Carbonyl Research Articles

Utilization of Silica Gel for the Synthesis of Geranyl Laurate and Citronellyl Laurate

Geraniol and citronellol are monoterpenoid alcohols with diverse pharmacological activities. This research focuses on synthesized of geranyl laurate and citronellyl laurate using silica gel as an esterification catalyst. The FTIR peak spectra of silica gel showed that Si-OH, Si-O-Si group were observed. XRD showed that the silica gel is an amorphous phase. The reaction was conducted under reflux using a Dean–Stark trap. The reaction was monitored by TLC and then the product was purified using column chromatography. This work reported that silica gel can be utilized as a catalyst for preparing geranyl laurate and citronellyl laurate which proven by the spectra of FTIR, 1H-NMR, and 13C-NMR of the geranyl laurate and citronellyl laurate formed. The IR spectra of geranyl laurate and citronellyl laurate showed the presence of a carbonyl group (C=O) at 1744-1745 cm-1 and C-O from ester at 1170-1176 cm-1. The peak number and its chemical shift on 1H-NMR and 13C-NMR spectra further verified the structure of geranyl laurate and citronelyl laurate. In conclusion, silica gel can be utilized as a catalyst for preparing geranyl laurat and citronellyl laurate. Therefore a silica gel-based catalyst is promising to be developed for esterification applications.

Non-benzenoid N-aryl oxalamide: synthesis of troponyl-oxalamide peptides by Pd(II)-catalyzed C(sp3)-H functionalization of glycinamides.

Aryl oxalamides are constituents of various promising drug-like molecules. Their aryl groups are derived from the benzenoid aromatic moiety. However, non-benzenoid aromatic molecules, troponoids, are found in various bioactive natural products. It would be thought-provoking to explore non-benzenoid aryl oxalamide derivatives. This report describes the synthesis of N-troponyl-oxalamide peptides by Pd(II)-catalyzed C(sp3)-H functionalization of N-troponyl glycinate peptides. This is the first instance of β-hydride elimination at the palladium complex of N-troponyl glycinates that generates imine in situ, rendering the synthesis of oxalamides. Importantly, the crystal structures of representative oxalamide derivatives form distinctive foldameric structures, such as β-sheet type structures, owing to the presence of additional troponyl carbonyl groups. Hence, these non-benzenoid oxalamides are potential scaffolds for tuning the structure and function of N-troponyl peptides, which could provide innovative avenues of research in the development of emerging structural and functional peptides.

Sorption of chromium from aqueous solutions using Fucus vesiculosus algae biosorbent

The presence of heavy metals in wastewater is an environmental concern and the current treatment procedures are very expensive so it is necessary to find effective and inexpensive biosorbents. In this study, Fucus vesiculosus was used as a biosorbent for the biosorption of Cr(III) ions from the aqueous solutions. Biosorption parameters, such as pH, adsorbent dose, contact time, and initial concentrations of Cr(III) had the most impact on the sorption process. The required pH value for sorption was 5, the biosorbent dose was 4.0 g/L, the contact time was seen to occur after 90 min, and the Cr(III) removal decreased from 98.9 to 92%. The maximum biosorption capacity of chromium was 14.12 mg/g. FTIR analysis of Fucus vesiculosus biomass before the sorption process contains carboxyl, amino, hydroxyl, alkyne, and carbonyl groups, and according to the analysis after the sorption process, it was found that Cr(III) metal ions were incorporated within the sorbent during the interaction with (=C–H) active functional groups. The biosorption data were found to be perfectly suited by Langmuir equilibrium isotherm model. According to the results of this study, Fucus vesiculosus is an effective biosorbent for the removal of Cr(III) from aqueous solutions.

Elucidation of Degradation Behavior of Barbiturates in Artificial Gastric Juice: Study on Degradability of Drugs in Stomach (V).

The gastric stability of eight barbiturates (BARs) (barbital, primidone, allobarbital, phenobarbital, cyclobarbital, pentobarbital, secobarbital, and thiobutabarbital (TBB)) was examined in artificial gastric juice using LC/UV detection. Among the eight BARs, only TBB was degraded at higher temperatures. Furthermore, the degradation product of TBB was isolated, structurally analyzed, and finally identified as 5-butan-2-yl-5-ethyl-1,3-diazinane-2,4,6-trione, also known as butabarbital. The study elucidated that butabarbital was formed by substituting the sulfur atom of the carbonyl group at the 2-position of TBB with an oxygen atom under acidic condition.

Acid-Mediated Multicomponent Domino Reaction for the Synthesis of N-substituted Isoindolinones

A one-pot multicomponent reaction of 2-carboxy-benzaldehyde, nitrile/aniline and a nucleophile (N, N- disubstituted aniline) generated a variety of functionalized N-substituted isoindolinone derivatives. The metal-free intramolecular cyclization reaction furnished products in good to excellent yields across various substrates. This environmentally friendly multi-component reaction offers a sustainable method for synthesizing a diverse library of N-substituted isoindolinone derivatives under acidic conditions. The cascade reaction triggers formation of a C-C and two C-N bonds involving carbonyl and carboxyl groups in the presence of nitrile/aniline. Additionally, in the absence of nitrogen source, 3-substituted isobenzofuran-1(3H)-ones were synthesized.

Effect of reactive fumes suppressant DOPO on the chemical composition and performance of asphalt

9,10-Dihydro-9-oxa-10-phosphorophenanthrene-10-oxide (DOPO), recognized for its role as an efficacious fume suppressant, has been shown to mitigate the emission of noxious vapors emanating from asphalt. However, the comprehensive influence of DOPO on the composition and properties of asphalt had remained unexplored. This study embarked on an in-depth examination of the effects of various DOPO dosages on the chemical composition of asphalt, employing hydrogen nuclear magnetic resonance spectroscopy (1H NMR) alongside an exhaustive analysis of asphalt components. Furthermore, the investigation elucidated the consequences of different DOPO dosages on the physical, rheological properties, and aging resistance of asphalt. The results of 1H NMR and component analysis of asphalt disclosed that DOPO engaged in chemical reactions with the unsaturated groups within the asphalt, catalyzing a metamorphosis of saturates into aromatics and resins. Such chemical transformations were instrumental in augmenting the softening point, viscosity, and rutting propensity of the asphalt while imposing a minimal impact on its penetration and ductility. Post exposure to the thin film oven test (TFOT), pressure aging vessel (PAV), and ultraviolet (UV) aging, the DOPO modified asphalt (DMA) exhibited a diminution in the increment of softening point and viscosity aging index relative to the control asphalt. Furthermore, the DMA showcased enhanced retention rates of penetration and ductility, coupled with substantially reduced shifts in complex modulus and phase angle post-aging, underlining its superior aging resistance. Fourier transform infrared spectroscopy analysis revealed a comparatively slower rate of change in carbonyl and sulfoxide groups in DMA after aging, as opposed to the control asphalt. Notably, DMA exhibited enhanced resistance to UV aging relative to TFOT and PAV aging scenarios, a trait attributable to remarkable UV absorption capabilities of DOPO. Fundamentally, DOPO enhanced the high-temperature performance and aging resistance of asphalt while simultaneously diminishing the emission of noxious fumes.

Study on the characteristics of novel fiber extracted from Foxtail palm fruits – A steps towards the sustainable development

This study explores the properties of fibers extracted from the fruits of the Foxtail palm (FPF) and assesses their potential for advancing sustainable development. Antibacterial assays demonstrated that these fibers significantly inhibit the growth of gram-negative bacteria, including Pseudomonas aeruginosa and Salmonella enterica, with inhibition zones of 24 mm and 30 mm, respectively. X-ray diffraction analysis revealed a predominantly crystalline structure, which is crucial for use as reinforcing materials, showing distinct peaks at 20° and 30° diffraction angles that signify the presence of cellulose I. Fourier-transform infrared spectroscopy confirmed the fibers’ complex composition of cellulose, hemicellulose, and lignin, indicated by the presence of hydroxyl, carbonyl, and aliphatic functional groups. Scanning electron microscopy analysis showed a rough and irregular surface texture adorned with numerous microfibrils and cavities, which are beneficial for mechanical interlocking with polymer matrices. The densely arranged cellulose microfibrils, approximately 210 µm in diameter, lend the fibers high tensile strength and stiffness. Although some surface imperfections were observed, the inherent porosity of the fibers facilitates resin absorption, enhancing their reinforcement capabilities in composite materials.

Highly Hydrophilic TiO2 Nanoparticles as Stabilizers of Pickering Emulsions with Photosensitive Lipophilic Compounds: Synthesis and Application.

Pickering emulsions are a very promising system for encapsulating and photoprotecting active ingredients. The highest photoprotection efficiency can be achieved when bare TiO2 nanoparticles are used as stabilizers. However, the main problem when using highly hydrophilic TiO2 nanoparticles is their inability to adsorb at the oil-water interface. Here, we developed emulsions stabilized by bare, highly hydrophilic TiO2 nanoparticles for the encapsulation and photoprotection of active lipophilic compounds. Emulsion stabilization occurs due to the formation of hydrogen bonds between hydroxyl groups on the particle surface and the carbonyl groups of the oil molecules. The stability and rheological properties of emulsions are explained by the properties of the initial hydrosols. The resulting Pickering emulsions demonstrated effective UV protection of α-lipoic acid. Our results pave the way for the formulation of Pickering emulsions with a widely used cosmetic oil and show for the first time the possibility of photoprotection of a lipophilic active substance using unmodified TiO2 nanoparticles.

Organocatalytic Synthesis of (Hetero)arylidene Malononitriles Using a More Sustainable, Greener, and Scalable Strategy.

The establishment of a green and sustainable Knoevenagel condensation reaction in organic chemistry is still crucial. This work aimed to provide a newly developed metal-free and halogen-free catalytic methodology for the synthesis of CS and (hetero-) arylidene malononitriles in the laboratory and industrial scale. The Knoevenagel condensation reaction of various carbonyl groups with malononitrile was investigated in ethanol, an ecofriendly medium, in the presence of seven nitrogen-based organocatalysts. A comparative study was conducted using two as-obtained and four commercially available nitrogen-based organocatalysts in Knoevenagel condensation reactions. The synthesis of CS gas (2-chlorobenzylidene malononitrile) using a closed catalytic system was optimized based on their efficiency and greener approach. The conversion of 100% and excellent yields were obtained in a short time. The products could be crystallized directly from the reaction mixture. After separating pure products, the residue solution was employed directly in the next run without any concentration, activation, purification, or separation. Furthermore, the synthesis of 2-chlorobenzylidenemahmonitrile (CS) was carried out on a large scale using imidazole as a selected nitrogen-based catalyst, afforded crystalline products with 95 ± 2% yield in five consecutive runs. Energy efficiency, cost saving, greener conditions, using only 5 mol% of organocatalyst, high recyclability of catalyst, prevention of waste, recycling extractant by a rotary evaporator for non-crystallized products, demonstrated the potential commercial production of CS using imidazole in ethanol as an efficient and highly recyclable catalytic system.

Green synthesis of silver nanoparticles from Brassaiopsis hainla extract for the evaluation of antibacterial and anticorrosion properties

Plant-mediated synthesis of silver nanoparticles (AgNPs) is an eco-friendly and convenient alternative to conventional methods. Brassaiopsis hainla (B. hainla) leaf extract (BHE) was used in this study to reduce metal salts and cap and stabilize nanoparticles (NPs), which were characterized and tested for antibacterial and anti-corrosion properties. Stirring the B. hainla extract with AgNO3 led to a color change, indicating nanoparticle formation. The absorption peak at 428 nm in the UV–visible spectrum further validated its formation. The AgNPs were characterized using various techniques such as FTIR, UV–visible, PXRD, HRTEM, SEM, and EDX. Powder X-ray diffraction analysis confirmed its nanocrystalline nature, with an average crystallite size of 17.92 nm. The FTIR spectrum showed hydroxyl, amine, amide, and carbonyl groups as capping and reducing agents for the AgNPs. SEM analysis revealed poly-dispersed NPs of various sizes, while EDX showed an intense peak for Ag, and TEM images revealed mostly hexagonal and triangular NPs. Antibacterial activity was tested against three human pathogens: Staphylococcus aureus (S. aureus), Pseudomonas, and Klebsiella oxytoca (K. oxytoca). Significant antibacterial activity was observed specifically against K. oxytoca, with an 11 mm inhibition zone. Both plant extracts and AgNPs inhibited acid-induced corrosion, with the highest inhibition efficiencies of 81.69 % and 69.54 % at 1000 ppm, respectively. With rising concerns over bacterial resistance and metal corrosion, this study addresses global challenges related to new antimicrobial agents, which are crucial for combating antibiotic resistance and protecting metals in various industries.

Sunlight-activated dye degradation of ZnO/CdO-decorated graphene oxide and its antibacterial activity

The pollution of water sources by hazardous substances such as sulfates, cyanides, and heavy metals represents a major environmental challenge. Addressing these issues requires the degradation of pollutants in wastewater to mitigate our environmental crises. Graphene oxide (GO) significantly enhances the mechanical and functional properties of GO-ZnO and GO-CdO nanocomposites, making them promising materials for applications in both sensors and catalysts. In this context, two optically active metal oxide-decorated graphene oxides (GO-ZnO and GO-CdO) were synthesized, and their photocatalytic efficacy against methylene blue (MB) was evaluated. Using an FT-IR spectrophotometer, the vibrational modes of hydroxyl (OH), carbonyl (C=O), and carboxylic (COOH) groups were identified. Raman spectroscopy analysis provided additional insights, confirming these vibrational properties. These materials exhibited peak photon absorption (λmax) at 242 nm and an optical band gap of 3.7 eV. Frontier molecular orbital (FMO) analyses indicated significant electronic charge transfer on the materials' surfaces, demonstrating their excellent capacity for adsorbing MB. An optimal catalyst dosage of 50 mg was found to be most effective in accelerating the degradation of MB. Additionally, variations in the initial pH of the solution showed a direct correlation, with higher pH levels leading to enhanced degradation efficiency, reaching up to 97% after 120 minutes. Quantum Theory of Atoms in Molecules (QTAIM) analyses revealed that MB is extensively adsorbed and degraded through a series of hydrogen bonding interactions. Moreover, experimental results indicate that both materials have a significant impact on bacterial destruction, suggesting their potential as novel antibacterial agents.

Selective Hydroboration of C-C Single Bonds without Transition-metal Catalysis.

Selective hydroboration of C-C single bonds presents a fundamental challenge in the chemical industry. Previously, only catalytic systems utilizing precious metals Ir and Rh, in conjunction with N- and P- ligands, could achieve this, ensuring bond cleavage and selectivity. In sharp contrast, we discovered an unprecedented and general transition-metal-free system for the hydroboration of C-C single bonds. This methodology is transition-metal and ligand-free and surpasses the transition-metal systems regarding chemo- and regioselectivities, substrate versatility, or yields. In addition, our system tolerates various functional groups such as Ar-X (X = halides), heterocyclic rings, ketones, esters, amides, nitro, nitriles, and C=C double bonds, which are typically susceptible to hydroboration in the presence of transition metals. As a result, a diverse range of γ-boronated amines with varied structures and functions has been readily obtained. Experimental mechanistic studies, density functional theory (DFT), and intrinsic bond orbital (IBO) calculations unveiled a hydroborane-promoted C-C bond cleavage and hydride-shift reaction pathway. The carbonyl group of the amide suppresses dehydrogenation between the free N-H and hydroborane. The lone pair on the nitrogen of the amide facilitates the cleavage of C-C bonds in cyclopropanes.

Effect of Dissolved Organic Matter on the Photodegradation of Decachlorobiphenyl (PCB-209) in Heterogeneous Systems: Experimental Analysis and Excited-State Theory Calculations.

Dissolved organic matter (DOM) can affect the transformation of pollutants through photosensitization, but most current research focuses on hydrophilic pollutants, making it such that less attention is paid to hydrophobic pollutants. In this paper, the effect and action mechanism of coexisting DOM on the photodegradation of decachlorobiphenyl (PCB-209) on suspended particles collected from the Yellow River were systematically investigated in a heterogeneous system using DOM standards and model compounds. Through molecular probe experiments, mass spectrometry analysis and theoretical calculations, we found that the excited triplet state of DOM (3DOM*) could excite PCB-209 to undergo dechlorination reaction. Due to the different modes of electron transition, the presence of carbonyl groups decreased the energy of 3DOM*, whereas the electron-donating groups made the energy of 3DOM* higher. DOM containing phenolic hydroxyl groups led to a higher steady-state concentration of •OH, and DOM containing phenyl ketone structures had a stronger ability to produce •O2-. Compared with aqueous •OH, •O2- produced from hydrophobic microregions could react more readily with PCB-209. This study deepens the understanding of the role of different functional groups of DOM in the photosensitized transformation of hydrophobic compounds.

Understanding the Sodium Storage Behavior of Closed Pores/Carbonyl Groups in Hard Carbon.

Hard carbon (HC) is a promising anode material for sodium-ion batteries. However, the intrinsic relationship between the closed pores/surface groups and sodium storage performance has been unclear, leading to difficulties in targeted regulation. In this study, renewable tannin extracts were used as raw materials to prepare HC anodes with abundant tunable closed pores and carbonyl groups through a pyrolytic modulation strategy. Combining ex situ characterizations reveals that closed pores and carbonyl groups are regulated by the pyrolytic process. Further, it is demonstrated that the plateau region is mainly contributed by the closed pores; highly stable fluorine-rich solid electrolyte interphase compositions are produced through carbonyl-induced interfacial catalysis. The optimized HC anode displays good cycling stability, exhibiting a high reversible capacity (360.96 mAh g-1) at 30 mA g-1 and capacity retention of up to 94% after 500 cycles at 1 A g-1. Moreover, the full battery assembled with Na3V2(PO4)3/C demonstrates a stable cycling performance. These findings provide a fresh knowledge of the structural design of high-performance HC anode materials and the mechanism of sodium storage in HC.

Microbial transformation of argentatins by Cunninghamella elegans

Microbial biotransformation of argentatin A (1), isoargentatin A (2) and argentatin B (3), the cycloartane- and lanostane-type triterpenoid constituents of guayule (Parthenium argentatum) resin, with Cunninghamella elegans ATCC 9245-A0 afforded eight new metabolites 4–11. These were identified as products formed as a result of: (i) α- and β-hydroxylation at C-7 and C-11; (ii) sequential oxidation of these newly formed alcohols to their corresponding carbonyl analogues; and (iii) rearrangement of the 9(10)-cyclopropane ring. The observed regiospecific hydroxylation reactions are possibly catalyzed by cytochrome P450 enzymes known to be produced by C. elegans. It is interesting that among the biotransformation products 9–11 of argentatin B (3) with a carbonyl group at C-11, only 11 had resulted from the rearrangement of the 9(10)-cyclopropane ring under the conditions used for biotransformation. This constitutes the first report of biotransformation of argentatins by C. elegans.

INFRARED SPECTRUM CHANGE OF UV IRRADIATED AND NATURAL WOOD SAMPLES DURING 12 YEARS OF STORAGE IN TOTAL DARKNESS

The stability of the surface of UV-irradiated wood samples was investigated after 12 years of storage in total darkness at room temperature. The investigated specimens were earlywood and latewood of Scots pine sapwood, earlywood and latewood of spruce, earlywood of ash, beech and hybrid poplar. The thin (1 mm tick) samples contained only earlywood or latewood, and the tangential surfaces were used for infrared spectrum measurement. For comparison, the non-irradiated natural surface (back side) of the specimens was used for infrared spectrum measurement. Natural wood surfaces were stable during the storage. Only ether linkages in hemicelluloses showed minor degradation at 1175 cm-1 wavenumber. Lignin molecules remained stable during the 12-year storage period on both UV irradiated and non-irradiated side of the specimens. In contrast, UV irradiated samples suffered alterations during the 12 years of thermal treatment at low temperature (20-25°C). Hemicelluloses in photodegraded surface layers underwent thermal degradation and oxidation processes, generating new carbonyl groups. Extractives also presented absorption increase in the conjugated carbonyl region.

Investigation of substituent effects on the electronic structure and antiviral activity of favipiravir derivatives for Covid-19 treatment using DFT and molecular docking

In this study, Density-functional theory/Time-dependent density-functional theory (DFT/TDDFT) and Molecular docking method was used to investigate the effect of methyl acetate, tetrahydrofuran and cyanobenzylidene substituents on the electronic structure and antiviral activity of favipiravir for treating COVID-19. The DFT and TDDFT computations were employed using the Gaussian 09 software package. The values were calculated using the 6-311++G(d, p) basis set and the hybrid B3LYP functional method. Autodock vina software was used for simulations to better predictions and to validate the modified compounds' binding affinities and poses. Results of the study indicate that compounds 1 to 6 all displayed a planar structure, where the pyrazine ring, carboxamide, hydroxyl groups, and other substituents are all situated within the same plane. In addition, the energy gaps (Egap) of these six compounds (Cpd 1, 2, 3, 4, 5, and 6) were compared. The significant dipole moment and binding affinity achieved implies a particular orientation for binding within the target protein, signaling the anticipated strength of the binding interaction. In all six compounds, the electrophilic domain is situated in the vicinity of the amine functional group within the carboxamide compound, whereas the nucleophilic domain encompasses both the carbonyl and hydroxyl groups. The most negatively charged sites are susceptible to electrophilic interactions. In conclusion, compounds 5 and 6 exhibit a high binding affinity of the target protein, while compound 6 has a high energy gap, which could enhance its antiviral activity against the COVID-19 virus.

Polyvinyl alcohol-modified β-cyclodextrin incorporated forward osmosis membranes with good chlorine resistance

The applications of β-cyclodextrin (β-CD) in chlorine-resistant membranes have always faced the challenge of agglomeration at high concentrations. In this study, polyvinyl alcohol (PVA) modified β-CD was used as a monomer to prepare forward osmosis (FO) membranes with high chlorine resistance. Scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FTIR), automated contact angle meter (CAM), electrodynamic analyzer (EA), X-ray photoelectron spectroscopy (XPS), and true color confocal microscopy (CSM) have been used to characterize the physicochemical properties of the FO membrane. The agglomerated β-CD affected the formation of the selective layer, resulting in reduced water fluxes ranging from 12.4 L m−2 h−1 to 1.75 L m−2 h−1. The modified TFC-PVA-β-CD FO membrane had a complete, defect-free selective layer, and water flux of 16.75 L m−2 h−1 at 1 M NaCl as a draw solution. FTIR spectra showed that the absorption peak intensity of the carbonyl (CO) group generated from β-CD and 1,3,5-Benzene tricarbonyl trichloride (TMC) increased after PVA modification. After 6 hours of chlorination, the reverse salt flux of the thin film composite (TFC) FO membranes abided by the following order: TFC (80.35 g m−2 h−1) > TFC-β-CD (60.95 g m−2 h−1) > TFC-PVA-β-CD (12.45 g m−2 h−1). The results indicated that the PVA effectively promotes uniform dispersion of β-CD. More chlorine-resistant ester bonds (-COO-) were formed in the TFC-PVA-β-CD FO membrane, so it possessed good chlorine resistance. This study provides a green, simple, and environmentally economical method for the preparation of chlorine-resistant FO membranes.

Elaborating the fluorescence regulation and quenching mechanism of sulfur-for-oxygen replacement for fluorophores.

Thio-caged fluorophores can be effectively desulfurized into their oxygenated derivatives through visible light, thereby restoring the strong emission, and are applied inlive cell super-resolution imaging. Herein, we theoretically investigated the reasons for the low fluorescence quantum yields of a series of thio-caged fluorophores and the underlying reasons for the differences in fluorescence quantum yields of their oxygenated derivatives. The calculation results show that the S atom on the thiocarbonyl group is more likely to excite n electrons to form the nπ* state, which reduces the energy of the nπ* state and leads to fluorescence quenching. In contrast, oxygenated derivatives is more likely to excite π electrons to form ππ* state, which is the main reason for restoring the strong emission of fluorophore. Meanwhile, the calculation results show that the difference of fluorescence intensity caused by oxygenated derivatives is determined by the number of the carbonyl group, which affects the vibronic coupling between ππ* and nπ* states and thereby leads to fluorescence quenching. These results can effectively reveal the fluorescence quenching mechanism of thio-caged fluorophores and the luminescence mechanism of their oxygenated derivatives, and provide correct and guiding design strategies for the development of new thio-caged fluorophores.

Synthesis, spectral analysis, XRD, molecular docking simulation of dithranol and glycine mixed ligand complexes and their potential role in suppressing breast cancer cells via down‐regulating the expression of protein metalloproteinase‐9

Five novel complexes of nickel (II)(1), zinc (II)(2), zirconium (IV)(3), lanthanum (III)(4), thorium (IV)(5), with the dithranol (Dithr) ligand and glycine (Gly) were synthesized and characterized. Their structures were investigated using elemental analysis, molar conductance (Λ), magnetic studies (μeff), spectroscopic methods (FT‐IR, UV–Vis., 1H NMR, XRD), mass spectrometry, TG/DTG and DTA. Findings revealed that Dithr was chelated via two hydroxyl oxygen atoms and carbonyl group while, Gly chelated through carboxylic oxygen and nitrogen atom. All complexes appeared with molar ratio 1:1:1 (M:Dithr:Gly) and were electrolytes with 1:1 for (1), (2) and (3) complexes, 1:2 for (4) complex, and 1:3 for (5) complex according to elemental analysis and molar conductivity data. All metal‐chelates, except Th (IV)‐complex, were confirmed to have lattice water molecules based on their thermal behavior. Average crystalline size of all compounds was calculated using XRD analysis and found in the range 35.50–55.57 nm, indicating the compounds existed as nanocrystalline structure, except zirconium (IV) complex. Then, we studied cytotoxic effects of our synthetic drugs on the survival of an aggressive‐breast‐cancer‐histotype“66cl‐4.” Given its involvement in cancer‐metastasis, matrix‐metalloproteinase‐(MMP)‐9 protein expression was evaluated using western‐blotting‐assays. Th(IV)‐complex emerged as the most effective option in inhibiting cancer‐cells‐proliferation (IC50: 9.39 μM), and suppressed expression MMP‐9 levels by 86%, at 25 μM dose, and drug‐binding‐affinity was interpreted via molecular modeling.