Schiff Base Copper Complexes Research Articles

Ultrahigh-Strength Textile Fiber-Supported Schiff Base Copper Complexes for Photocatalytic Degradation of Methyl Orange

Ultrahigh-Strength Textile Fiber-Supported Schiff Base Copper Complexes for Photocatalytic Degradation of Methyl Orange

Hydroxylation of Phenol by an Azomethine Quinoxaline Schiff Base Copper (II) Complex

Introduction: A binuclear azomethine quinoxaline Schiff base copper (II) complex, [Cu2LCl2], having square-planar environment around each copper (II), has been synthesized. Method: The coordination of the azomethine quinoxaline Schiff base with copper (II) and its structure was studied by various physicochemical and spectroscopic measurements. Results: Catalytic activity of this complex in phenol hydroxylation reaction has been examined using H2O2 as a green oxidant. Conclusion: Catalytic reaction conditions were optimized and under these conditions, 18.32 % conversion of phenol has been obtained for this catalyst

Novel copper complex inhibits the proteasome in skin squamous cell carcinoma induced by DMBA in mice

The proteasomal system is becoming a target for the treatment of several diseases, especially in cancer therapy. The present study aims to develop a novel copper complex that inhibits the proteasome in skin squamous cell carcinoma. New molecules based on the copper complex were synthesized for the first time to assess their potential as proteasome inhibitors, specifically targeting squamous cell carcinoma induced by 7,12-dimethylbenz(a)anthracene (DMBA) in mouse models. Fourier Transform Infrared (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), nuclear magnetic resonance (NMR), and energy dispersive X-ray analysis (EDX) were carried out to characterize this new copper complex. Notably, the presence of a papilloma (skin tumor) was confirmed by histopathological analysis. Subsequent investigation included the quantification of proteasome levels using a sandwich ELISA test, and the catalytic activity of the 20S proteasome was determined by measuring the fluorescence emitted after the cleavage of 7-amino-4-methylcoumarin (AMC). Hence, X-ray crystallography indicates that all Cu atoms are five-coordinated in a square-pyramidal configuration and biological activity of copper Schiff base complex, which exhibits high proteasome inhibitory activities with particular selectivity of β5 subunit. The pharmacokinetic properties (ADMET) of the copper complex named Cu(L1) showed encouraging results with very low toxicity, distribution, and absorption. Structure–activity relationship (SAR) information obtained from Cu(L1) demonstrated its selectivity and potent inhibition for β5 subunit. In this regard, this copper complex has emerged as a novel therapy for skin cancer.

An Insight Into Experimental and Theoretical Investigation of Structure, Photophysical Property by ESIPT Processes and Biological Activities of Schiff Base Copper Complex

ABSTRACTA novel Schiff base (BSSMO) and its copper complex have been synthesized, and their structure was delineated using single crystal XRD studies. Computational techniques were used to design and evaluate BSSMO‐based luminophores, revealing a significant intramolecular hydrogen bond within the molecule. Understanding ESIPT is crucial for optimizing photophysical and luminophore properties of organic molecules, especially for advancing optoelectronic devices. The study also explored the mechanisms of GSIPT and ESIPT for these BSSMO‐based luminophores using transition state theory, charge distribution, molecular orbital analysis, and quantum theory of atoms in molecules. Results advocated that BSSMO‐L2 exhibits higher absorption compared with BSSMO‐L1 and the same trend is observed in emission spectral studies. However, the intensity of enol emissions in BSSMO‐L2 is lower than that of keto (BSSMO‐L3) emissions and the S1 (Keto form) emission of BSSMO‐L3 shows significantly larger values, making it attractive for optoelectronic devices. The findings offer valuable insights for the development of ESIPT emitters with distinct photophysical properties. The in silico antidiabetic study of BSSMO‐L2 explores the interaction with PPAR‐γ protein, revealing a moderate affinity and stable complex, enhancing its bio‐potential for future applications. The in vitro anticancer study of Cu‐BSSMO‐L2 complex shows a potential anticancer effect through mitochondrial and extrinsic death receptor mediated pathways. These insights contribute to the design of novel benzenesulfonamide‐based bioactive molecules.

Cellular Effects of Cationic Copper(II) Schiff Base Complexes: Anti-Inflammatory and Antiproliferative Properties.

A series of potassium isothiocyanato-(N-salicylidene-aminoacidato) cuprates (1-5) with the general formula of the monomeric unit K[Cu(sal-aa)(NCS)] ⋅ xH2O (x=0 or 2), containing a Schiff-base ligand (H2sal-aa) derived from natural amino acids such as glycine, DL-α-alanine, DL-valine, DL-phenylalanine and β-alanine, and salicylaldehyde, was screened for in vitro antiradical and major cellular effects against selected cancerous and normal cells. The complexes exhibited strong antioxidant properties against superoxide in vitro and a protective effect on DNA under Fenton-like reaction conditions. Screening of their cellular effects revealed moderate in vitro cytotoxicity against human cancer cell lines (A2780, A2780R and MCF-7), with IC50 values of 25-35 μM, and relatively low toxicity to normal fibroblast MRC-5 cells (with IC50 values>50 μM). Additional experiments performed on A2780 cells revealed that the most potent complex 5 significantly increased the number of A2780 cells arrested in the G2/M phase of the cell cycle and triggered intracellular oxidative stress. The selected flow cytometry experiments (detection of apoptosis/autophagy and activation of caspases 3/7 and depletion of mitochondrial membrane potential) did not reveal the dominant mechanism underlying the cytotoxicity of the complexes but clearly differentiated their molecular effects from those of the reference drug cisplatin. All the complexes exerted anti-inflammatory effects by modulating the levels of the proinflammatory cytokines TNF-α and IL-1β in LPS-activated THP-1 macrophage-like cells. Complex 5 also slightly influenced the activity of the upstream NF-κB transcription factor, while no effect on PPARγ activation was detected.

Verification of the Inverse Scale Effect Hypothesis on Viscosity and Diffusion by Azo-Amino Acid Schiff Base Copper Complexes

Microdroplets generated in microfluidic devices are attracting attention as a new chemical reaction field and are expected to improve reactivity. One of the effects of microscaling is that the ratio of the force that acts on the diffusion and movement of substances to gravity is different from that of ordinary solvents. Recently, we proposed a hypothesis for determining reaction acceleration through micro-miniaturization: If a reaction is inhibited by setting the volume and viscosity of the solution to conditions that are unfavorable to the reaction on a normal scale, that reaction can be promoted in microfluidics. Therefore, for the purpose of this verification, (1) we used an amino acid Schiff base copper(II) complex with an azobenzene group to demonstrate the polarization-induced orientation in a polymer film (the redirection that is mechanically maintained in a soft matter matrix). Numerical data on optical anisotropy parameters were reported. (2) When the reaction is confirmed to be promoted in laminar flow in a microfluidic device and its azo derivative, a copper(II) complex is used to increase the solvent viscosity or diffusion during synthesis on a normally large scale. We will obtain and discuss data on the investigation of changing the solvent volume as a region. The range of experimental conditions for volume and viscosity did not lead to an improvement in synthetic yield, nor did (3) the comparison of solvents and viscosity for single-crystal growth of amino acid Schiff base copper(II) complexes having azobenzene groups. A solvent whose viscosity was measured was used, but microcrystals were obtained using the diffusion method.

Investigation of Nanostructure of Schiff Base Copper (II) Complex: Synthesis, Characterization, Textural, and Thermal Property Analysis for Evaluating their Effectiveness as Cadmium Sensors with QCM-Based Sensing Method

Investigation of Nanostructure of Schiff Base Copper (II) Complex: Synthesis, Characterization, Textural, and Thermal Property Analysis for Evaluating their Effectiveness as Cadmium Sensors with QCM-Based Sensing Method

Photocatalytic dye degradation and hydrogen peroxide sensing by a novel copper-Schiff base complex prepared via mechanochemical method

ABSTRACT Water pollution, primarily caused due to hazardous organic and inorganic substances, is a cause of concern for human health and development, for it manifests adverse repercussions across health, economic, and social dimensions. The footprints of its adverse effects are also left on aquatic/marine life forms. In the light of the negative impacts of such substances, the development of efficient remediation techniques becomes pertinent. In this article, we report a water-soluble glutamic acid Schiff base copper complex (Cu-GSb) that has been synthesised by taking recourse to a mechanochemical approach, relying upon solid-state reagent interactions in a benign environmental setting, eluding a rigorous refluxing condition and overuse of solvents. The experimental results revealed that the ligand coordinates to the metal centre in a bidentate fashion through the imine nitrogen and carboxylate oxygen, respectively, adopting a distorted square planar geometry. Further, the complex’s utility in mitigating chemical hazards has been demonstrated through the studies involving degradation of organic dyes like methylene blue and bromocresol green, and decomposition/sensing of H2O2. Notably, as a photocatalyst towards the degradation of above-mentioned dyes under visible light irradiation, our study showed the photocatalytic efficiency of Cu-GSb to be ~95% in 50–60 min. The rate of degradation reaction has been found to follow first-order kinetics with rate constant values of 6 × 10−2 and 5.66 × 10−2 min−1 for MB and BCG, respectively. Furthermore, the results of H2O2 sensing evaluation revealed that the complex is capable of potentially decomposing H2O2 in about 20–30 min. The compounds have been routinely characterised by UV–visible spectroscopy, Fourier transform infrared (FT-IR) spectroscopy, and proton nuclear magnetic resonance (1H NMR).

Metallo-organic complexes as precursors for nanostructured metal oxides and their studies on protein interactions and drug loading characteristics

In the current study, we have synthesized and characterized Schiff base copper and zinc complexes based on (E)-2,4-dichloro-6-(((2-hydroxy-4-methyl-phenyl)-imino) methyl) phenol ligand obtained from 3,5-dichloro salicylaldehyde and 2-amino,4-methyl phenol. The interactions of these complexes with the protein, Bovine Serum Albumin (BSA) were monitored through the fluorescence spectral technique. The quenching of fluorescence with the incremental addition of the ligand and the complexes provides important information regarding the binding propensity of the tested compounds with the protein. Furthermore, these metal complexes are used as precursors to obtain the pure phases of copper oxide and zinc oxide nanostructures by the thermal decomposition method. The phase formation of the metal oxides was confirmed by powder X-ray diffraction (p-XRD) technique. The metal oxides prepared from their respective metal complexes have unique characteristics in terms of particle size, morphology, and band gap and are compared with the literature reports based on conventional solid-state methods. The studies on the interaction of the prepared metal oxide and curcumin with and without BSA, the drug carrier, have been investigated and the drug loading capacity is assessed.

Synthesis and Characterization of Slow-Release Chitosan Oligosaccharide Pyridine Schiff Base Copper Complexes with Antifungal Activity.

Herein, a series of chitosan oligosaccharide copper complexes modified with pyridine groups (CPSx-Cu complexes) were successfully prepared via the Schiff base reaction and ion complexation reaction for slow-release fungicide. The structures of the synthesized derivatives were characterized via Fourier transform infrared spectroscopy and 1H and 13C nuclear magnetic resonance spectroscopy, and the unit configuration of the complexes was calculated using Gaussian software. The slow-release performance experiment demonstrated that the cumulative copper ion release rate of CPSx-Cu complexes was dependent on the type of substituents on the pyridine ring. Furthermore, the in vitro and in vivo antifungal activities of the CPSx-Cu complexes were investigated. At a concentration of 0.4 mg/mL, CPSx-Cu complexes completely inhibited the growth of Pythium vexans and Phytophthora capsici. Results indicated that CPSx-Cu complexes with slow-release ability exhibited better antifungal activity than thiodiazole-copper and copper sulfate basic. This study confirmed that combining chitosan oligosaccharide with bioactive pyridine groups and copper ions is an effective approach to further developing slow-release copper fungicides, providing new possibilities for the application of copper fungicides in green agriculture. This study lays the foundation for further studies on biogreen copper fungicides.

Schiff Base Complex of Copper Immobilized on Core-Shell Magnetic Nanoparticles Catalyzed One-Pot Syntheses of Polyhydroquinoline Derivatives under Mild Conditions Supported by a DFT Study.

We synthesized a stable and reusable Schiff base complex of copper immobilized on core-shell magnetic nanoparticles [Cu(II)-SB/GPTMS@SiO2@Fe3O4] with simple, efficient, and available materials. A variety of characterization analyses including Fourier transform infrared (FT-IR), X-ray photoelectron spectroscopy (XPS), field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), Brunauer-Emmett-Teller (BET), thermogravimetric analysis (TGA), X-ray diffraction (XRD), vibrating-sample magnetometry (VSM), energy-dispersive X-ray spectrometry (EDX), and inductively coupled plasma (ICP) confirm that our synthesized nanocatalyst was obtained. The particle size distribution from the TEM image was obtained in the range of 42-55 nm. The existence of cupric species (Cu2+) in the catalyst was determined with XPS analysis and clearly indicated two peaks at 933.7 and 953.7 eV for Cu 2p3/2 and Cu 2p1/2, respectively. BET results showed that our catalyst synthesized with a mesoporous structure and with a specific area of 48.82 m2 g-1. After detailed characterization, the resulting nanocatalyst exhibited excellent catalytic performance for the explored catalytic reactions in the one-pot synthesis of polyhydroquinoline derivatives by the Hantzsch reaction of dimedone, ethyl acetoacetate, ammonium acetate, and various aldehydes under sustainable and mild conditions. The corresponding products 5a-l are achieved in yields of 88-97%. Additionally, density functional theory (DFT) calculations were carried out to investigate the electrostatic potential root (ESP), natural bond orbital (NBO), and molecular orbitals (MOs), drawing the reaction mechanism using the total energy of the reactant and product and the study of structural parameters.

Advances in chromone-based copper(ii) Schiff base complexes: synthesis, characterization, and versatile applications in pharmacology and biomimetic catalysis.

Chromones are well known as fundamental structural elements found in numerous natural compounds and medicinal substances. The Schiff bases of chromones have a much wider range of pharmacological applications such as antitumor, antioxidant, anti-HIV, antifungal, anti-inflammatory, and antimicrobial properties. A lot of research has been carried out on chromone-based copper(ii) Schiff-base complexes owing to their role in the organometallic domain and promise as potential bioactive cores. This review article is centered on copper(ii) Schiff-base complexes derived from chromones, highlighting their diverse range of pharmacological applications documented in the past decade, as well as the future research opportunities they offer.

Synthesis of a Novel Nanomagnetic N4 Bis Schiff Base Complex of Copper (II) As an Efficient Catalyst for Click Synthesis of Tetrazoles

Synthesis of a Novel Nanomagnetic N4 Bis Schiff Base Complex of Copper (II) As an Efficient Catalyst for Click Synthesis of Tetrazoles

Investigation of the inherent characteristics of copper(ii) Schiff base complexes as antimicrobial agents

The copper(ii) Schiff base complexes (1–3) are promising candidates for antifungal/antibacterial activity.

Zeolite-encapsulated copper(II) complexes with NNO-tridentate Schiff base ligands: catalytic activity for methylene blue (MB) degradation under near neutral conditions.

Three novel copper Schiff base complexes, L1Cu(OAc)-L3Cu(OAc), bearing NNO tridentate ligands were synthesized and successfully entrapped in zeolite. All free and encapsulated complexes were fully characterized through experiments combined with theoretical calculations, and were subsequently employed as catalysts to activate H2O2 for degradation of methylene blue (MB). The catalytic activity of free complexes was tunable by substitution effects. The complex L3Cu(OAc) displayed enhanced efficiency by adopting bulky and donor substitutions due to the lower oxidation states. However, the free complexes exhibited modified structural and catalytic properties upon encapsulation into the zeolite. The constraint from the zeolite holes and coordination geometry caused the alteration of electronic structures and subsequently modified the reactivity. This study revealed that upon encapsulation, the larger molecular dimension of L3Cu(OAc) resulted in additional distorted geometry, leading to higher catalytic efficiency for MB degradation with more blue shifts in the UV-Vis spectrum. There was high catalytic activity by LnCu(OAc)-Y compared to that of the free complex, and high recyclability under near neutral conditions. In addition, the catalytic efficiency of L3Cu(OAc)-Y was higher or equivalent compared to other catalysts. This work provides new complexes with NNO tridentate ligands encapsulated inside zeolite and explains the relationship between the modified structure and functionality.

Promising in vitro and in silico biological activity of tetradentate Schiff base copper(ii) complexes with a propylenediamine bridge

Analyzed tetradentate Schiff base copper(ii) complexes (with a propylenediamine bridge) show promising antioxidant and antiproliferative activity and the ability to bind to macromolecular targets such as HSA and DNA.

UV-assisted photochemical transformation of a tetranuclear copper(II) complex: a DFT supported study on β-lactamase inhibitory activity towards antibiotic resistance.

Herein, we present a dark-green crystalline tetranuclear Cu(II) Schiff base complex {C1 = [Cu4L4](ClO4)4(DMF)4(H2O)} using a N,N,O donor ligand (HL), namely 2-(((2-hydroxypropyl)imino)methyl)-6-methoxyphenol. Spectro-photometrical investigation on the β-lactamase-like activity of this coordinately saturated system revealed its catalytic inefficiency towards hydrolysis of nitrocefin as a model substrate. This complex has attracted significant interest as a promising photo-catalyst owing to its narrow band gap (2.40 eV) as predicted from DFT calculations and its higher responsivity towards UV light. Therefore, C1 is effectively involved in the photocatalytic reduction of perchlorate to Cl- in the presence of a hole scavenger (H2O-MeOH) under prolonged UV irradiation and itself becomes photo-cleaved to yield a new dark-brown colored chlorobridged dinuclear crystalline complex C2 {[CuL(H2O)2Cl3]H2O}. Furthermore, C2 was deployed as a functional β-lactamase model and was found to show a remarkable catalytic proficiency towards the hydrolysis of nitrocefin in 70 : 30 (V/V) MeOH-H2O medium. This pro-catalyst C2 has been speculated to generate an aqua bridged active catalyst that plays a crucial factor in hydrolysis. This phenomenon was again experimentally established by potentiometric pH titration where C2 displays only one pKa value (7.11) in the basic pH range, indicating the deprotonation of the bridged water molecule. Based on several other kinetic studies, it may be postulated that the hydrolysis of nitrocefin is initiated by the nucleophilic attack of a bridging hydroxide, followed by very fast protonation of the intermediate to furnish the hydrolyzed product. It is noteworthy that the rate of nitrocefin hydrolysis is greatly inhibited in the presence of external chloride concentration. To the best of our knowledge, this is the first report on the photochemical behavior of such a tetranuclear copper(II) Schiff base complex. Our current interest is focused on inventing a potent β-lactamase inhibitory therapeutic as well as elucidating its mechanism through comprehensive chemical analysis.

A Simple Flow Injection System for Amperometric Detection of Ascorbic Acid Using Carbon Paste/Copper Schiff Base Composite Electrode

AbstractIn this paper, a simple, sensitive, and precise flow injection system was optimized and applied to ascorbic acid determination with a carbon paste electrode modified with the Schiff base copper complex. The modified sensor showed increased sensitivity toward ascorbic acid oxidation with a decrease of oxidation potential by 200 mV. Under optimized flow parameters, working potential, gasket thickness, sample and reaction coil volumes, and flow rate, the developed flow system gave a linear response from 5 to 75 μmol/L of ascorbic acid. The calculated limit of detection was 4.5 μmol/L, calculated as 3σ/s which corresponds to the absolute value of 40 ng for the 50 μL sample coil. The precision for six consecutive injections of 5 and 75 μmol/L ascorbic acid solutions was determined as a relative standard deviation of 5.8 % and 1.5 %, respectively. The flow injection system enabled up to 120 analyses per hour. An optimized flow system was applied to the determination of ascorbic acid in dietary supplements, after simple preparation.

Anti-cancer activity of novel Schiff base copper (II) complex: synthesis and characterization

A novel thiosemicarbazone substituted schiff base ligand and its Cu(II) complex have been prepared and characterized. Schiff bases are considered as an important pro ligand in coordination chemistry because they easily form stable complexes with biologically active transition metal ions. Such as Cu 2+, Zn2+, Ni2+ etc. In this paper, novel Cu (II) complexes of thiosemicarbazone ligands were synthesised by refluxing thiosemicarbazone substituted pro ligands with copper salts in 1:1 molar ratio in absolute ethanol under thermal condition at 80o c for 5-6 hour. The resulting brown coloured copper complexes were filtered and recrystallized from petroleum ether. In this synthesis, we use absolute ethanol as a polar environment for the synthesis of copper complexes from schiff base ligands because the use of polar solvent medium in synthesis plays a very important role in reducing minimum possibilities of side reactions which hinders the proper conversion of ligands into copper complexes and also reducing the reaction time. All synthesized compounds were characterized through various spectroscopic and pharmacological techniques. FT-IR, UVVis, NMR, Mass, TGA-DTA, XRD spectra techniques were used to confirm the structures of copper complexes and ligands. All compounds are thermal stable up to 350o c. The good results of pharmacological activities of compounds like in-vitro anti -oxidant and anti - cancer activity against DPPH and cisplatin drug, explained the presence of biologically active functional groups are present in ligands as well as their copper complexes. Results found that the copper complexes were more active than the ligands. The synthesis of copper complexes from thiosemicarbazone schiff base ligands in proper stoichiometic ratio is an excellent method of preparing pharmacological active compounds which can be considered as good anti -cancer drug candidate for the treatment of cancer.

The new Schiff‐base complex of copper(II) grafted on mesoporous KIT‐6 as an effective nanostructure catalyst for the homoselective synthesis of various tetrazoles

In this work, KIT‐6 mesoporous silica material was used to create heterogeneous catalyst due to its excellent surface area, substantial pore volume, and highly functionalized surface. A copper(II) Schiff‐base complex was fabricated on the surface of KIT‐6. For this purpose, (3‐iodopropyl)trimethoxysilane (IPTMS) was synthesized as a linker from (3‐choloropropyl)trimethoxysilane through a simple SN2 reaction using NaI. On the other hand, ligand (a) was synthesized from condensation of diethylenetriamine (DETA) and salicylaldehyde (SA), which was identified by IR and 1H‐NMR techniques. In order to, prepare Sal(PMeOSi)DETA (b), ligand (a) was reacted with IPTMS. One of the challenges of this synthesis was to prove the linkage between the ligand (a) and the IPTMS, which was proved by 1H‐NMR technique. In the next step, the Schiff base complex of copper(Cu(II)[Sal(PMeOSi)DETA]) (c) was synthesized using a complexation reaction of Cu(NO3)2.3 H2O and b. Finally, the obtained copper complex was fixed on KIT‐6, {Cu(II)[Sal(PMeOSi)DETA]} as the new reusable and practical catalyst. This catalyst has been identified using IR, BET, EDS, XRD, SEM, and TGA methods and employed in the synthesis of different tetrazoles for the first time. All tetrazoles were prepared with high yields, and good TOF and TON values, indicating excellent catalytic performance. This catalyst shows excellent homoselectivity in the synthesis of five‐substituted 1H‐tetrazoles. Also, it can be recovered and reused several times without a significant decrease in its catalytic activity or copper leaching.