Synthesis, characterization and reactivity of amine-phenolate complexes towards the ROP of rac-lactide and the cycloaddition reactions of carbon dioxide and epoxides

Polylactide (PLA) is an important polymer due to its mechanical properties, biodegradability, biocompatibility, and renewable nature. Two main pathways to produce polylactide have been described in the literature: the polycondensation of lactic acid and the ring-opening polymerization (ROP) of lactide (LA). The latter is the most efficient route to produce high molecular weight polymers of low dispersity in the presence of a catalyst and/or an initiator. Furthermore, the transformation of CO₂ into cyclic carbonates is economical and uses a waste feedstock (i.e., CO₂ emissions). In this thesis, tetradentate amino-bis(phenolate) ligands were used to prepare catalysts for rac-lactide polymerization and the cycloaddition reactions of epoxides and CO₂. In these ligands, the substituents on the phenolate groups can be varied. Tetrametallic lithium and sodium complexes were synthesized and characterized; both of these metals are appealing for research in this area because of their low toxicity and cost. The complexes were fully characterized by elemental analysis, nuclear magnetic resonance spectroscopy, X-ray crystallography, and mass spectrometry. The ROP reactions of rac-lactide using tetrametallic lithium and sodium complexes were studied in the melt and solution phase in the presence and absence of benzyl alcohol as co-initiator. All complexes were capable of ring-opening rac-lactide to produce polylactide with and without benzyl alcohol. Data also showed that the complex containing the earth-abundant metal, sodium, gave excellent results. The isolated polymer was characterized by nuclear magnetic resonance spectroscopy, mass spectrometry, and gel permeation chromatography (GPC). In addition, iron(III), cobalt(II), and cobalt(III) amino-bis(phenolate) complexes were synthesized and characterized. Their activity in the cycloaddition reaction of propylene oxide and various epoxides with CO₂ to yield cyclic carbonates was investigated. The effect of factors such as reaction conditions and the electronic and steric properties of the substituents on the phenolate rings was studied. The activation energy for the formation of cyclic propylene carbonate using iron(III) complexes was also determined to be close to previously reported values in the literature

Iron amino-bis(phenolate) complexes for the formation of organic carbonates from CO2 and oxiranes

A series of iron(III) compounds supported by tetradentate amino-bis(phenolate) ligands were synthesized and characterized using electronic absorption spectroscopy, magnetic moment measurement and MALDI-TOF mass spectrometry. The solid-state structures of 1 and 2 were determined by X-ray diffraction and reveal iron(III) square pyramidal compounds. The complexes were studied as catalysts for the reaction of carbon dioxide and epoxides in the presence of a co-catalyst, under solvent free conditions to yield cyclic carbonates. Catalytic testing with TBAB as a co-catalyst shows that 4 bearing electron withdrawing groups in the ortho and para-positions of the phenolate ring exhibits the highest catalytic activity. Kinetic studies using 1 revealed that the cycloaddition reaction is affected by temperature as expected and the activation energy for propylene carbonate formation is 98.4 kJ mol−1

Ring-opening polymerization of rac-lactide mediated by tetrametallic lithium and sodium diamino-bis(phenolate) complexes

Lithium and sodium compounds supported by tetradentate amino-bis(phenolato) ligands, [Li2(N2O2BuBuPip)] (1), [Na2(N2O2BuBuPip)] (2) (where [N2O2BuBuPip] = 2,2′-N,N’-homopiperazinyl-bis(2-methylene-4,6-tert-butylphenol), and [Li2(N2O2BuMePip)] (3), [Na2(N2O2BuMePip)] (4) (where [N2O2BuMePip] = 2,2′-N,N’-homopiperazinyl-bis(2-methylene-4-methyl-6-tert-butylphenol) were synthesized and characterized by NMR spectroscopy and MALDI-TOF mass spectrometry. Variable temperature NMR experiments were performed to understand solution-phase dynamics. The solid-state structures of 1 and 4 were determined by X-ray diffraction and reveal tetrametallic species. PGSE NMR spectroscopic data suggests that 1 maintains its aggregated structure in CD2Cl2. The complexes exhibit good activity for controlled ring-opening polymerization of rac-lactide (LA) both solvent free and in solution to yield PLA with low dispersities. Stoichiometric reactions suggest that the formation of PLA may proceed by the typical coordination–insertion mechanism. For example, 7Li NMR experiments show growth of a new resonance when 1 is mixed with 1 equiv. LA and 1H NMR data suggests formation of a Li-alkoxide species upon reaction of 1 with BnOH

Fabrication and Biological Assessment of Antidiabetic α-Mangostin Loaded Nanosponges: In Vitro, In Vivo, and In Silico Studies

From MDPI via Jisc Publications RouterHistory: accepted 2021-10-29, pub-electronic 2021-11-01Publication status: PublishedFunder: King Saud University; Grant(s): RSP-2021/406Type 2 diabetes mellitus has been a major health issue with increasing morbidity and mortality due to macrovascular and microvascular complications. The urgent need for improved methods to control hyperglycemic complications reiterates the development of innovative preventive and therapeutic treatment strategies. In this perspective, xanthone compounds in the pericarp of the mangosteen fruit, especially α-mangostin (MGN), have been recognized to restore damaged pancreatic β-cells for optimal insulin release. Therefore, taking advantage of the robust use of nanotechnology for targeted drug delivery, we herein report the preparation of MGN loaded nanosponges for anti-diabetic therapeutic applications. The nanosponges were prepared by quasi-emulsion solvent evaporation method. Physico-chemical characterization of formulated nanosponges with satisfactory outcomes was performed with Fourier transform infra-red (FTIR) spectroscopy, differential scanning calorimetry (DSC), and scanning electron microscopy (SEM). Zeta potential, hydrodynamic diameter, entrapment efficiency, drug release properties, and stability studies at stress conditions were also tested. Molecular docking analysis revealed significant interactions of α-glucosidase and MGN in a protein-ligand complex. The maximum inhibition by nanosponges against α-glucosidase was observed to be 0.9352 ± 0.0856 µM, 3.11-fold higher than acarbose. In vivo studies were conducted on diabetic rats and plasma glucose levels were estimated by HPLC. Collectively, our findings suggest that MGN-loaded nanosponges may be beneficial in the treatment of diabetes since they prolong the antidiabetic response in plasma and improve patient compliance by slowly releasing MGN and requiring less frequent doses, respectively

Evaluation of Green-Synthesized Cuprospinel Nanoparticles as a Nanosensor for Detection of Low-Concentration Cd(II) Ion in the Aqueous Solutions by the Quartz Crystal Microbalance Method

Cd(II) heavy metal is an extremely dangerous hazardous material for both humans and the environment. Its high toxicity is the reason behind the examination of new techniques for detecting very small concentrations of Cd(II). Recently, Quartz Crystal Microbalance (QCM) has been one of the techniques that have been widely used to detect trace heavy metal ions in solutions. It is a simple, inexpensive, portable, and sensitive gravimetric sensor due to its quality sensitivity lowest to nanograms. In this work, Cuprospinel nanoparticles were synthesized through the green synthesis approach using Psidium guajava L. leaf extract as a reducing agent, which is the first scientific description to report the preparation of these nanoparticles by this method. Subsequently, the synthesized nanoparticles were subjected to the characterization of their crystallinity, structure, and morphology by the XRD, N2 adsorption–desorption, zeta potential, DLS, AFM, SEM, and TEM analyzers. The prepared Cuprospinel nanoparticles were evaluated as a nanosensor for the detection of the very low concentration of Cd(II) ions in aqueous solutions using the QCM technique. The results of the characterization proved that the Cuprospinel nanoparticles have formed in the nanoscale with sub-spherical shapes and particles size ranging from 20 to 80 nm. The BET surface area and pore size analysis revealed that the synthesized Cuprospinel nanoparticles possess a surface area of 47.3 m2/g, an average pore size of 1.5 nm, and a micropore volume of 0.064 cc/g. The QCM results demonstrated the success of the Cuprospinel nanoparticles sensor in detecting the tiny amounts of Cd(II) ions in the aqueous solutions with concentrations reaching about 3.6 ng/L

Design of a Novel Nanosensors Based on Green Synthesized CoFe2O4/Ca-Alginate Nanocomposite-Coated QCM for Rapid Detection of Pb(II) Ions

Pb(II) is a significant contaminant that is known to have negative effects on both humans and animals. Recent industrial operations have exacerbated these consequences, and their release of several contaminants, including lead ions, has drawn attention to the potential effects on human health. Therefore, there is a lot of interest in the rapid, accurate, and selective detection of lead ions in various environmental samples. Sensors-based nanomaterials are a significant class among the many tools and methods developed and applied for such purposes. Therefore, a novel green synthesized cobalt ferrite (CoFe2O4) nanoparticles and functionalized CoFe2O4/Ca-alginate nanocomposite was designed and successfully synthesized for the fabrication of nanoparticles and nanocomposite-coated quartz crystal microbalance (QCM) nanosensors to detect the low concentrations of Pb(II) ions in the aqueous solutions at different temperatures. The structural and morphological properties of synthesized nanoparticles and nanocomposite were characterized using different tools such as X-ray diffraction (XRD), N2 adsorption–desorption isotherm, dynamic light scattering (DLS), zeta potential analyzer (ζ-potential), atomic force microscopy (AFM), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and energy-dispersive X-ray spectroscopy (EDX). The QCM results revealed that the green synthesized CoFe2O4 nanoparticles and functionalized CoFe2O4/Ca-alginate nanocomposite-coated QCM nanosensors exhibited high sensitivity, stability, and rapid detection of Pb(II) ions in the aqueous solutions at different temperature. The lowest detection limit for Pb(II) ions in the aqueous solutions could reach 125 ng, which resulted in a frequency shift of 27.49 ± 0.81, 23.63 ± 0.90, and 19.57 ± 0.86 Hz (Δf) for the QCM detector coated with green synthesized CoFe2O4 nanoparticles thin films, and 25.85 ± 0.85, 33.87 ± 0.73, and 6.87 ± 0.08 Hz (Δf) for the QCM detector coated with CoFe2O4/Ca-Alg nanocomposite thin films in a real-time of about 11, 13, and 13 min at 25 °C, 35 °C, and 45 °C, respectively. In addition, the resonance frequency change results showed the superiority of functionalized CoFe2O4/Ca-alginate nanocomposite coated QCM nanosensor over CoFe2O4 nanoparticles towards Pb(II) ions detecting, which attributed to the beneficial properties of alginate biopolymer

Ammonia Bioremediation from Aquaculture Wastewater Effluents Using Arthrospira platensis NIOF17/003: Impact of Biodiesel Residue and Potential of Ammonia-Loaded Biomass as Rotifer Feed

The present work evaluated the capability of Arthrospira platensis complete biomass (ACDW) and the lipid-free biomass (LFB) to remove ammonium ions (NH4+) from aquaculture wastewater discharge. Under controlled conditions in flasks filled with 100 mL of distilled water (synthetic aqueous solution), a batch process ion-exchange was conducted by changing the main parameters including contact times (15, 30, 45, 60, 120, and 180 min), initial ammonium ion concentrations (10, 20, 30, 40, 50, and 100 mg·L−1), and initial pH levels (2, 4, 6, 8, and 10) at various dosages of ACDW and LFB as adsorbents (0.02, 0.04, 0.06, 0.08, and 0.1 g). After lab optimization, ammonia removal from real aquaculture wastewater was also examined. The removal of ammonium using ACDW and LFB in the synthetic aqueous solution (64.24% and 89.68%, respectively) was higher than that of the real aquaculture effluents (25.70% and 37.80%, respectively). The data of IR and Raman spectroscopy confirmed the existence of various functional groups in the biomass of ACDW and LFB. The adsorption equilibrium isotherms were estimated using Freundlich, Langmuir, and Halsey models, providing an initial description of the ammonia elimination capacity of A. platensis. The experimental kinetic study was suitably fit by a pseudo-second-order equation. On the other hand, as a result of the treatment of real aquaculture wastewater (RAW) using LFB and ACDW, the bacterial counts of the LFB, ACDW, ACDW-RAW, and RAW groups were high (higher than 300 CFU), while the LFB-RAW group showed lower than 100 CFU. The current study is the first work reporting the potential of ammonia-loaded microalgae biomass as a feed source for the rotifer (Brachionus plicatilis). In general, our findings concluded that B. plicatilis was sensitive to A. platensis biomass loaded with ammonia concentrations. Overall, the results in this work showed that the biomass of A. platensis is a promising candidate for removing ammonia from aquaculture wastewater

The Effect of Plasticizers on the Polypyrrole-Poly(vinyl alcohol)-Based Conducting Polymer Electrolyte and Its Application in Semi-Transparent Dye-Sensitized Solar Cells

In this work, the quasi-solid-state polymer electrolyte containing poly(vinyl alcohol)-polypyrrole as a polymer host, potassium iodide (KI), iodine (I2), and different plasticizers (EC, PC, GBL, and DBP) was successfully prepared via the solution casting technique. Fourier transform infrared spectroscopy (FTIR) was used to analyze the interaction between the polymer and the plasticizer. X-ray diffraction confirmed the reduction of crystallinity in the polymer electrolyte by plasticizer doping. The ethylene carbonate-based polymer electrolyte showed maximum electrical conductivity of 0.496 S cm−1. The lowest activation energy of 0.863 kJ mol−1 was obtained for the EC-doped polymer electrolyte. The lowest charge transfer resistance Rct1 was due to a faster charge transfer at the counter electrode/electrolyte interface. The polymer electrolyte containing the EC plasticizer exhibited an average roughness of 23.918 nm. A photo-conversion efficiency of 4.19% was recorded in the DSSC with the EC-doped polymer electrolyte under the illumination of 100 mWcm−2

Fabrication and Biological Assessment of Antidiabetic α-Mangostin Loaded Nanosponges: In Vitro, In Vivo, and In Silico Studies

Type 2 diabetes mellitus has been a major health issue with increasing morbidity and mortality due to macrovascular and microvascular complications. The urgent need for improved methods to control hyperglycemic complications reiterates the development of innovative preventive and therapeutic treatment strategies. In this perspective, xanthone compounds in the pericarp of the mangosteen fruit, especially α-mangostin (MGN), have been recognized to restore damaged pancreatic β-cells for optimal insulin release. Therefore, taking advantage of the robust use of nanotechnology for targeted drug delivery, we herein report the preparation of MGN loaded nanosponges for anti-diabetic therapeutic applications. The nanosponges were prepared by quasi-emulsion solvent evaporation method. Physico-chemical characterization of formulated nanosponges with satisfactory outcomes was performed with Fourier transform infra-red (FTIR) spectroscopy, differential scanning calorimetry (DSC), and scanning electron microscopy (SEM). Zeta potential, hydrodynamic diameter, entrapment efficiency, drug release properties, and stability studies at stress conditions were also tested. Molecular docking analysis revealed significant interactions of α-glucosidase and MGN in a protein-ligand complex. The maximum inhibition by nanosponges against α-glucosidase was observed to be 0.9352 ± 0.0856 µM, 3.11-fold higher than acarbose. In vivo studies were conducted on diabetic rats and plasma glucose levels were estimated by HPLC. Collectively, our findings suggest that MGN-loaded nanosponges may be beneficial in the treatment of diabetes since they prolong the antidiabetic response in plasma and improve patient compliance by slowly releasing MGN and requiring less frequent doses, respectively

Hydrothermal Microwave Synthesis of Co3O4/In2O3 Nanostructures for Photoelectrocatalytic Reduction of Cr(VI)

Co3O4/In2O3 nanocomposites were prepared via a microwave-hydrothermal method and directly used as photoanodes for the photoelectrocatalytic (PEC) process to reduce Cr(VI). The as-prepared Co3O4/In2O3 composites show a rod-like structure, which is composed of nanoparticles. The PEC experiments indicated that after 120 min of irradiation with 0.7 V bias voltage and visible light, the Cr(VI) reduction efficiency of Co3O4/In2O3 composites in aqueous solution was 100%, which was superior to the samples prepared by other methods. Moreover, the Co3O4/In2O3 composite still had a high catalytic activity after five runs of PEC experiments. Elimination experiments demonstrate that photo-generated electrons (e–) performed a key role in the catalytic reduction of Cr(VI). The significantly improved PEC performance can be attributed to the bias voltage and the p-n heterojunction formed between Co3O4 and In2O3. Therefore, Co3O4/In2O3 nanocomposites have a considerable potential for the PEC reduction of Cr(VI)