts for methylene blue dye degradation: Synthesis, characterization, mechanistic insights, kinetic study and recyclability assessment

This manuscript investigates the catalytic potential of terpyridine-based metal complexes (C1–C6) in the efficient degradation of methylene blue dye. The synthesized terpyridine complexes were characterized using various spectroscopic techniques, and their catalytic activity was evaluated in the degradation of methylene blue dye under different experimental conditions. The study reveals that the target complex compounds exhibit notable catalytic efficiency, leading to the effective degradation of the envisioned dye. The reaction kinetics, mechanism, and the influence of various parameters on the catalytic performance were systematically explored. Among different synthesized complexes, Zn-complexes showed better performance than Fe-complexes. Remarkably, the complex C5 showed the best photocatalytic efficiency with a degradation of 79.84 % at optimized conditions of initial dye concentration = 15 mg/L, catalyst dosage = 10 mg, pH = 4, and temperature = 323 K. The recyclability test indicated good stability of the photocatalyst over five cycles with a very small loss of photocatalytic efficiency (∼11.64 %) and the photocatalytic reaction followed pseudo-first order kinetics with a high-rate constant of 0.009 min−1. The trapping experiment revealed the active role of hydroxyl radicals (OH•) and superoxide anions (•O2−) as reactive species on the basis of which a plausible degradation mechanism is proposed. This research contributes valuable insights into the development of terpyridine-based catalysts for the degradation of organic dyes, paving the way for further advancements in the field of catalysis and environmental remediation.

Synthesis, Molecular Docking, and antibacterial evaluation of Quinoline-Derived Ni(II), Cu(II) and Zn(II) complexes

We hereby report the synthesis of novel Ni(II), Cu(II) and Zn(II) complexes of (E)-2-(((7-chloro-2-hydroxyquinolin-3-yl)methylene)amino)-3-methylbutanoic acid ligand obtained by reacting 2,7-dichloroquinoline-3-carboaldehyde and amino acid, valine for antibacterial applications. The ligand and the metal complexes were characterized using FT-IR, UV–Vis, TGA/DTA, pXRD spectroscopic techniques and density functional theory (DFT) calculations. The Schiff base ligand was tridentate with ONO active binding sites as confirmed from its FT-IR spectral analysis. Disc diffusion method was used to assess the antibacterial potential of the Schiff base ligand and its metal complexes. The Schiff base ligand shows antibacterial activities of 8.33 ± 0.471 mm at concentration of 100 µg/ml and 9.33 ± 0.471 mm at concentration of 200 µg/ml against S. aureus. However, the copper complex exhibited zone of inhibition of 11.50 ± 0.408 mm at concentration of 100 µg/ml and 12.67 ± 0.471 mm at concentration of 200 µg/ml against S. aureus. This indicates that the copper complex has better antibacterial activity than the free Schiff base ligand. The overall result revealed the promising potential of the metal complexes for application as antibacterial agents. The DFT calculated absorption spectra agree with the corresponding experimental results. The molecular docking analyses also provided important insights on the interaction of the synthesized complexes with the target proteins.

Discovery of Novel p53-MDM2 Inhibitor (RG7388)-Conjugated PlatinumIV Complexes as Potent Antitumor Agents.

While a number of p53-MDM2 inhibitors have progressed into clinical trials for the treatment of cancer, their progression has been hampered by a variety of problems, including acquired drug resistance, dose-dependent toxicity, and limited clinical efficiency. To make more progress, we integrated the advantages of MDM2 inhibitors and platinum drugs to construct novel PtIV-RG7388 (a selective MDM2 inhibitor) complexes. Most complexes, especially 5a and 5b, displayed greatly improved antiproliferative activity against both wild-type and mutated p53 cancer cells. Remarkably, 5a exhibited potent in vivo tumor growth inhibition in the A549 xenograft model (66.5%) without apparent toxicity. It arrested the cell cycle at both the S phase and the G2/M phase and efficiently induced apoptosis via the synergistic effects of RG7388 and cisplatin. Altogether, PtIV-RG7388 complex 5a exhibited excellent in vitro and in vivo antitumor activities, highlighting the therapeutic potential of PtIV-RG7388 complexes as antitumor agents.

Monofluorophos-Metal Complexes: Ripe for Future Discoveries in Homogeneous Catalysis.

The discovery that cyclic (ArO)2PF can support Rh-catalysts for hydroformylation with significant advantages in tuning regioselectivity transformed the study of metal complexes of monofluorophos ligands from one of primarily academic interest to one with potentially important applications in catalysis. In this review, the syntheses of monofluorophosphites, (RO)2PF, and monofluorophosphines, R2PF, are discussed and the factors that control the kinetic stability of these ligands to hydrolysis and disproportionation are set out. A survey of the coordination chemistry of these two classes of monofluorophos ligands with d-block metals is presented, emphasising the bonding of the fluorophos to d-block metals, predominantly in low oxidation states. The application of monofluorophos ligands in homogeneous catalysis (especially hydroformylation and hydrocyanation) is discussed, and it is argued that there is great potential for monofluorophos complexes in future catalytic applications.

Peculiarities of investment and innovation potential in the assessment of the development of agribusiness enterprises

Three main criteria of investment-innovation potential of agricultural sector enterprises are identified: investment-innovation potential is a set of resources necessary for investment-innovation activities; investment and innovation potential is primarily related to the possibility and conditions (both internal and external) of using resources; investment and innovation potential should be aimed at the optimal use of investment and innovation resources to ensure the effective operation of this development subject. This allows for the identification of resource, organizational, economic and performance components that are key components of investment and innovation opportunities. A step-by-subject characterization of the investment-innovation potential of agro-industrial complex enterprises and a methodology for assessing the investment-innovation potential have been developed, which allows to qualitatively assess the investment-innovation potential of agricultural and processing enterprises (including special groups of indicators that take into account the specifics of their activities) and evaluate and compare them among themselves. It is proved that the inactivity of agricultural commodity producers in mastering the achievements of science and technology is due to the lack of a developed intermediate connection between science and production, which provides the most complete information about the modern achievements of science and technology to producers of raw materials. According to the results of the conducted research, it was established that at the current stage of development in domestic agriculture, the main subjects of innovative infrastructure can become agricultural technology parks and information and consulting centers, which are part of a single information and consulting service. Considering the peculiarities of the domestic agro-industrial complex, it is considered most expedient to create an agro-technological park in the form of a non-commercial partnership, which will contribute to the integration of multifaceted resources. organizations, mainly highly efficient agricultural commodity producers and educational establishments of higher education institutions, capable of carrying out innovative activities to achieve a common goal - innovative development of the agrarian sector of the economy. Agrotechnoparks should be created based on the product base, that is, their activities should be aimed at innovative development of agricultural production and the development of certain types of products. Agrotechnopark can be considered as a set of administrative, production, educational, research and marketing divisions.

Electronic Structure of Metallophlorins: Lessons from Iridium and Gold Phlorin Derivatives.

Phlorins have long remained underexplored relative to their fully conjugated counterparts, such as porphyrins, hydroporphyrins, and corroles. Herein, we have attempted to bridge that knowledge gap with a scalar-relativistic density functional theory (DFT) study of unsubstituted iridium and gold phlorin derivatives and a multitechnique experimental study of iridium-bispyridine and gold complexes of 5,5-dimethyl-10,15,20-tris(pentafluorophenyl)phlorin. Theory and experiments concur that the phlorin derivatives exhibit substantially smaller HOMO-LUMO gaps, as reflected in a variety of observable properties. Thus, the experimentally studied Ir and Au complexes absorb strongly in the near-infrared (NIR), with absorption maxima at 806 and 770 nm, respectively. The two complexes are also weakly phosphorescent with emission maxima at 950 and 967 nm, respectively. They were also found to photosensitize singlet oxygen formation, with quantum yields of 40 and 28%, respectively. The near-infrared (NIR) absorption and emission are consonants with smaller electrochemical HOMO-LUMO gaps of ∼1.6 V, compared to values of ∼2.1 V, for electronically innocent porphyrins and corroles. Interestingly, both the first oxidation and reduction potentials of the Ir complex are some 600 mV shifted to more negative potentials relative to those of the Au complex, indicating an exceptionally electron-rich macrocycle in the case of the Ir complex.

Optimizing Surgical Management of Tibial Plateau Fractures: A Comparative Study of Minimally Invasive Versus Open Reduction Techniques.

Tibial plateau fractures pose a significant challenge to orthopedic surgeons due to their complex nature and potential for long-term morbidity. Surgical intervention is often necessary to restore anatomical alignment and optimize functional outcomes. This study aimed to evaluate the efficacy of minimally invasive percutaneous plate osteosynthesis (MIPPO) compared to open reduction and internal fixation (ORIF) in the management of tibial plateau fractures. The present hospital-based observational study was conducted at Agartala Government Medical College for two years. Seventy adult patients with tibial plateau fractures were included, with surgical interventions performed based on fracture characteristics. Postoperative outcomes, including knee range of movements, functional recovery, and complication rates, were assessed at six months. MIPPO demonstrated superior outcomes compared to ORIF, with a higher proportion of participants achieving knee range of movements > 120 degrees (66.7% versus 36%; p = 0.030), excellent functional outcomes (66.7%versus 36%; p = 0.046), and lower postoperative complication rates (2.2% versus28%; p = 0.001). Fracture union times were significantly shorter in MIPPO (12.49 weeks) when compared to ORIF (14 weeks) (p = 0.009). MIPPO offers advantages over conventional ORIF in terms of functional recovery and complication rateswhile demonstrating comparable fracture union times. These findings advocate for the adoption of MIPPO as a preferred surgical technique for tibial plateau fractures.

Effect of pH and salt on the protonation state of fatty aniline investigated by sum-frequency vibrational spectroscopy.

Langmuir monolayers of fatty aniline (C16-aniline) were investigated using sum-frequency vibrational spectroscopy at various pH levels and NaCl concentrations. To analyze the sum-frequency generation (SFG) spectra of aniline, a multi-peak Lorentzian model, in accordance with the theory of SFG for a charged interface, was applied. First, SFG spectra of C16-aniline from pH 2 to 6 at a constant ionic strength of 10mM (where the phase of the complex potential of the dc-induced signal was suppressed to a few degrees) were fitted with the above-mentioned method. The mean-field theory that considers the chemical equilibrium of the aniline headgroup was used to analyze the fitting results to find that the pKa of aniline is 4.4 ± 0.3. The protonation fraction of the aniline headgroup was estimated to be less than 5% at pH 6 and NaCl concentrations were up to 1M. The generalized Poisson-Boltzmann equation in the Gouy-Chapmann model effectively explained the observed SFG spectra in the OH region for fatty aniline at pH as low as 2, even for the systems without addition of any salt.

Crystal structure and in vitro biological studies of a Pt(II) complex based on gallic acid and triphenylphosphine

Gallic acid is a natural polyphenol found in a variety of fruits, plants and nuts that has several biological properties, such as anti-oxidant, anti-inflammatory, and antitumor, among other activities. Some studies have proven that metal complexation could be an interesting strategy to enhance its pharmacological activities. Taking that into account, we report here the synthesis, spectral characterization (FTIR, 1H, 13C{1H}, 31P{1H} and 195Pt{1H} NMR), structural analysis, and biological activities of a new platinum(II) complex bearing gallic acid (ga) and triphenylphosphine (PPh3) as ligands. Spectral data suggest that a gallic acid molecule chelates the metal via two deprotonated phenolic oxygen atoms and two monodentate triphenylphosphines complete the coordination sphere. Furthermore, X-ray data support that the platinum(II) ion adopts a slightly distorted square-planar coordination environment. Time-dependent 1H NMR spectra at room temperature suggest that the complex is very stable in DMSO for at least 48 h. Subsequently, the cytotoxic activity of the platinum(II) complex was assessed against chronic myelogenous leukemia cells (k562) and in a non-cancerous cell line (LLCMK2). The complex was more active than gallic acid, cisplatin and carboplatin against the K562 cell line, exhibiting outstanding activity (IC50 = 0.75 μM). When tested against Mycobacterium tuberculosis, the complex showed good activity with a MIC value of 3.75 μg/mL. The results reported here reinforce the antitumor and antimycobacterial potential of metal complexes containing gallic acid and derivatives.

New mono and dinuclear half-sandwiched organoruthenium(II) complexes: Effect of dinuclearity on the biomolecular interaction and cytotoxicity

The present work describes the syntheses and structural characterization of new half sandwiched mono (complex 1) and dinuclear (complex 2) organoruthenium complexes derived from thiosemicarbazone ligand (L1). The molecular structures of compounds were characterized by analytical and multispectroscopic methods which corroborate well with single crystal XRD studies. DFT and TD-DFT studies of compounds revealed that HOMO electron density in L1 is localised on the thiosemicarbazide moiety while the LUMO electron density is evenly distributed over the ligand. However, in complex 1, the HOMO and LUMO is localised on the arene moiety and partially distributed over metal ion while HOMO and LUMO in complex 2 is equally delocalised throughout the complex. The collaborative preliminary DNA binding studies revealed that complexes 1 and 2 exhibited intercalative mode of interaction. The magnitude of DNA binding strength was determined by calculating Kb, K and Ksv values which demonstrated higher DNA binding propensity of complex 2. Furthermore, HSA binding studies of complexes also revealed better binding efficiency of dinuclear complex in contrast to mononuclear complex. The cytotoxic potential of dinuclear complex 2 was examined against triple negative breast cancer cell lines (MDA-MB-468 and MDA-MB-231) via MTT assay.

Fertiliser supplementation with a PGR complex of chlormequat chloride (CCC) and paclobutrazol (PBZ) alters Cannabis sativa growth

ABSTRACT Cannabis (Cannabis sativa) is a high-value crop, wherein growth within controlled environments is common for the purposes of maximising yield, quality, and uniformity, however, uncontrolled-growth in proximity to artificial lighting can compromise yields. Within the floricultural industry it is common practice to apply plant growth regulators (PGRs) to retard plant growth and maximise yield and quality, with two well-established PGRs being chlormequat chloride (CCC) and paclobutrazol (PBZ). Accordingly, the aim of this study was to investigate the potential of a PGR complex of CCC and PBZ for novel application to cannabis to control plant height. Treatment of cannabis with the PGR complex within an indoor hydroponic growth system resulted in a 91.1% reduction in post-treatment plant growth (p < 0.001) leading to plants with end-point height and internodal spacing (INS) 0.568-fold (p < 0.001) and 0.469-fold (p < 0.001) shorter than control plants, respectively. These results demonstrate the capacity of CCC and PBZ to beneficially halt the growth of cannabis. Accordingly, application of these PGRs in combination may be utilised to restrict cannabis height without compromising yield within commercial cultivation.

ГОСУДАРСТВЕННАЯ ПОДДЕРЖКА СУБЪЕКТОВ МАСЛОЖИРОВОГО ПОДКОМПЛЕКСА РЕГИОНОВ СИБИРСКОГО ФЕДЕРАЛЬНОГО ОКРУГА В УСЛОВИЯХ РАЗВИТИЯ АГРОЭКСПОРТА

The paper is devoted to the current problem of the export and raw materials model of development of the Russian agro-industrial complex. The purpose of the study is to determine the characteristics of state support for subjects of the oil and fat subcomplex of the regions of Siberia and assess its impact on the development of export activities. Objectives of the study: analysis of trends in the development of the oil and fat subcomplex in the regions of the Siberian Federal District (SFO) and characterization of the current state of export activities; assessment of the impact of state support on the development of production and export of oil and fat subcomplex products in the regions of the Siberian Federal District. The study presents a ranking of the Siberian Federal District entities by the level of export potential of the agro-industrial complex; a strategic portfolio analysis of the agroexport of the Siberian Federal District for 2019–2021; the dynamics of sown areas, gross harvest of oilseeds and spring rape, production of vegetable oils and their fractions, export of oil and fat products of the entities of the Siberian Federal District. Using the example of the Krasnoyarsk Region, current measures to support oilseed production are considered and an assessment is made of the impact of government funding on the efficiency of oilseed production. A conclusion is made about the dependence of the efficiency of small-scale production on budget financing of the sub-sector. The main attention is paid to the need to develop processing and deep processing of oilseeds in the regions of Siberia. Measures are proposed to support the development of the oil and fat subcomplex of the agro-industrial complex of the regions of the Siberian Federal District in a number of areas, as well as strengthening their financial support. According to the authors, the organization of high-tech production facilities in the oil and fat industry will make it possible to fully realize the export potential of the oil and fat subcomplex of the agro-industrial complex of the regions of Siberia.

Reduction of Thorium Tris(amido)arene Complexes: Reversible Double and Single C-C Couplings.

The reduction chemistry of thorium complexes is less explored compared to that of their uranium counterparts. Here, we report the synthesis, characterization, and reduction chemistry of two thorium(IV) complexes, (AdTPBN3)ThCl (1) and (DtbpTPBN3)ThCl(THF) (4) [RTPBN3 = 1,3,5-[2-(RN)C6H4]3C6H3; R = 1-adamantyl (Ad) or 3,5-di-tert-butylphenyl (Dtbp); THF = tetrahydrofuran], supported by tripodal tris(amido)arene ligands with different N-substituents. Reduction of 1 with excessive potassium in n-pentane yielded a double C-C coupling product, [(AdTPBN3)ThK(Et2O)2]2 (3), featuring a unique tetraanionic tricyclic core. On the other hand, reduction of 4 with 1 equiv of KC8 in hexanes/1,2-dimethoxyethane (DME) afforded a single C-C coupling product, [(DtbpTPBN3)Th(DME)]2 (5), with a dianionic bis(cyclohexadienyl) core. The solid- and solution-state structures of dinuclear thorium(IV) complexes 3 and 5 were established by X-ray crystallography and NMR spectroscopy. In addition, reactivity studies show that 3 and 5 can behave as thorium(II) and thorium(III) synthons to reduce organic halides. For instance, 3 and 5 are able to reduce 4 and 2 equiv of benzyl chloride, respectively, to regenerate 1 and 4 with concomitant formation of dibenzyl. Reversible C-C couplings under redox conditions provide an alternative approach to exploiting the potential of thorium arene complexes in redox chemistry.

Antiviral potential of selenium complexes from Brassicaceae by inhibiting protein bond between MAP4 and the spike of SARS-CoV-2

Context: Coronavirus disease 2019 (COVID-19), a highly contagious viral disease caused by severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2), has become a worldwide pandemic. Selenium derived from the plants of the Brassicaceae family plays an important role in several biological functions, often as an antioxidant or antiviral. In particular, selenium can be used as an adjuvant in the treatment of various viral infections. Aims: To determine the potential drug, as well as the affinity and the bond energy associated with chemical interaction bonds between the complex selenium compounds from Brassicaceae as inhibitors of the SARS-CoV-2 spike protein and MAP4 through the use of in silico studies. Methods: The methods used in this study consisted of receptor and ligand data collection, ADMET analysis, molecular docking, and molecular dynamics. Results: The results of this study indicate that the selenium complex compounds have the potential to be used as a spike inhibitor drug for SARS-CoV-2, as they have passed the Lipinski test and showed promise in the pharmacokinetic analysis. The results of the bond docking show that several complex selenium compounds, such as ethaselen, selenomethionine, and selenocystine, have stronger binding affinity values than the controls. This is compared to the control MAP4, which yielded binding affinities of -6.1 kcal/mol and spike protein -7 kcal/mol, respectively. Controlled bisoxatin and estramustine are drugs with mechanisms targeted to MAP4 and spike protein, which are the usual standards used. Conclusions: The similarity of sites, the binding of several amino acid residues dominated by hydrogen bonds, and the result of molecular dynamic results for the selenium compound derived from Brassicaceae showed a stable bond to the spike protein and MAP4 with low fluctuation levels.

Machine Learning-Based Prediction of Reduction Potentials for PtIV Complexes.

Some of the well-known drawbacks of clinically approved PtII complexes can be overcome using six-coordinate PtIV complexes as inert prodrugs, which release the corresponding four-coordinate active PtII species upon reduction by cellular reducing agents. Therefore, the key factor of PtIV prodrug mechanism of action is their tendency to be reduced which, when the involved mechanism is of outer-sphere type, is measured by the value of the reduction potential. Machine learning (ML) models can be used to effectively capture intricate relationships within PtIV complex data, leading to highly accurate predictions of reduction potentials and other properties, and offering significant insights into their electrochemical behavior and potential applications. In this study, a machine learning-based approach for predicting the reduction potentials of PtIV complexes based on relevant molecular descriptors is presented. Leveraging a data set of experimentally determined reduction potentials and a diverse range of molecular descriptors, the proposed model demonstrates remarkable predictive accuracy (MSE = 0.016 V2, RMSE = 0.13 V, R2 = 0.92). Ab initio calculations and a set of different machine learning algorithms and feature engineering techniques have been employed to systematically explore the relationship between molecular structure and similarity and reduction potential. Specifically, it has been investigated whether the reduction potential of these compounds can be described by combining ML models across different combinations of constitutional, topological, and electronic molecular descriptors. Our results not only provide insights into the crucial factors influencing reduction potentials but also offer a rapid and effective tool for the rational design of PtIV complexes with tailored electrochemical properties for pharmaceutical applications. This approach has the potential to significantly expedite the development and screening of novel PtIV prodrug candidates. The analysis of principal components and key features extracted from the model highlights the significance of structural descriptors of the 2D Atom Pairs type and the lowest unoccupied molecular orbital energy. Specifically, with just 20 appropriately selected descriptors, a notable separation of complexes based on their reduction potential value is achieved.

A review of hydrazide-hydrazone metal complexes’ antitumor potential

Cancer inflicts a tremendous burden on modern society, and more effective and selective treatments need to be developed. Metallodrugs have been extensively explored as alternatives to current chemotherapeutic regimens that suffer from shortcomings such as severe side effects and acquired resistance. Hydrazide-hydrazones are a family of organic molecules containing the hydrazone functionality attached to a carbonyl group (−C=N−NH−CO). These molecules are extremely versatile and can be obtained from modular reactions between hydrazides and aldehydes or ketones, of which a large library is commercially available. Hydrazide-hydrazones show numerous therapeutic effects, and typically, their metal complexes exhibit increased potency. This review aims to highlight the potential of hydrazide-hydrazone metal complexes in the field of anticancer research. It focuses on the literature published in the last 10 years (2013-2023) and describes their biological effects, their antiproliferative activity and their mechanisms of action. It is organized by metal ion, including Cu, Ru, Pt, Pd, V, other d-block, lanthanide, and Ga and Sn ions. It highlights the diversity of molecules being developed and can be used as a guide for developing new hydrazide–hydrazones as efficient anticancer agents.

Tuning NaCo(II) Bimetallic Cooperativity to Perform Co-H Exchange / C-F Bond Activation Processes in Polyfluoroarenes.

Recent advances in cooperative chemistry have shown the potential of heterobimetallic complexes combining an alkali-metal with an earth abundant divalent transition metal for the functionalisation of synthetically relevant aromatic molecules via deprotonative metalation. Pairing sodium with cobalt (II), here we provide an overview of the reactivity of bimetallic [NaCo(HMDS)3] [HMDS = N(SiMe3)2] towards C-H and C-F functionalisation of a wide range of perfluorinated molecules. These studies also uncover the enormous potential of this heterobimetallic base to perform Co-H exchanges with excellent selectivity and exceptional stoichiometric control as well as shedding light on the key role played by the alkali-metal.

A multiscale micromechanical progressive elastic-damage model for cementitious composites featuring superabsorbent polymer (SAP)

A multiscale micromechanics-based progressive damage model is developed to investigate the overall mechanical behavior and the interfacial microcrack evolutions of the cementitious composites featuring superabsorbent polymer (SAP) under uniaxial tension. Elastic properties, progressive damage process, and homogenization procedure of cementitious composites are systematically integrated in this model. The effective elastic moduli of the composites are determined based on a multiscale micromechanical framework. According to the small strain assumption, the total strain tensor and the elastic-damage compliance tensor are additively decomposed into elastic and damage-induced components. The damage-induced strains and compliances are then deduced from micromechanics. To characterize the progressive elastic-damage induced by microcracks, stages of microcrack propagation are identified from the interface contact stress and the matrix cleavage stress. The complex potentials and stress intensity factors for kinked interface cracks are derived from the distributed dislocations method. By implementing the homogenization process, the macroscopic mechanical behavior is obtained from the micro/mesoscale. The results indicate that the material parameters have clear mechanical significance. Different parameters, such as the SAP addition ratio, aggregate content, initial interfacial crack size, and initial interfacial crack location, are revealed to be influential in the overall mechanical behavior of the composites. The proposed model can be generalized to other particle-reinforced composites with different constituent properties, which can potentially contribute to the design and optimization of durable composites.