A new tricarbonyl rhenium(i) complex featuring 6,7-dimethyl-2-(pyridin-2-yl)quinoxaline (1) was synthesized and characterized using spectroscopic and crystallographic techniques, supported by density functional theory (DFT) calculations. Ligand 1 acts as a bidentate N,N '-donor, coordinating through the pyridyl and quinoxaline nitrogen atoms to form a fac-[ReCl(CO)3(1)] (2) complex. Single-crystal X-ray diffraction analysis revealed an octahedral geometry around the Re(i) centre, with the three carbonyl ligands adopting a facial arrangement. Hirshfeld surface analysis indicated that weak C-H & ctdot;Cl interactions play a significant role in crystal packing stabilization. DFT and time-dependent DFT (TDDFT) calculations confirmed the observed experimental geometry and provided insights into the metal-ligand bonding, charge distribution, and electronic transitions. The combined results highlight the structural and electronic features that contribute to the stability and potential bioactivity of this rhenium(i) tricarbonyl complex. The antimicrobial assay indicated that the rhenium metal complex (2) was superior to the ligand (1) in activity against six different microbial species, but inferior to the standard antimicrobial agents.

Rhenium tricarbonyl complexes have been investigated primarily due to their remarkable inhibitory effects against cancerous cells. This study presents the synthesis, solid-state crystallography, and in vitro biological evaluation of four rhenium(I) tricarbonyl complexes. The synthesized complexes: fac-[Re(Pico)(CO)3(L1)] (1), fac-[Re(Pico)(CO)3L2] (2), fac-[Re(5-Br-3-F-Pico)(CO)3L1] (3) and fac-[Re(5-Br-3-F-Pico)(CO)3L3] (4); where L1 = 3,5-dimethyl-1H-pyrazole, L2 = 3-(trifluoromethyl)-5-methyl-1H-pyrazole, and L3 = 3,5-diphenyl-1H-pyra-zole; were characterized with FT-IR, NMR (1H and 13C), UV-Vis spectroscopy, and single-crystal X-ray diffraction technique. Preliminary in vitro biological screening of these complexes at a concentration of 10 mu M in DMSO (solvent) indicated that only complex 3 exhibited significant cell viability against HeLa (61.38 f 9.55), CaSki (52.00 f 2.78), and MDA-MB-231 (30.50 f 4.72) cancer cell lines. Consequently, this complex was further evaluated for its half-maximal effective concentration (EC50). The EC50 values for complex 3 were determined to be 45.6 f 0.09 mu M (selectivity index [SI] = 0.31), 19.87 f 0.21 mu M (SI = 0.71), and 6.0 f 0.15 mu M (SI = 2.36) against HeLa, CaSki, and MDA-MB-231 cells, respectively, with an EC50 value of 14.15 f 0.23 mu M against MRC-5 (normal human cells). Moreover, apoptosis and Western blot analyses reveal that complex 3 successfully induces apoptosis in cervical cancer cell lines (HeLa and CaSki) as well as in the triple-negative breast cancer cell line (MDA-MB-231).

Theoretical examination of hydroxyurea adsorption capabilities toward the cyclodextrin surface for proper drug delivery systems was carried out utilizing DFT simulations. The study aims to assess the efficacy of doped cyclodextrin (doped with boron, nitrogen, phosphorus, and sulfur atoms) in increasing its stability and efficiency in intermolecular interactions, hence facilitating optimal drug delivery. The adsorption energies were found to follow a decreasing order of B@ACD-HU>N@ACD-HU>P@ACD-HU>S@ACD-HU with energies of −0.046, −0.0326, −0.015, and 0.944 kcal/mol, respectively. The S@ACD-HU complex, unlike previous systems, had a physical adsorption energy. The N@ACD-HU and B@ACD-HU complexes had the shortest bond lengths of 1.42 Å (N122-C15) and 1.54 Å (B126-C15), respectively. The HOMO and LUMO values were also high in identical systems, −6.367 and −2.918 eV (B@ACD-HU) and −6.278 and −1.736 eV (N@ACD-HU), respectively, confirming no chemical interaction. The N@ACD-HU has the largest energy gap of 4.54 eV. For the QTAIM analysis and plots, the maximum electron density and ellipticity index were detected in B@ACD-HU, 0.600 au (H70-N129) and 0.8685 au (H70-N129), respectively, but N@ACD-HU exhibited a high Laplacian energy of 0.7524 a.u (H133-N122). The fragments' TDOS, OPDOS, and PDOS exhibited a strong bond interaction of greater than 1, and they had different Fermi levels, with the highest value of −8.16 eV in the N@ACD-HU complex. Finally, the NCI analysis revealed that the complexes were noncovalent. According to the literature, the van der Waals form of interactions is used in the intermolecular forces of cyclodextrin cavities. The B@ACD-HU and N@ACD-HU systems were more greenish in color with no spatial interaction. These two systems have outperformed other complexes in intermolecular interactions, resulting in more efficient drug delivery. They had the highest negative adsorption energies, the shortest bond length, the highest HOMO/LUMO energies, the highest energy gap, the highest stabilization energy, the strongest bonding effect, the highest electron density, the highest ellipticity index, and a strong van der Waals interaction that binds the drug and the surface together.

In view of the research-substantiated comparative efficiency of nontoxic and bioavailable nanomaterials synergic with human systems for drug delivery, this work was aimed at studying the comparative efficiency of transition metal (Au, Os, and Pt)-decorated B12N12 nanocages in the adsorption of fluorouracil (5Fu), an antimetabolite-classed anticarcinogen administered for cancers of the breast, colon, rectum, and cervix. Three different metal-decorated nanocages interacted with 5Fu drug at the oxygen (O) and fluorine (F) sites, resulting in six adsorbent-adsorbate systems whose reactivity and sensitivity were investigated using density functional theory computation at the B3LYP/def2TZVP level of theory with special emphasis on the structural geometry, electronic, and topology analysis as well as the thermodynamic properties of the systems. While the electronic studies predicted Os@F as having the lowest and most favorable Egp and Ead of 1.3306 eV and -11.9 kcal/mol, respectively, the thermodynamic evaluation showed Pt@F to have the most favorable thermal energy (E), heat capacity (Cp), and entropy (ΔS) values as well as negative ΔH and ΔG while the adsorption studies showed that the greatest degree of chemisorption with Ead magnitude of -204.5023 kcal/mol was observed in energies ranging from -12.0 to 138.4 kcal/mol with Os@F and Au@F at the lower and upper borders. The quantum theory of atoms in molecules results show that the six systems had noncovalent interactions as well as a certain degree of partial covalency but none showed covalent interaction while the noncovalent interaction analysis corroborated this by showing that the six systems had favorable interactions, though of varying degrees, with very little trace of steric hindrance or electrostatic interactions. Overall, the study showed that notwithstanding the good performance of the six adsorbent systems considered, the Pt@F and Os@F showed the most favorable potential for the delivery of 5Fu.

The hydrogen evolution reaction (HER) from water-splitting electrolysis in a non-acidic medium produces pure hydrogen gas on a large scale. Therefore, exploring highly abundant electrocatalysts free from precious group metals is significant because it addresses the critical issues of high cost. Hence, this study examines the effect of a zinc-based metal-organic framework (Zn-MOF) decorated with black tea-derived activated carbon (AC) as a suitable electrocatalyst for hydrogen production. The structural composition and properties of the synthesised Zn-MOF/AC composite and its precursors (i.e. carbon (C), AC, and Zn-MOF) were characterised using scanning electron microscopy, Raman, x-ray diffraction, Fourier transform infrared and thermogravimetric analysis. The electrochemical performance of the screen-printed electrodes fabricated with active materials (i.e. C, AC, Zn-MOF, and Zn-MOF/AC composite) for HER applications was investigated using cyclic voltammetry, scan rate-dependence analyses, electrochemical impedance spectroscopy, linear sweep voltammetry, turnover frequency (TOF), and Tafel measurements. The Zn-MOF/AC composite exhibits the lowest overpotential (0.32 V at 6 mAcm-2) and the largest electrochemically active surface area (ECSA = 31.81 cm2), indicating abundant accessible active sites and improved charge transfer. The composite shows a lower Tafel slope (113.3 mV·dec-1) than that of Zn-MOF (135.9 mV dec-1) with a TOF of 10.14 × 10-4mol H2·s-1. Taken together, these results show that Zn-MOF/AC offers the best balance of low overpotential and high active-surface exposure, demonstrating synergistic enhancement for practical hydrogen evolution.

[This retracts the article DOI: 10.1021/acsomega.2c07250.].

Rhenium tricarbonyl complexes in their monometallic forms have been extensively studied, mainly for their potent inhibitory activity against cancer cells. However, far fewer dinuclear complexes have been investigated for similar applications. In this study, we report the synthesis, crystal structure, DFT analysis, in vitro biological screening, and in silico molecular docking of the complex NEt4[{Re(CO)3}2-μ-(OCH3)2-μ-(3,5-Me2py)], C1 (where OCH3 = methoxy; 3,5-Me2py = 3,5-dimethyl-1H-pyrazolate). This dinuclear complex, C1, was characterised spectroscopically by FT-IR, 1H and 13C NMR, UV-Vis, as well as single-crystal X-ray diffraction. Preliminary in vitro screening at a single dose of 10 μM in DMSO revealed excellent cytotoxicity of C1 against cervical (HeLa and CaSki), pancreatic (PANC-1 and CFPAC-1), and breast (MCF-7) cancer cell lines. It was further evaluated for its half-maximal inhibitory concentration (IC50) which was determined as 1.59 ± 0.34 (SI = 6.39), 1.06 ± 0.35 (SI = 9.59), 0.74 ± 0.22 (SI = 13.73), 3.58 ± 0.10 (SI = 2.83) and 2.24 ± 0.45 (SI = 4.54) μM against HeLa, CaSki, CFPAC-1, PANC-1 and MCF-7, respectively, while the IC50 against MRC-5 (non-cancerous human fibroblast cells) was 10.16 ± 0.8 μM. The DFT calculations indicated that C1 is both reactive and conductive, with an energy gap (EHOMO-ELUMO) of 4.11 eV. Additionally, C1 was docked against tubulin to illustrate its potential binding modes to the target tubulin, and the in silico molecular docking results revealed binding affinities ranging from -5.43 to -4.37 kcal/mol.

The use of metal-based complexes is currently taking centre stage in the field of nanomedicine for the treatment and control of various ailments. Rhenium(I) tricarbonyl complexes have frequently been evaluated in vitro for their anticancer activities, and a few have advanced to in vivo and clinical trials, owing to the distinct application characteristics of these complexes. Their inception in drug development is key. This study explores a detailed chronological overview of the medical applications of Re(I) tricarbonyl complexes over the past six years (2019–2024), focusing on their applications and clinical tests in the control and management of various ailments. An in-depth examination of their activities in anticancer treatments, Chagas disease, antifungal infections, antimalarial, and microbial infections was conducted, comparing the complexes to various standard antibiotics, conventional antimalarial drugs, antifungals, and standard anticancer agents.

C21H18N2OS, monoclinic, P21/c, a = 8.4888(2) & Aring;, b = 10.2133(3) & Aring;, c = 19.9581(6) & Aring;, beta = 97.015(2)degrees, V = 1717.39(8) & Aring;3, Z = 4, T = 150(2) K, R gt (F) = 0.0361, wR ref (F 2) = 0.0913.

C 21 H 18 N 2 OS, monoclinic, P 2 1 / c , a = 8.4888(2) Å, b = 10.2133(3) Å, c = 19.9581(6) Å, β = 97.015(2)°, V = 1717.39(8) Å 3 , Z = 4, T = 150(2) K, R gt ( F ) = 0.0361, wR ref ( F 2 ) = 0.0913.

Five pyrazole-based compounds, 3,5-dimethyl-1H-pyrazole, L1; 3,5-diphenyl-1H-pyrazole, L2; 3-(trifluoromethyl)-5-phenyl-1H-pyrazole, L3; 3-(trifluoromethyl)-5-methyl-1H-pyrazole, L4; and 3,5-ditert-butyl-1H-pyrazole, L5 were synthesized from a typical condensation reaction of β-diketone derivatives with hydrazine hydrate reagent and characterized using various spectroscopic techniques such as FT-IR, UV-vis, 1H and 13C NMR, and LC-MS spectroscopy. L1 was further analyzed by single-crystal X-ray diffraction, and the N1-N1' bond distance was found to be 1.361(3) Å and correlated well with other pyrazole-based compounds. The short-term cytotoxicity of 10 μM pyrazole compounds (L1-L5) was evaluated against pancreatic (CFPAC-1 and PANC-1), breast (MDA-MB-231 and MCF-7), and cervical (CaSki and HeLa) cancer cell lines using the MTT cell viability assay. Cisplatin and gemcitabine were included as positive control drugs followed by the determination of the half-maximal effective concentrations of prospective compounds. L2 and L3, respectively, displayed moderate cytotoxicity against CFPAC-1 (61.7 ± 4.9 μM) and MCF-7 (81.48 ± 0.89 μM) cell lines.

Breast cancer continues to be the biggest cause of mortality for women worldwide, taking the lives of millions each year. As a result, scientists are now exploring the possibility of metal-based complexes as anticancer therapies. Notwithstanding, polypyridyl coordinated Re(I) complexes have demonstrated tremendous promise as cancer-fighting medications. Therefore, the intent of this research is to investigate theoretically the spectral properties, compute density functional theory (DFT), and simulate molecular docking of polypyridyl coordinated Re(I) complexes containing functionalized 2,2′-bipyridine N,N′-donor bidentate ligands: 5,5′-DiMBpy coordinated in (1a), 4,4′-DiMBpy coordinated in (2a), and 4,4′-DiMoxBp coordinated in (3a) for cancer therapy application. Intriguingly, the complex Re(2a) achieved the greatest MolDock score and H-bond energy following interactions with the target receptors utilized, followed by Re(1a) and Re(3), respectively. Thus elucidating the studied compounds to be efficient in the mitigation of breast cancer.

Prostate Cancer (PCa) is the second most diagnosed urological cancer among men worldwide. Conventional methods used for diagnosis of PCa have several pitfalls which include lack of sensitivity and specificity. On the other hand, traditional treatment of PCa poses challenges such as long-term side effects and the development of multidrug resistance (MDR). Hence, there is a need for novel PCa agents with the potential to lessen the burden of these adverse effects on patients. Nanotechnology has emerged as a promising approach to support both early diagnosis and effective treatment of tumours by ensuring precise delivery of the drug to the targeted site of the disease. Most cancer-related biological processes occur on the nanoscale hence application of nanotechnology has been greatly appreciated and implemented in the management and therapeutics of cancer. Nuclear medicine plays a significant role in the non-invasive diagnosis and treatment of PCa using appropriate radiopharmaceuticals. This review aims to explore the different radiolabelled nanomaterials to enhance the specific delivery of imaging and therapeutic agents to cancer cells. Thereafter, the review appraises the advantages and disadvantages of these modalities and then discusses and outlines the benefits of radiolabelled nanomaterials in targeting cancerous prostatic tumours. Moreover, the nanoradiotheranostic approaches currently developed for PCa are discussed and finally the prospects of combining radiopharmaceuticals with nanotechnology in improving PCa outcomes will be highlighted. Nanomaterials have great potential, but safety and biocompatibility issues remain. Notwithstanding, the combination of nanomaterials with radiotherapeutics may improve patient outcomes and quality of life.

Innovative modified cancer therapeutic techniques are anticipated to outperform existing kinds of treatment and harm healthy cells less closely surrounding the tumor location. It took many years to develop monoclonal antibodies as an effective cancer therapy. However, antibody-based therapy's effectiveness remains limited and urgently requires enhancement. The recombinant adjustable domains of heavy-chain-only antibodies are known as nanobodies, and they have several distinctive properties, including small size (15 kDa), outstanding solubility, greater stability, ease of manufacture, rapid blood clearance, and deep tissue penetration. Nanobodies are becoming increasingly popular as diagnostic and therapeutic tools, as well as potential building blocks for chimeric antigen receptors and targeted drug delivery. The use of nanobodies is one of the encouraging innovative breakthroughs that can solve the shortcomings of monoclonal antibody-based therapeutics. This book chapter informs readers of the critical aspects of nanobodies' structural and biochemical characteristics and the prospects and challenges of nanobodies research in cancer diagnosis and treatment.

In this study, (z)-5-((3-(2,3-dihydroxyphenyl) acryloyl) oxy)- 1,3,4-trihydroxycyclohexa-2,4-diene-1-carboxylic acid (chlorogenic acid) was isolated and characterized using UV-Visible, H-1 NMR and C-13 NMR, FT-IR, along with detailed investigation using density functional theory (DFT), in-silico molecular docking, and molecular dynamics (MD) simulation. Results from DFT calculation indicates that the titled compound is very stable with energy gap of 3.7-7.8 for variable functionals, and similarly, the structural parameters show very close agreement with X-ray data for bond lengths and angles. The FT-IR spectrum results revealed stretching vibration O-H (3366 cm(-1)), C=O (1689 cm(-1)), C-H (1636, 1606, 1522, and 1442 cm(-1)), C-O (1192 and 1122 cm(-1)). The drug-likeness analyses and ADME studies showed drug-likeness ability and good oral behavior of the investigated compound as it obeys Lipinski, Ghose, Veber and Egan rules. Hepatotoxic and immunotoxic activities were indicated for the toxicity/toxicological endpoints of the studied compound. The molecular docking indicates a binding affinity of -8.30 and 9.5 kcal/mol for the titled compound, which is higher than the standard drug. From the molecular dynamic simulation results, chlorogenic-2H14 (complex B) revealed variations in RMSD values of less than 3 angstrom, indicating that the protein structure underwent minor conformational changes throughout the simulation. Chlorogenic-protein complexes had average RGyr values of 3.704 - 4.907 angstrom, which indicates compaction during the simulation. Therefore, it can be said that the titled compound has potential to be effective as an agent for cholera management, and the results obtained can be platform further in-vitro, vivo and clinical trials.