Benign-by-design plant extract-mediated preparation of copper oxide nanoparticles for environmentally related applications.

A facile, cost-competitive, scalable and novel synthetic approach is used to prepare copper oxide (CuO) nanoparticles (NPs) using Betel leaf (Piper betle) extracts as reducing, capping, and stabilizing agents. CuO-NPs were characterized using various analytical techniques, including Fourier-transform infrared (FTIR) spectroscopy, ultraviolet-visible (UV-Vis) spectroscopy, scanning electron microscopy (SEM), X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), as well as photoluminescence (PL) measurements. The activity of CuO-NPs was investigated towards Congo red dye degradation, supercapacitor energy storage and antibacterial activity. A maximum of 89% photodegradation of Congo red dye (CR) was obtained. The nanoparticle modified electrode also exhibited a specific capacitance (Csp) of 179 Fg-1. Furthermore, the antibacterial potential of CuO NPs was evaluated against Bacillus subtilis and Pseudomonas aeruginosa, both strains displaying high antibacterial performance.

A novel and efficient voltammetric sensor for the simultaneous determination of alizarin red S and tartrazine by using poly(leucine) functionalized carbon paste electrode.

In the current work, a rapid, selective, and sensitive technique was developed for the detection of Alizarin Red S (ARS) by applying poly leucine modified carbon paste electrode (PLMCPE). Electrochemical impedance spectroscopy (EIS) and Scanning electron microscopy (SEM) were utilized to study the surface morphology of unmodified carbon paste electrode (UMCPE) and PLMCPE. The active surface area for UMCPE and PLMCPE was found to be 0.0012 cm2 and 0.0026 cm2 respectively. The electrochemical response of ARS at UMCPE and PLMCPE was analyzed using cyclic voltammetry (CV) in the potential window of 0.4 to 1.0 V. The cyclic voltammogram obtained for varying the pH of 0.2 M phosphate buffer (PB) solution showed maximum current for the oxidation of ARS at pH 6.5. The electrochemical reaction of ARS was found to be irreversible and adsorption controlled. The effect of variation of concentration of ARS on the oxidation peak current was evaluated using CV and linear scan voltammetry (LSV). A linear relationship between the concentration variation and current was obtained in the linear range of 1.5 µM-3.5 µM and 0.2 µM-5.0 µM for CV and LSV respectively. The limit of detection (LOD) of 0.68 µM for the CV method and 0.29 µM for the LSV method was exhibited by the developed sensor. The simultaneous study of ARS along with tartrazine (TZ) showed good selectivity for ARS. The interferents of foreign molecules showed no effect on the selectivity of the electrode. The applicability of PLMCPE on real samples gave good recovery ranging from 97.46-101.2%; hence, the sensor can be utilized on real samples. The developed sensor has good stability and sensitivity.

Open-Mouthed Hollow Carbons: Systematic Studies as Cobalt- and Nitrogen-Doped Carbon Electrocatalysts for Oxygen Reduction Reaction.

Although hollow carbon structures have been extensively studied in recent years, their interior surfaces are not fully utilized due to the lack of fluent porous channels in the closed shell walls. This study presents a tailored design of open-mouthed particles hollow cobalt/nitrogen-doped carbon with mesoporous shells (OMH-Co/NC), which exhibits sufficient accessibility and electroactivity on both the inner and outer surfaces. By leveraging the self-conglobation effect of metal sulfate in methanol, a raspberry-structured Zn/Co-ZIF (R-Zn/Co-ZIF) precursor is obtained, which is further carbonized to fabricate the OMH-Co/NC. In-depth electrochemical investigations demonstrate that the introduction of open pores can enhance mass transfer and improve the utilization of the inner active sites. Benefiting from its unique structure, the resulting OMH-Co/NC exhibits exceptional electrocatalytic oxygen reduction performance, achieving a half-wave potential of 0.865 V and demonstrating excellent durability.

Design of tropinium-functionalized anion exchange membranes for acid recovery via diffusion dialysis process.

Diffusion dialysis (DD) process utilizing anion exchange membranes (AEMs) is an environmentally-friendly and energy-efficient technology. From acidic wastewater, DD is needed for acid recovery. This research reports the development of a series of dense tropinium-functionalized AEMs via solution casting method. Fourier Infrared transform (FTIR) spectroscopy verified the successful preparation of AEMs. The developed AEMs exhibited a dense morphology, featuring 0.98-2.42 mmol/g of ion exchange capacity (IEC), 30-81% of water uptake (WR) and 7-32% of linear swelling ratio (LSR). They displayed exceptional mechanical, thermal and chemical stability and were employed for acid waste treatment from HCl/FeCl2 mixtures via DD process. AEMs possessed 20 to 59 (10-3 m/h) and 166 to 362 of acid diffusion dialysis coefficient (UH+) and separation factor (S) respectively at 25 °C. Compared to DF-120 commercial membrane (UH+ = 0.004 m/h, S = 24.3), their DD efficiency was improved under identical experimental conditions.

Investigation on synthesis of ternary g-C3N4/ZnO-W/M nanocomposites integrated heterojunction II as efficient photocatalyst for environmental applications.

The rapid industrialization of the world is disparagingly manipulating our environment and natural ecosystem. The researchers are taking keen interest to invent novel material as photocatalyst for non-degradable organic pollutants. Solar energy-driven practices employing semiconductors are a novel approach towards wastewater remediation. Here in, we successfully synthesized a vigorous photocatalysts comprising of g-C3N4 and doped ZnO-W/M (M = Co, Ce, Yb, Sm) by co-precipitation followed by metals doping via calcination approach. The structural, morphological, and photocatalytic applications for organic pollutants of synthesized heterostructure nanocomposites were examined by XRD, FTIR, SEM, EDX and UV visible spectrophotometer. Diffraction peaks attributed to both g-C3N4 and ZnO-W were detected in the XRD spectra. The FTIR spectra also inveterate the formation of g-C3N4/ZnO-W/M composites. The SEM images reveal an agglomerated morphology and EDS analysis also confirmed close contact between g-C3N4, ZnO-W and doped metals. The abridged energy band gap of g-C3N4/ZnO-W/M (M = Ce, Yb, Sm, Co) nanocomposites calculated via Tauc plot are 2.68, 2.88, 3.24 and 3.29 eV respectively. Narrowing of bandgap is considered an imperative triumph for the degradation of industrial effluents. The photocatalytic activity was performed against four different dyes and follows the trend Ce > Yb > Sm > Co. The recyclability tests were carried out for different dyes and no substantial catalytic activity loss was observed even after the fourth experimental run, which proves that reported ternary heterojunctions exhibit high mechanical stability and reusability.The species trapping experiment exposed that generated h+ are the principal active specie for dye photodegradation reactions. This work disseminates a novel photocatalyst for the removal of synthetic dyes.

Silica-derived materials from agro-industrial waste biomass: Characterization and comparative studies.

The management and final disposal of agro-industrial wastes are one of the main environmental problems. Due to the presence of silica in some agricultural by-products, it is possible to convert waste into materials with advanced properties. This contribution was aimed to extract and characterize silica materials from various feedstocks including sugarcane bagasse (SCB), corn stalk (CS), and rice husk (RH). Silica yields of 17.91%, 9.39%, and 3.25% were obtained for RH, CS, and SCB. On the other hand, the textural properties show that the siliceous materials exhibited mesoporous structures, with high silica composition in the materials due to the formation of crystalline SiO2 for SCB and CS and amorphous for RH. XPS spectra demonstrate the presence of Si4+ species in RH, and Si3+/Si4+ tetrahedra in SCB and CS.

Valorization of sewage sludge for facile and green wood bio-adhesives production.

A method is presented herein for the design of wood bio-adhesives using sewage sludge extracts (SSE). SSE was extracted from SS using deep eutectic solvents and processed with glycerol triglycidyl ether (GTE) to disrupt the secondary structure of proteins. An additive was also used to improve mechanical performance. The resulting bio-adhesive (SSE/GTE@TA) had a wet shear strength of 0.93 MPa, meeting the Chinese national standard GB/T 9846-2015 (≥0.7 MPa). However, the high polysaccharide content in SSE would weaken the mechanical properties of wood bio-adhesives. The key to improve bio-adhesive quality was the formation of a strong chemical bond via Maillard reaction as well as higher temperatures (140 °C) to reduce polysaccharide content via dehydration. This approach has lower environmental impact and higher economic efficiency compared to incineration and anaerobic digestion of sewage sludge. This work provides a new perspective on the high-value utilization of SS and offers a novel approach to developing bio-adhesives for the wood industry.

Highly efficient and stable catalysts-covalent organic framework-supported palladium particles for 4-nitrophenol catalytic hydrogenation.

A covalent organic framework (COF) was used as the support of the catalyst in this work in order to obtain an environmentally friendly catalyst with high catalytic performance, selectivity and stability for 4-nitrophenol hydrogenation. Pd tiny particles are fixed in the cavity of COF to obtain Pd/COF catalysts, which has a quite narrow particle size distribution (5.09 ± 1.30 nm). As-prepared Pd/COF catalysts (Pd loading-2.11 wt%) shows excellent catalytic performance (conversion - 99.3%, selectivity >99.0% and turnover frequency (TOF)-989.4 h-1) for 4-nitrophenol hydrogenation under relatively mild reaction conditions of reaction temperature-40 °C and reaction pressure-3.0 MPa H2, and Pd/COF catalysts have high stability. Pd/COF catalysts were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscope energy-dispersive X-ray spectroscopy (SEM-EDS), transmission electron microscope (TEM), high resolution TEM (HRTEM), Brunauer-Emmett-Teller (BET), scanning TEM energy-dispersive X-ray spectroscopy (STEM-EDS) elemental analysis techniques to prove that the Pd nanoparticles are highly dispersed on the COF. Pd/COF catalysts have good stability and reusability hence with certain industrial application value.

Glycerol Valorization towards a Benzoxazine Derivative through a Milling and Microwave Sequential Strategy.

Glycerol and aminophenol intermolecular condensation has been investigated through a milling and microwave-assisted sequential strategy, towards the synthesis of a benzoxaxine derivative. Mechanochemical activation prior to the microwave-assisted process could improve the probability of contact between the reagents, and greatly favors the higher conversion of aminophenol. At the same time, following a mechanochemical-microwave sequential approach could tune the selectivity towards the formation of a benzoxazine derivative, which could find application in a wide range of biomedical areas.

Appliance of the piperidinyl-hydrazidoureido linker to benzenesulfonamide compounds: Synthesis, in vitro and in silico evaluation of potent carbonic anhydrase II, IX and XII inhibitors.

Herein we report on a new series of hydrazidoureidobenzensulfonamides investigated as inhibitors of the cytosolic human (h) hCA I and II isoforms, as well as the transmembrane, tumor-associated enzymes hCA IX and XII. The reported derivatives contain a 4-substituted piperidine fragment in which the hydrazidoureido linker has been involved as spacer between the benzenesulfonamide fragment which binds the zinc ion from the active site, and the tail of the inhibitor. Depending on the substitution pattern at the piperidine ring, low nanomolar inhibitors were detected against hCA II, hCA IX and hCA XII, making the new class of sulfonamides of interest for various pharmacologic applications.

Benzothiazole derivatives as anticancer agents.

Benzothiazole (BTA) belongs to the heterocyclic class of bicyclic compounds. BTA derivatives possesses broad spectrum biological activities such as anticancer, antioxidant, anti-inflammatory, anti-tumour, antiviral, antibacterial, anti-proliferative, anti-diabetic, anti-convulsant, analgesic, anti-tubercular, antimalarial, anti-leishmanial, anti-histaminic and anti-fungal among others. The BTA scaffolds showed a crucial role in the inhibition of the metalloenzyme carbonic anhydrase (CA). In this review an extensive literature survey over the last decade discloses the role of BTA derivatives mainly as anticancer agents. Such compounds are effective against various types of cancer cell lines through a multitude of mechanisms, some of which are poorly studied or understood. The inhibition of tumour associated CAs by BTA derivatives is on the other hand better investigated and such compounds may serve as anticancer leads for the development of agents effective against hypoxic tumours.

Synthesis, characterisation, biological evaluation and in silico studies of sulphonamide Schiff bases.

Sulphonamides are biologically important compounds with low toxicity, many bioactivities and cost-effectiveness. Eight sulphonamide derivatives were synthesised and characterised by FT-IR, 13C NMR, 1H NMR, LC-MS and elemental analysis. Their inhibitory effect on AChE, and carbonic anhydrase I and II enzyme activities was investigated. Their antioxidant activity was determined using different bioanalytical assays such as radical scavenging tests with ABTS•+, and DPPH•+ as well as metal-reducing abilities with CUPRAC, and FRAP assays. All compounds showed satisfactory enzyme inhibitory potency in nanomolar concentrations against AChE and CA isoforms with KI values ranging from 10.14 ± 0.03 to 100.58 ± 1.90 nM. Amine group containing derivatives showed high metal reduction activity and about 70% ABTS radical scavenging activity. Due to their antioxidant activity and AChE inhibition, these novel compounds may be considered as leads for investigations in neurodegenerative diseases.

Inhibition survey with phenolic compounds against the δ- and η-class carbonic anhydrases from the marine diatom thalassiosira weissflogii and protozoan Plasmodium falciparum.

The inhibition of δ- and η-class carbonic anhydrases (CAs; EC 4.2.1.1) was poorly investigated so far. Only one δ-CA, TweCA from the diatom Thalassiosira weissflogii, and one η-CA, PfCA, from Plasmodium falciparum, have been cloned and characterised to date. To enrich δ- and η-CAs inhibition profiles, a panel of 22 phenols was investigated for TweCA and PfCA inhibition. Some derivatives showed effective, sub-micromolar inhibition of TweCA (KIs 0.81-65.4 µM) and PfCA (KIs 0.62-78.7 µM). A subset of compounds demonstrated a significant selectivity for the target CAs over the human physiologically relevant ones. This study promotes the identification of new potent and selective inhibitors of TweCA and PfCA, which could be considered as leads for finding molecular probes in the study of carbon fixation processes (in which TweCA and orthologue enzymes are involved) or drug candidates in the treatment of malaria.

Phosphonamidates are the first phosphorus-based zinc binding motif to show inhibition of ß-class carbonic anhydrases from bacteria, fungi, and protozoa.

A primary strategy to combat antimicrobial resistance is the identification of novel therapeutic targets and anti-infectives with alternative mechanisms of action. The inhibition of the metalloenzymes carbonic anhydrases (CAs, EC 4.2.1.1) from pathogens (bacteria, fungi, and protozoa) was shown to produce an impairment of the microorganism growth and virulence. As phosphonamidates have been recently validated as human α-CA inhibitors (CAIs) and no phosphorus-based zinc-binding group have been assessed to date against ß-class CAs, herein we report an inhibition study with this class of compounds against ß-CAs from pathogenic bacteria, fungi, and protozoa. Our data suggest that phosphonamidates are among the CAIs with the best selectivity for ß-class over human isozymes, making them interesting leads for the development of new anti-infectives.

Benzenesulfonamides incorporating nitrogenous bases show effective inhibition of ß-carbonic anhydrases from the pathogenic fungi Cryptococcus neoformans, Candida glabrata and Malassezia globosa.

There is an urgent need for new chemotherapic agents to treat human fungal infections due to emerging and spreading globally resistance mechanisms. Among the new targets that have been recently investigated for the development of antifungal drugs there are the metallo-enzymes Carbonic Anhydrases (CAs, EC 4.2.1.1). The inhibition of the ß-CAs identified in many pathogenic fungi leads to an impairment of parasite growth and virulence, which in turn leads to a significant anti-infective effect. Based on antifungal nucleoside antibiotics, the inhibition of the ß-CAs from the resistance-showing fungi Candida glabrata (CgNce103), Cryptococcus neoformans (Can2) and Malasszia globosa (MgCA) with a series of benzenesulfonamides bearing nitrogenous bases, such as uracil and adenine, is here reported. Many such compounds display low nanomolar (<100 nM) inhibitory potency against Can2 and CgNce103, whereas the activity of MgCA is considerably less affected (inhibition constants in the range 138.8-5601.5 nM). The ß-CAs inhibitory data were compared with those against α-class human ubiquitous isoforms. Interesting selective inhibitory activities for the target fungal CAs over hCA I and II were reported, which make nitrogenous base benzenesulfonamides interesting tools and leads for further investigations in search of new antifungal with innovative mechanisms of action.

Extending the γ-class carbonic anhydrases inhibition profiles with phenolic compounds.

γ-Class carbonic anhydrases (CAs; EC 4.2.1.1) lack of extended inhibition characterization in comparison to α- and ß-class isozymes. For this reason, a panel of 22 phenols was investigated here for the inhibition of the γ-CAs from the pathogenic bacteria Burkholderia pseudomallei (BpsCAγ), Porphyromonas gingivalis (PgiCA), Vibrio cholerae (VchCAγ) and from the antarctic bacteria Pseudoalteromonas haloplanktis (PhaCAγ) and Colwellia psychrerythraea (CpsCAγ). The exploration of the chemical space around the main phenolic group led to the discovery of a number of such derivatives showing effective, sometimes sub-micromolar inhibition against BpsCAγ (KIs 0.45-8.6 µM), PgiCA (KIs 0.36-9.8 µM) and VchCAγ (KIs 0.47-9.6 µM). A subset of compounds even demonstrated a significant selectivity for the target γ-CAs over the human physiologically most relevant isoform CA II. This study enriches the inhibitory profiles database for γ-class CAs and promotes the identification of new potent and selective inhibitors against bacterial isoforms over human off-target ones. These agents are of remarkable interest and importance in the search of novel, worldwide required, antibiotic agents possessing alternative mechanisms of action as a strategy to overcome the spread to antimicrobic resistance.

Click-tailed benzenesulfonamides as potent bacterial carbonic anhydrase inhibitors for targeting Mycobacterium tuberculosis and Vibrio cholerae.

A series of 1,2,3-triazole-bearing benzenesulfonamides was assessed for the inhibition of carbonic anhydrases (CA, EC 4.2.1.1) from bacteria Vibrio cholerae (VchCAα and VchCAß) and Mycobacterium tuberculosis (ß-mtCA3). Growing resistance phenomena against existing antimicrobial drugs are globally spreading and highlight a urgent need of agents endowed with alternative mechanisms of action. Two global WHO strategies aim to reduce cholera deaths by 90% and eradicate the tuberculosis epidemic by 2030. The derivatives here reported represent interesting leads towards the optimization of new antibiotic agents showing excellent inhibitory efficiency and selectivity for the target CAs over the human (h) off-target isoform hCA I. In detail, the first subset of derivatives potently inhibits VchCAα in a low nanomolar range (KIs between 0.72 and 22.6 nM). Compounds of a second subset, differing from the first one for the position of the spacer between benzenesulfonamide and triazole, preferentially inhibit VchCAß (KIs in the range 54.8-102.4 nM) and ß-mtCA3 (KIs in the range 28.2-192.5 nM) even more than the clinically used AAZ, used as the standard.

Appraisal of anti-protozoan activity of nitroaromatic benzenesulfonamides inhibiting carbonic anhydrases from Trypanosoma cruzi and Leishmania donovani.

Chagas disease and leishmaniasis are neglected tropical disorders caused by the protozoans Trypanosoma cruzi and Leishmania spp. Carbonic anhydrases (CAs, EC 4.2.1.1) from these protozoans (α-TcCA and ß-LdcCA) have been validated as promising targets for chemotherapic interventions. Many anti-protozoan agents, such as nitroimidazoles, nifurtimox, and benznidazole possess a nitro aromatic group in their structure which is crucial for their activity. As a continuation of our previous work on N-nitrosulfonamides as anti-protozoan agents, we investigated benzenesulfonamides bearing a nitro aromatic moiety against TcCA and LdcCA, observing selective inhibitions over human off-target CAs. Selected derivatives were assessed in vitro in different developmental stages of T. cruzi and Leishmania spp. A lack of significant growth inhibition has been found, which has been connected to the low permeability of this class of derivatives through cell membranes. Further strategies necessarily need to be designed for targeting Chagas disease and leishmaniasis with nitro-containing CA inhibitors.

Activation Studies of the γ-Carbonic Anhydrases from the Antarctic Marine Bacteria Pseudoalteromonas haloplanktis and Colwellia psychrerythraea with Amino Acids and Amines.

The γ-carbonic anhydrases (CAs, EC 4.2.1.1) present in the Antarctic marine bacteria Pseudoalteromonas haloplanktis and Colwellia psychrerythraea, herein referred to as PhaCA and CpsCA, respectively, were investigated for their activation with a panel of 24 amino acids and amines. Both bacteria are considered Antarctic models for the investigation of photosynthetic and metabolic pathways in organisms adapted to live in cold seawater. PhaCA was much more sensitive to activation by these compounds compared to the genetically related enzyme CpsCA. The most effective PhaCA activators were d-Phe, l-/d-DOPA, l-Tyr and 2-pyridyl-methylamine, with the activation constant KA values of 0.72-3.27 µM. d-His, l-Trp, d-Tyr, histamine, dopamine, serotonin anddicarboxylic amino acids were also effective activators of PhaCA, with KA values of 6.48-9.85 µM. CpsCA was activated by d-Phe, d-DOPA, l-Trp, l-/d-Tyr, 4-amino-l-Phe, histamine, 2-pyridyl-methylamine and l-/d-Glu with KA values of 11.2-24.4 µM. The most effective CpsCA activator was l-DOPA (KA of 4.79 µM). Given that modulators of CAs from Antarctic bacteria have not been identified and investigated in detail for their metabolic roles to date, this research sheds some light on these poorly understood processes.

Synthesis of N'-phenyl-N-hydroxyureas and investigation of their inhibitory activities on human carbonic anhydrases.

A series of N'-phenyl-N-hydroxyureas has been prepared by reacting hydroxylamine with aromatic isocyanates. These compounds were investigated as inhibitors of human carbonic anhydrases (hCAs, EC 4.2.1.1), considering four physiologically relevant isoforms, the cytosolic isoforms hCA I and II, and tumor associated, transmembrane isoforms hCA IX and XII. The new compounds reported here did not inhibit the widespread cytosolic isoforms hCA I and II, but they inhibited the tumor associated isoforms with interesting potencies. The most effective inhibitors showed KIs ranging between 72.8 and 78.9 nM against hCA IX and between 6.9 and 7.2 against hCA XII, making them of interest as candidates for antitumor studies.