Medicinal bismuth: Bismuth-organic frameworks as pharmaceutically privileged compounds

Historically organometallic compounds have been used to cure certain diseases with limited applications. Although bismuth belongs to the category of heavy metals, many of its derivatives have found applications in modern drug discovery research, mainly because of its low toxicity and higher bioavailability. Being an eco-friendly mild Lewis acid, compounds having bismuth as a central atom are capable of binding several proteins in humans and other species. Bismuth complexes demonstrated antibacterial potential in syphilis, diarrhea, gastritis, and colitis. Apart from antibacterial activities, bismuth compounds exhibited anticancer, antileishmanial, and some extent of antifungal and other medicinal properties. This article discusses major synthetic methods and pharmacological potentials of bismuth complexes exhibiting in vitro activity to significant clinical performance in a systematic and timely manner.Copyright © 2022 Elsevier Ltd

Anticancer Podophyllotoxin Recovery from Juniper Leaves at Atmospheric and High Pressure Using Eco-Friendly Solvents.

Podophyllotoxin (PPT) is a precursor for the synthesis of drugs against cancer and other diseases. The present sources of PPT (Sinopodophyllum hexandrum and Podophyllum peltatum) are endangered species, with PPT production highly dependent on their growing conditions. In connection with the identification of new sources of PPT, the present study aimed to recover PPT from Juniperus virginiana leaves via atmospheric or high pressure extraction methods with a focus on using eco-friendly solvents. PPT quantification was determined by UHPLC/HRMS/MS. A thorough study of conventional extraction was carried out to reveal the optimal conditions (solvent ethyl acetate at room temperature and a duration of 1 h) for maximizing the PPT recovery (about 30 mg/g of dry extract and 3 mg/g of dry initial plant material). Peleg's equation was applied for process kinetics modeling. The best PPT content in the final dry extract (42-45 mg/g of dry extract) was obtained by high pressure methods under supercritical (scCO2 with ethanol or ethyl acetate, 30 MPa, 50 °C and 100 min) or accelerated solvent extraction conditions (solvent ethyl acetate, 10.35 MPa, 20 °C and 3 cycles for 15 min). Seasonal stability and storage stability of the raw material were also determined. The present results have potential applications in the pharmacy for the delivery of PPT from juniper leaves.

Photocatalytic mineralization of pharmaceutical contaminants in water by heterogeneous photocatalysis in the presence of LED-irradiation: A green and sustainable approach

There is an urgent need to mineralize organic pollutants such as antibiotics and other toxic organic materials discharged by various pharmaceutical and chemical industries into freshwater. These organic pollutants affect the aquatic ecosystem and human health due to bioaccumulation in the food chains and food webs. Heterogeneous photocatalysis is an advanced oxidation-based green technique by which these pharmaceutics can be degraded in the wastewater by using nontoxic and eco-friendly catalysts in the presence of light-emitting diodes (LEDs) as a source of irradiation. The main aim of the chapter is to disseminate information regarding the degradation of antibiotics and other pharmaceutics by green, non-toxic, and effective catalysts via economically viable techniques. Antibiotics are oxidized by hydroxyl radicals and superoxides generated during the irradiation of light on the surface of the catalyst. In this chapter, the authors discuss the most commonly prescribed antibiotics in the COVID-19 pandemic and how these antibiotics become environmental contaminants. They have also proposed the mechanism of degradation of these antibiotics in the presence of LED irradiation to attain a green and sustainable environment. © 2023 Nova Science Publishers, Inc. All rights reserved.

Green methodologies for the synthesis of 2-aminothiophene.

Pollution and the rising energy demand have prompted the design of new synthetic reactions that meet the principles of green chemistry. In particular, alternative synthesis of 2-aminothiophene have recently focused interest because 2-aminothiophene is a unique 5-membered S-heterocycle and a pharmacophore providing antiprotozoal, antiproliferative, antiviral, antibacterial or antifungal properties. Here, we review new synthetic routes to 2-aminothiophenes, including multicomponent reactions, homogeneously- or heterogeneously-catalyzed reactions, with focus on green pathways.

Green fitted second derivative synchronous spectrofluorometric method for simultaneous determination of remdesivir and apixaban at Nano gram scale in the spiked human plasma.

Remdesivir and apixaban have been included in the treatment guidelines of several countries for severe COVID-19 infections. To date, no analytical method has been developed for the determination of remdesivir and apixaban in plasma matrix. The main objective of this work was to develop a highly sensitive, green-adapted spectrofluorometric method for the determination of remdesivir and apixaban at the Nanoscale. Remdesivir and apixaban showed overlapping fluorescence emission spectra at 403 nm and 456 nm when excited at 246 nm and 285 nm, respectively. This overlap was resolved in two steps. The first step was synchronous fluorescence scanning of remdesivir and apixaban, and the second step was manipulation of the second-order derivative for the obtained spectra. These steps allowed complete resolution of the overlapping fluorescence spectra and selective determination of remdesivir and apixaban at 410 and 469 nm, respectively. The variables affecting the synchronous scanning of the aforementioned drugs were optimized in terms of sensitivity parameters and principles of green analytical chemistry. The described method allowed sensitive determination of remdesivir and apixaban over the concentration range of 5-200 ng/mL and 50-3000 ng/mL, respectively. The described method was validated and successfully applied for the simultaneous determination of the mentioned drugs in pure form and in spiked human plasma.

Role and the importance of green approach in biosynthesis of nanopropolis and effectiveness of propolis in the treatment of COVID-19 pandemic

The most fascinating product of honeybee is propolis. It has an immense role in dentistry, dermatology, and otorhinolaryngology. The increased popularity of propolis as an important remedy is due to its constituents, which have anti-inflammatory, immunomodulatory, antihepatotoxic, anti-cancerous, antifungal, antioxidant, antidiabetic, and antiviral activities. The diverse biological and pharmacological activities of propolis have piqued the interest of many scientists. Many techniques like gas chromatography-mass spectrometry, chromatography, and spectroscopy are being used to identify different propolis constituents. Flavonoids, phenolic acids, and their esters are the most pharmacologically active molecules of propolis and are known to disrupt the replication machinery of the virus corroborating the anti-coronavirus activity of propolis. The main aim of this article is to provide an insight of the increasing theragnostic uses of propolis and its nanoparticles, including their chemical analysis, diverse biological activities, and the necessity for chemical standardization. In this review, we have focused at the promising effects of propolis, its optimization, and its liposomal formulation as a therapeutic intervention for COVID-19 and its accompanying comorbidities. © 2023 the author(s), published by De Gruyter.

Green and efficient one-pot three-component synthesis of novel drug-like furo[2,3-d]pyrimidines as potential active site inhibitors and putative allosteric hotspots modulators of both SARS-CoV-2 MPro and PLPro.

In this paper, an environmentally benign, convenient, and efficient one-pot three-component reaction has been developed for the regioselective synthesis of novel 5-aroyl(or heteroaroyl)-6-(alkylamino)-1,3-dimethylfuro[2,3-d]pyrimidine-2,4(1H,3H)-diones (4a‒n) through the sequential condensation of aryl(or heteroaryl)glyoxal monohydrates (1a‒g), 1,3-dimethylbarbituric acid (2), and alkyl(viz. cyclohexyl or tert-butyl)isocyanides (3a or 3b) catalyzed by ultra-low loading ZrOCl2•8H2O (just 2 mol%) in water at 50 ˚C. After synthesis and characterization of the mentioned furo[2,3-d]pyrimidines (4a‒n), their multi-targeting inhibitory properties were investigated against the active site and putative allosteric hotspots of both SARS-CoV-2 main protease (MPro) and papain-like protease (PLPro) based on molecular docking studies and compare the attained results with various medicinal compounds which approximately in three past years were used, introduced, and or repurposed to fight against COVID-19. Furthermore, drug-likeness properties of the mentioned small heterocyclic frameworks (4a‒n) have been explored using in silico ADMET analyses. Interestingly, the molecular docking studies and ADMET-related data revealed that the novel series of furo[2,3-d]pyrimidines (4a‒n), especially 5-(3,4-methylendioxybenzoyl)-6-(cyclohexylamino)-1,3-dimethylfuro[2,3-d]pyrimidine-2,4(1H,3H)-dione (4g) as hit one is potential COVID-19 drug candidate, can subject to further in vitro and in vivo studies. It is worthwhile to note that the protein-ligand-type molecular docking studies on the human body temperature-dependent MPro protein that surprisingly contains zincII (ZnII) ion between His41/Cys145 catalytic dyad in the active site, which undoubtedly can make new plans for designing novel SARS-CoV-2 MPro inhibitors, is performed for the first time in this paper, to the best of our knowledge.

Antibiotics sustainability: another issue in the fight against antimicrobial resistance.

The spread of antimicrobial resistance (AMR) is still a major threat to global health that is likely to worsen also as a consequence of the COVID-19 pandemic. For this reason, there is an urgent need to develop new compounds and novel alternative treatments. Furthermore, the new lines of action must consider the issue of the antibiotic's sustainability. Within this editorial, we have highlighted the main points on which actions in this perspective are possible.

Valorization of discarded face mask for bioactive compound synthesis and photodegradation of dye.

To keep COVID-19 at bay, most countries have mandated the use of face masks in public places and imposed heavy penalties for those who fail to do so. This has inadvertently created a huge demand for disposable face masks and worsened the problem of littering, where a large number of used masks are constantly discarded into the environment. As such, an efficient and innovative waste management strategy for the discarded face mask is urgently needed. This study presents the transformation of discarded face mask into catalyst termed 'mask waste ash catalyst (MWAC)' to synthesise bisindolylmethanes (BIMs), alkaloids that possess antibacterial, antioxidant and antiviral properties. Using commercially available aldehydes and indole, an excellent yield of reaction (62-94%) was achieved using the MWAC in the presence of water as the sole solvent. On the other hand, the FT-IR spectrum of MWAC showed the absorption bands at 2337 cm-1, 1415 cm-1 and 871 cm-1, which correspond to the signals of calcium oxide. It is then proposed that the calcium oxides mainly present in MWAC can protonate oxygen atoms in the carbonyl molecule of the aldehyde group, thus facilitating the nucleophile attack by indole which consequently improved the product yield. Moreover, the MWAC is also observed to facilitate the photodegradation of methylene blue with an efficiency of up to 94.55%. Our results showed the potential applications of the MWAC derived from discarded face masks as a sustainable catalyst for bioactive compound synthesis and photodegradation of dye compounds.

One-Pot Consecutive Reductive Amination Synthesis of Pharmaceuticals: From Biobased Glycolaldehyde to Hydroxychloroquine

Reductive amination plays a paramount role in the synthesis of amines. It is often proposed as a more ecofriendly synthesis process than the traditional SN2-type reactions of amines as it avoids toxic alkylation reagents such as alkyl halides. This work demonstrates the versatility of the reductive amination reaction via the synthesis of hydroxychloroquine (HCQ), one of the most renowned pharmaceuticals during this coronavirus pandemic. The novel green synthesis strategy is based on three consecutive reductive amination reactions conducted in a one-pot system, avoiding intermediary purification steps. Furthermore, a biobased C2 platform molecule, glycolaldehyde, was selected as a starting reagent. The newly developed reductive amination pathway was appraised using the CHEM21 Green Metric toolkit and compared with the commercially operating method. © 2022 American Chemical Society.

Estimation and development of some biophysical characteristics of the drug Favipiravir used in the treatment of corona-virus using green chemistry technology

This study included the preparation and identification of copper oxide nanoparticles (CuNPs) prepared from eucalyptus leaf extract using modern and advanced detection and analysis devices: XRD, AFM, SEM, UV-Vis, and TEM. The results of the tests indicated that the prepared particles are spherical and rod-shaped, with average diameters ranging from 32.55-37.94 nm, and the results showed that the copper oxide nanoparticles were within the nano-scale, and the wavelength of the drug is (322) nanometers. The factors affecting the loading of the drug (Favipiravir) at a concentration of (40 µg/mL) on the surface of activated charcoal prepared from eucalyptus leaves were studied, as well with a weight of 0.1 g and in the presence of copper oxide nanoparticles with different concentrations. It was found that the equilibrium time is 25 minutes, and the thermodynamic functions were calculated at different temperatures. The results illustrated that the loading process by using exothermic adsorption (physical adsorption), is less random process and spontaneously. The possibility of using the loaded substance (Favipiravir:CuNPs) to inhibit microorganisms such as viruses, bacteria, and fungi was studied, and by the presence of the surface active substance sodium dodecyl sulphate SDS, it was found that it has the ability to inhibit by 100%, as a result of the merging of the tail of the superficial active substances with the fatty membrane of the virus, the other microorganisms, its dismantling, and encapsulation of its parts. The vaccines and therapeutic drugs developed on the basis of nano-medicine, which are currently undergoing clinical trials, have the potential to become innovative alternatives to defeat COVID-19 in the future. Copyright © 2022 by SPC (Sami Publishing Company).

Functionalization of Porphyrins Using Metal-Catalyzed C–H Activation

The review is devoted to the C–H functionalization of porphyrins. Porphyrins exhibit the properties of organic semiconductors, light energy converters, chemical and electrochemical catalysts, and photocatalysts. The review describes the iridium- and palladium-catalyzed direct functionalization of porphyrins, with more attention given to the results obtained in our laboratory. The development and improvement of synthetic methods that do not require preliminary modification of the substrate with various functional groups are extremely important for the preparation of new organic materials based on porphyrins. This makes it possible to simplify the synthetic procedure, to make the synthesis more economical, environmentally safe, and simple to perform.

The “End Life” of the Grape Pomace Waste Become the New Beginning: The Development of a Virtuous Cycle for the Green Synthesis of Gold Nanoparticles and Removal of Emerging Contaminants from Water

During the last decades, the demand for processes developed according to the Circular Economy Principles has increased, searching for an alternative life for wastes. For this purpose, a one-pot green approach is exploited during this work to synthesize gold nanoparticles (AuNPs) by using grape pomace waste from Vitis vinifera. A raw aqueous extract of grape seeds, skin, and stems is used for AuNPs synthesis. UV-Vis, XPS, SEM, and ATR-FTIR spectroscopies demonstrate the main role of the extract’s polyphenolic components in stabilizing nanoparticles. XRD, DLS, and Zeta Potential analyses were used to characterize AuNPs. Moreover, the ionic strength, pH, and temperature role was investigated through the Surface Plasmon Resonance (SPR) band observation to assess AuNPs’ stability and photostability. For foreseeing the as-synthesized AuNPs’ potential use in cosmetic and biomedical fields as multifunctional platforms, their antioxidant, and skin-lightening properties were tested, together with their sunscreen ability. A preliminary in-vitro evaluation is reported about the AuNPs’ cytoprotective effects against H2O2 oxidative stress-induced in normal human dermal fibroblasts. Briefly, the possibility of reusing the grape pomace waste after the AuNPs synthesis as an adsorbent for the efficient removal of emergent contaminants is preliminarily discussed in the paper, further valorizing the use of waste according to a bio circular approach.

Synthesis of antiviral drugs by using carbon-carbon and carbon-heteroatom bond formation under greener conditions

Antiviral medications are a branch of medicines notably used to treat that cause many significant diseases in humans and animals. This monograph mainly focuses on recent developments and synthesis of antiviral drugs using carbon-carbon and carbon-hetero bond cross-coupling chemistry. Viral infections exact several severe human diseases, accounting for remarkably high mortality rates. In this sense, academia and the pharmaceutical industry continuously search for novel compounds with better antiviral activity. The researchers face the challenge of developing greener and economical ways to synthesize these compounds and make significant progress.

Is the Plastic Pandemic a Greater Threat to Humankind than COVID-19?

The advent of the COVID-19 pandemic has initiated a radical attention shift of society toward the severe consequences it has had over human health, shadowing a symmetrically, if not more, important issue of the rapid intensification in the amount of plastic waste that has been generated over the due course of time. Such a growth in the plastic footprint across the globe has led to a carbon positive environment with an increased amount of greenhouse gases (GHGs) released due to the processing of the waste plastic. We aim to address and provide our perception to this pressing challenge that can be decoded via the advancement of upcycling technologies, utilized and augmented worldwide. With the establishment of such sustainable policies and strategies, the global plastic footprint can be systematically mitigated, accelerating the world into economic circularity and environmental sustainability.

"Green Is the Color": An Update on Ecofriendly Aspects of Organoselenium Chemistry.

Organoselenium compounds have been successfully applied in biological, medicinal and material sciences, as well as a powerful tool for modern organic synthesis, attracting the attention of the scientific community. This great success is mainly due to the breaking of paradigm demonstrated by innumerous works, that the selenium compounds were toxic and would have a potential impact on the environment. In this update review, we highlight the relevance of these compounds in several fields of research as well as the possibility to synthesize them through more environmentally sustainable methodologies, involving catalytic processes, flow chemistry, electrosynthesis, as well as by the use of alternative energy sources, including mechanochemical, photochemistry, sonochemical and microwave irradiation.

Silver and Gold Nanoparticles for Antimicrobial Purposes against Multi-Drug Resistance Bacteria.

Several pieces of research have been done on transition metal nanoparticles and their nanocomplexes as research on their physical and chemical properties and their relationship to biological features are of great importance. Among all their biological properties, the antibacterial and antimicrobial are especially important due to their high use for human needs. In this article, we will discuss the different synthesis and modification methods of silver (Ag) and gold (Au) nanoparticles and their physicochemical properties. We will also review some state-of-art studies and find the best relationship between the nanoparticles' physicochemical properties and potential antimicrobial activity. The possible antimicrobial mechanism of these types of nanoparticles will be discussed in-depth as well.

Development of Mining Assets in the Mining Industry

In practice, the industry and the business sector have felt the impact of the coronavirus that has spread around the world. Today it is not known when the system will recover, but it is already quite clear that the post-covid reality will require radically new approaches to the organization of mining operations. Usually, the conservative mining industry in Russia has felt the influence of new trends set by the pandemic, such as, for example, the transition of employees to remote work, which has spurred an accelerated transition to automated work;a change in the distribution chain, are inseparable from the closure of borders, the acquisition of new skills from staff, and others. This article focuses on the development of mining assets in the mining industry. The article concretizes the essence of geometry. Appropriate solutions for end-to-end optimization of the “mine-factory” system are outlined due to a deep understanding of the characteristics of the ore and the introduction of digital tools. The most popular innovations necessary for implementation into the modern mining process have been identified, ranked according to the categories “Production materials, technologies and equipment”, “Automation and digitalization”, “Field development”, “Technologies of deep processing of raw materials: green chemistry”, “Technologies of deep processing “processing of raw materials: green metallurgy”. The production assets of the Polar Division are analyzed using the example of PJSC Mining and Metallurgical Company Norilsk Nickel. As a project initiative to improve the efficiency of ore mining within the mine field, the reconstruction of a skip ventilation shaft from a cage to a skip-cage is being created. A variant of solving the geomechanical problems of the company is being considered.

Green by Design: Convergent Synthesis, Computational Analyses, and Activity Evaluation of New FXa Inhibitors Bearing Peptide Triazole Linking Units.

Green chemistry implementation has led to promising results in waste reduction in the pharmaceutical industry. However, the early sustainable development of pharmaceutically active compounds and ingredients remains a considerable challenge. Herein, we wish to report a green synthesis of new pharmaceutically active peptide triazoles as potent factor Xa inhibitors, an important drug target associated with the treatment of diverse cardiovascular diseases. The new inhibitors were synthesized in three steps, featuring cycloaddition reactions (high atom economy), microwave-assisted organic synthesis (energy efficiency), and copper nanoparticle catalysis, thus featuring Earth-abundant metals. The molecules obtained showed FXa inhibition, with IC50-values as low as 17.2 µM and no associated cytotoxicity in HEK293 and HeLa cells. These results showcase the environmental potential and chemical implications of the applied methodologies for the development of new molecules with pharmacological potential.

Application of Ionic Liquids for the Recycling and Recovery of Technologically Critical and Valuable Metals

Population growth has led to an increased demand for raw minerals and energy resources;however, their supply cannot easily be provided in the same proportions. Modern technologies contain materials that are becoming more finely intermixed because of the broadening palette of elements used, and this outcome creates certain limitations for recycling. The recovery and separation of individual elements, critical materials and valuable metals from complex systems requires complex energy-consuming solutions with many hazardous chemicals used. Significant pressure is brought to bear on the improvement of separation and recycling approaches by the need to balance sustainability, efficiency, and environmental impacts. Due to the increase in environmental consciousness in chemical research and industry, the challenge for a sustainable environment calls for clean procedures that avoid the use of harmful organic solvents. Ionic liquids, also known as molten salts and future solvents, are endowed with unique features that have already had a promising impact on cutting-edge science and technologies. This review aims to address the current challenges associated with the energy-efficient design, recovery, recycling, and separation of valuable metals employing ionic liquids.