The following set of Publications intends to highlight internationality and diversity of Scientific Themes
🟡 Alkane Functionalization / 🟡 CO2 Utilization
🟡 Dyes Adsorption /🟡 Energy Conversion Reactions
🟡 Other Sustainable Catalytic Systems / 🟡 Pharmacologically Oriented
🟡 Selective Chemosensors
Combination of Phenylsilsesquioxane and Acetate Ligands as an Approach to a Record High Nuclear Cu13Na2-Cage. Synthesis, Unique Structure, and Catalytic Activity
The complex was evaluated as precatalyst in the Baeyer–Villiger oxidation of cyclohexanone towards ϵ-caprolactone, employing hydrogen peroxide, tert-butyl hydroperoxide (TBHP) or m-chloroperoxybenzoic acid (mCPBA) as oxidants, in an aqueous acidic acetonitrile medium. The direct formation of the lactone from cyclohexane via a tandem peroxidative oxidation/Baeyer–Villiger oxidation was also studied.
Metal-free and iron(II)-assisted oxidation of cyclohexane to adipic acid with ozone: A theoretical mechanistic study
Mechanism of cyclohexane oxidation with ozone to adipic acid was theoretically investigated. Both metal-free and catalysed by a Fe(II)-scorpionate complex reactions were considered.
Halogen-Decorated Metal–Organic Frameworks for Efficient and Selective CO2 Capture, Separation, and Chemical Fixation with Epoxides under Mild Conditions
The gas adsorption analysis of halogen-appended cadmium(II) metal–organic frameworks demonstrate that they display high uptake of CO2 over N2 and CH4. Configurational bias Monte Carlo simulation studies confirm that the interaction between these MOFs and CO2 is stronger compared to those with N2 and CH4. Noncovalent interactions may be a reason for the higher carbon dioxide adsorption. These MOFs act as heterogeneous catalysts for the CO2 fixation reactions with different epoxides in the presence of tetrabutyl ammonium bromide (TBAB), for conversion into industrially valuable cyclic carbonates. They can be reused up to four cycles without compromising their structural integrity as well as without losing their activity significantly.
Fe(III)-Based Phenylsilsesquioxane/Acetylacetonate Complexes: Synthesis, Cage-like Structure, and High Catalytic Activity
Unprecedented iron-based silsesquioxane/acetylacetonate complexes were synthesized. The intriguing cage-like structure of compounds is alkaline metal-dependent: the Fe2Li2 complex includes condensed Si6-silsesquioxane and four acetylacetonate ligands; the Fe4Na4 complex exhibits two cyclic Si4-silsesquioxane and eight acetylacetonate ligands, while the Fe3K3 complex features two cyclic Si3-silsesquioxane and six acetylacetonate ligands. The latter case is the very first observation of small trimeric silsesquioxane ligands in the composition of cage-like metallasilsesquioxanes. The Fe4Na4-based complex exhibits a record high activity in the oxidation of inert alkanes with peroxides. It also acts as a catalyst in the cycloaddition of CO2 with epoxides, leading to cyclic carbonates in good yields .
Thiophene-Functionalized Cadmium(II)-Based Metal–Organic Frameworks for CO2 Adsorption with Gate-Opening Effect, Separation, and Catalytic Conversion
Porous 3D cadmium(II) metal–organic frameworks (MOFs) containing thiophene-appended carboxylate ligands, specifically capture CO2. They show a gate-opening–closing phenomenon, which features the S-shaped isotherms with impressive hysteretic desorption during the CO2 adsorption–desorption process at 195 K. Ideal adsorbed solution theory (IAST) calculations displayed selectivity values for CO2/CH4 (50:50) and CO2/N2 (15:85) of approximately 8.6–23 and 93–565, respectively. Configurational bias Monte Carlo simulation was performed. The MOFs demonstrated high conversion of epichlorohydrin to the corresponding cyclic carbonate.
Novel anthracene and pyrene containing Cd(II)-based coordination polymers for adsorptive removal of toxic dyes from aqueous medium
1D and 2D Cd(II) coordination polymers (CPs) with functionalized anthracene and pyrene groups were and characterized. Both CPs are highly effective for the removal of cationic dyes in comparison to anionic ones. The adsorption kinetics and isotherms for both CPs were determined. An insight into the removal of the organic dyes is provided by in silico studies. The stability and recyclability of both CPs were tested under adsorption conditions.
Highly Efficient Adsorptive Removal of Organic Dyes from Aqueous Solutions Using Polyaromatic Group-Containing Zn(II)-Based Coordination Polymers
We have constructed four new Zn(II) coordination polymers (CPs) using carboxylate functionalized polyaromatic groups as ligands. The synthesized CPs were used for the adsorption of various cationic and anionic organic dyes in aqueous media. One of the CPs is most effective for the removal of both types of dyes with an efficiency of 96−99%, featuring a rare example where a single CP can adsorb multiple (at least five) cationic and anionic dyes. The adsorption kinetics and the adsorption isotherms obey a pseudo-second-order model and the Langmuir model, respectively. In silico studies were performed.
Advanced materials for energy harvesting: Exploring the potential of MOFs and MXene membranes in osmotic energy applications
In this paper we studied new and emerging concepts in advanced materials for energy harvesting, specifically exploring the potential of MOFs and MXene membranes in osmotic energy applications. The primary focus of my research was a comprehensive analysis of osmotic energy harvesting (OEH) systems that utilize advanced materials. MOFs and MXenes exhibit promising properties for efficient osmotic-to-electric energy conversion. A critical emphasis on MOFs and MXenes highlights their unique structural advantages, including high surface areas, tunable pore structures, and robust ion transport channels. These attributes make them ideal candidates for OEH applications. Through a detailed exploration of the synthetic processes, structural modifications, and integration techniques of these materials, I have come to understand and emphasize their suitability for scalable and efficient OEH devices.
Benzimidazole Schiff base copper(II) complexes as catalysts for environmental and energy applications: VOC oxidation, oxygen reduction and water splitting reactions
Two novel copper(II) complexes were synthesized and fully characterized, a dimeric structure for 1 and a polymeric infinite 1D metal-organic chain for 2. The complexes were evaluated as catalysts for the oxidation of toluene, a volatile organic compound (VOC), and for oxygen reduction and water splitting reactions. 1 exhibits a higher activity for the peroxidative conversion of toluene to oxygenated products, whereas 2 demonstrates a superior performance for electrochemical energy conversion applications, i.e., for oxygen reduction (ORR), oxygen evolution (OER) and hydrogen evolution (HER) reactions..
Nickel(ii) complexes with 14-membered bis-thiosemicarbazide and bis-isothiosemicarbazide ligands: synthesis, characterization and catalysis of oxygen evolution reaction
Design and development of novel, low-cost and efficient electrocatalysts for oxygen evolution reaction (OER) in alkaline media is crucial for lowering the reaction overpotential and thus decreasing the energy input during the water electrolysis process. The activity of nickel(II) complexes towards OER is reported. The high performance of NiIILSEt might be attributed to its high surface area and thus abundant active sites with the observed low charge-transfer resistance enabling the effective current flow through the electrocatalyst. Square-planar coordination geometry and increment in Ni oxidation state are believed to favor its OER performance. Beside high activity towards OER, NiIILSEt demonstrated excellent long-term stability with continuous operation, advocating its possible application in commercial systems.
Catalyzing towards clean energy: tuning the oxygen evolution reaction by amide-functionalized Co(II) and Ni(II) pristine coordination polymers
Pristine multifunctional amide-based bimetallic Co–Ni coordination polymer and monometallic counterparts as efficient electrocatalysts for the oxygen evolution reaction.
Tandem Deacetalization−Knoevenagel Condensation Reactions for the Synthesis of Benzylidene Malononitrile Using Ruthenium(II) Cymene Complexes
Novel ruthenium(II) cymene complexes with the general formula [Ru(cym)(L’)Cl], featuring N,O- and N,N-coordinating pyrazolone-based hydrazone ligands, present multiple catalytic sites. They demonstrated high efficiency in catalyzing one-pot cascade deacetalization–Knoevenagel condensation reactions under mild conditions. DFT calculations provided insight into the catalytic mechanism, suggesting a pathway driven by metal–ligand cooperation, assisted by the basic oxygen site of the pyrazolone ring and by the weakly acidic character of the NNH proton of the hydrazone group.
Bioinspired copper-catalysed nitrous oxide reduction with simultaneous N–H or O–H bond oxidation
The process enables the oxidation of amines to imines and the formation of aminoacetal/aminal through the addition and oxidation of methanol, our catalyst simultaneously mimecking the nitrous oxide reductase (N2OR) and the alcohol oxidase (AO). The catalyst is formed in situ from inexpensive and commercially available precursors. The approach is attractive for the synthetic valorisation of organic molecules and utilisation of nitrous oxide, which remains a critical greenhouse gas and a byproduct of large-scale industrial processes, such as fertilizer production. These reactions, facilitated by a robust and affordable catalyst, are easy to carry out, making them highly practical for industrial applications.
Highly efficient Cu(II) coordination polymer catalyst for the conversion of hazardous volatile organic compounds
The copper CP [Cu(μ-1κO,2κN-L)2]n (HL = 4-(pyrimidin-5-ylcarbamoyl) benzoic acid) demonstrates an excellent catalytic activity in the peroxidative oxidation of toluene and p-xylene.
Novel cyano-activated Cu(ii) complexes of arylhydrazones of active methylene nitriles and their catalytic application for azide–alkyne cycloaddition in water and glycerol
Novel copper complexes of various nuclearities, based on arylhydrazones of active methylene nitriles (AAMN) ligands, were obtained through a simple one-pot template syntheses involving the activation of one nitrile group promoted by ressonance assisted hydrogen bonding (RAHB), and the presence of copper(ii). The nuclearity and structures of the prepared complexes are dependent on the auxiliary basic ligands and the carboxylate group at the aromatic moiety of the arylhydrazone ligands. The catalytic activity of the complexes was investigated for the microwave assisted CuAAC in glycerol, following the “Click” rules. The protocol constitutes the first example of using copper–AAMN complexes as homogeneous catalysts for the regioselective preparation of 1,4-disubstituted-1,2,3-triazoles in aqueous medium.
Non-Covalent Interactions in Enantioselective Organocatalysis: Theoretical and Mechanistic Studies of Reactions Mediated by Dual H-Bond Donors, Bifunctional Squaramides, Thioureas and Related Catalysts
Chiral bifunctional dual H-bond donor catalysts have become one of the pillars of organocatalysis. They include squaramide, thiosquaramide, thiourea, urea, and even selenourea-based catalysts combined with chiral amines, cinchona alkaloids, sulfides, phosphines and more. They can promote several types of reactions affording products in very high yields and excellent stereoselectivities in many cases: conjugate additions, cycloadditions, the aldol and Henry reactions, the Morita–Baylis–Hilman reaction, even cascade reactions, among others.
Click chemistry to allow in vivo conjugation of a fluorophore porphyrin (Por)–tetrazine (Tz) with the human epidermal growth factor receptor 2 (HER2)–targeting trastuzumab conjugated with trans-cyclooctene (TCO) is described. In vitro experiments confirmed successful click reactions between Por–Tz and trastuzumab–TCO and validated preserved trastuzumab immunoreactivity. The preclinical data demonstrate a pretargeted approach for dual PET and optical imaging of HER2-expressing tumors.
Positron Emission Tomography and Optical Imaging to Monitor Bioorthogonal Diels–Alder Click Chemistry of Trastuzumab with a Porphyrin
Encapsulation of glycosylated porphyrins in silica nanoparticles to enhance the efficacy of cancer photodynamic therapy
In this study, we encapsulated S-galactosylated and S-glucosylated porphyrins (Pors) into amorphous silica nanoparticles (SNPs) to enhance the photodynamic therapy (PDT) activity. The resulting galacto- and gluco-nanoformulations were demonstrated to be spherical in shape with diameters of 197.3 ± 29.0 nm and 128.3 ± 22.2 nm. The galacto- and gluco-nanoparticles (NPs) were able to produce a high amount of singlet oxygen (1O2) and were stable under the conditions of the experiments. In vitro studies show that the nanoformulations were effectively taken up by the human bladder cancer cell lines HT-1376 and UM-UC-3. The PDT results show that these photoactive nanoformulations are 3 to 5 times more efficient than the non-encapsulated/free Pors. These Por–silica nanoformulations could be successfully used as novel nanocarriers for the delivery of photosensitizer materials for cancer PDT.
Mesoporous silica nanoparticles (MSNPs) have attracted much attention in many biomedical applications. One of the fields in which smart functional nanosystems have found wide application is cancer treatment. Here, we present new silica nanoparticle-based systems which have been explored as efficient vehicles to transport and deliver photosensitizers (PSs) into tumor tissues during photodynamic therapy (PDT). In this work, we report the preparation, characterization, and in vitro studies of distinct shaped MSNPs grafted with S-glycoside porphyrins (Pors). The ensuing nanomaterials were fully characterized, and their properties as third-generation PSs for PDT against two bladder cancer cell lines, HT-1376 and UM-UC-3, were examined. The best uptake results were obtained for MSNP-PS2, while MSNP-PS1 showed the lowest cellular uptake among the nanocarriers tested, but revealed the best phototoxicity in both cancer cells.
Organotin(IV) complexes derived from 2,6-diacetylpyridine bis(2-hydroxybenzoylhydrazone) as prospective anti-proliferative agents: Synthesis, characterization, structures and in vitro anticancer activity
Six organotin(IV) complexes and characterized. Their anti-proliferative activity was tested against prostate cancer cells (DU-145) and normal human embryonic kidney cells (HEK-293). Among the compounds, dibutyltin compound 2 exhibited increased anti-proliferative activity. The investigation of its mechanism of action involved using AO/EB (acridine orange/ethidium bromide) and ROS (reactive oxygen species) generation assays. This detected apoptotic morphological alterations in the nucleus of the cells, with ROS generation ultimately leading to apoptosis and cell death. The superior activity of 2 may be attributed to the C···H contacts and respective higher de outside and di inside distances from the Hirshfeld surface.
Highly Efficient Singlet Oxygen Generators Based on Ruthenium Phthalocyanines: Synthesis, Characterization and in vitro Evaluation for Photodynamic Therapy
The synthesis of ruthenium(II) phthalocyanines (RuPcs) endowed with one carbohydrate unit—that is, glucose, galactose and mannose—and a dimethylsulfoxide (DMSO) ligand at the two axial coordination sites, respectively, is described. Two series of compounds, one unsubstituted at the periphery, and the other one bearing eight PEG chains at the isoindole meta-positions, have been prepared. The presence of the axial DMSO unit significantly increases the phthalocyanine singlet oxygen quantum yields, related to other comparable RuPcs. The compounds have been evaluated for PDT treatment in bladder cancer cells. In vitro studies have revealed high phototoxicity for RuPcs unsubstituted at their periphery. The phototoxicity of PEG-substituted RuPcs has been considerably improved by repeated light irradiation. The choice of the axial carbohydrate introduced little differences in the cellular uptake for both series of photosensitizers, but the phototoxic effects were considerably higher for compounds bearing mannose units.
Advancements in metal-organic, enzymatic, and nanocomposite platforms for wireless sensors of the next generation
This paper shows advanced wireless sensors, incorporating metal-organic frameworks (MOFs), enzymatic systems, and nanocomposites, offer unparalleled solutions for monitoring analytes and human physiological signals. When used with external devices, these cutting-edge sensors enable real-time monitoring of analytes and physicochemical processes within the human body, enhancing the understanding of complex biological systems. This paper presents an investigation into wireless sensor development, fabrication techniques, and user-friendly protocols. The performance of these sensors is evaluated based on their selectivity, sensitivity, and detection limits.
A benzimidazole-based new fluorogenic differential/sequential chemosensor for Cu2+, Zn2+, CN-, P2O74-, DNA, its live-cell imaging and pyrosequencing applications
A benzimidazole-based chemosensor (DFB) shows “off-on” responses upon differential detection of Cu2+ and Zn2+. The DFB derived Cu2+ & Zn2+ complexes act as efficient sensors toward CN−, PPi and DNA in an aqueous medium, as a sequential fluorescent probe to detect Cu2+, Zn2+ and PPi in living cancer cells, and can detect the PPi in the PCR amplified DNA products.
Optimized cleansing techniques: Engineered covalent-organic frameworks (COF) adsorbents for mycotoxin removal from food products
This review explores the challenges in optimizing covalent organic frameworks (COFs) materials for mycotoxin removal and proposes strategies to overcome these hurdles. By focusing on surface engineering, pore structure optimization, and functional group modifications, it emphasizes the need for further research to improve COF efficiency. The insights presented here are intended to encourage continued innovation in COF-based technologies, ultimately contributing to improved food safety and public health protection.
Understanding the Electrochemical MOF Sensors in Detecting Cancer with Special Emphasis on Breast Carcinoma Biomarkers
The paper discusses cancer’s impact, electrochemical sensing with MOFs, and recent advances in detecting biomarkers in real samples. It focuses on using MOFs for breast cancer detection in women, highlighting their potential in identifying cancer biomarkers. It also explores strategies to enhance sensor capacity, address challenges, and outline prospects to inspire researchers to develop advanced cancer detection tools.
Humidity-Resistant CeO2/In2O3 Nanocomposite-Based Chemiresistor for Selective Detection of Formaldehyde
This paper finds that formaldehyde is a common indoor pollutant posing risks to health and is suspected as a carcinogen. Achieving high sensitivity and selectivity for real-time applications is challenging. This study develops a room-temperature formaldehyde chemiresistor using a CeO2/In2O3 nanocomposite. The nanocomposite, synthesized hydrothermally, features CeO2 nanospheres on In2O3 nanocubes, enhancing detection capabilities. It can detect formaldehyde and shows response to other substances like methanol, ethanol, aniline, benzene, toluene, acetone, and ammonia. The CeO2/In2O3 sensor demonstrates moderate to high selectivity, sensitivity, stability, quick response/recovery times, and humidity resilience. This work offers a promising approach for indoor formaldehyde detection.
