A Review on Recent Advances in the Application of Nanocatalysts in A3 Coupling Reactions.

A3 coupling is one of the few transition-metal catalyzed carbon-carbon bond forming reactions that have been established as a most direct, efficient and atom-economical synthetic approach to afford propargylamine derivatives using various catalysts. A large number of nanosized heterogeneous catalysts for three-component coupling reactions between an aldehyde, an amine, and a terminal alkyne have been popularly introduced as an A3 coupling in the last decade. The coupling product has found a broad application as a key intermediate for a variety of heterocyclic useful compounds and numerous biologically active molecules such as ß-lactams, conformationally restricted peptides, isosteres, herbicides, fungicides, indolizines, pyrroles, quinolines and therapeutic drug molecules. This review aims to give an overview of the current progress made towards the preparation and application of various nanocatalysts-catalyzed A3 coupling transformations for the synthesis of propargylamines from 2007 to 2017. Several nanocatalysts based on metal and metal oxide nanoparticles (NPs) such as copper, gold, silver, iron, nickel, cobalt and zinc have successfully been employed in A3 coupling reactions. Besides, core-shells NPs, polymers, complexes, graphenes, metal-organic frameworks and ionic liquids have also been used in these reactions. Abundant examples have been given in this area. Different aspects of the reactions, disparate methods of preparation of nanocatalysts, characterization and their reusability have been perused.

Sulfonic acid functionalized cellulose-derived (nano)materials: Synthesis and application.

The preparation/application of heterogeneous (nano)materials from natural resources has currently become increasingly fascinating for researchers. Cellulose is the most abundant renewable polysaccharide on earth. The unique physicochemical, structural, biological, and environmental properties of this natural biopolymer have led to its increased application in many fields. The more desirable features of cellulose-based (nano)materials such as biodegradability, renewability, biocompatibility, cost-effectiveness, simplicity of preparation, environmentally friendly nature, and widespread range of applications have converted them into promising compounds in medicine, catalysis, biofuel cells, and water/wastewater treatment processes. Functionalized cellulose-based (nano)materials containing sulfonic acid groups may prove to be one of the most promising sustainable bio(nano)materials of modern times in the field of cellulose science and (nano)technology owing to their intrinsic features, high crystallinity, high specific surface area, abundance, reactivity, and recyclability. In this review, the developments in the application of sulfonated cellulose-based (nano)materials containing sulfonic acid (-SO3H) groups in catalysis, water purification, biological/biomedical, environmental, and fuel cell applications have been reported. This review provides an overview of the methods used to chemically modify cellulose and/or cellulose derivatives in different forms, including nanocrystals, hydrogels, films/membranes, and (nano)composites/blends by introducing sulfonate groups on the cellulose backbone, focusing on diverse sulfonating agents utilized and substitution regioselectivity, and highlights their potential applications in different industries for the generation of alternative energies and products.

Correction to "Upgraded Valorization of Biowaste: Laser-Assisted Synthesis of Pd/Calcium Lignosulfonate Nanocomposite for Hydrogen Storage and Environmental Remediation".

[This corrects the article DOI: 10.1021/acsomega.9b04149.].

Synthesis of bentonite/Ag nanocomposite by laser ablation in air and its application in remediation.

In this research, a simple, green, and efficient approach is described to produce novel bentonite/Ag nanocomposite wherein the preparation of Ag nanoparticles (Ag NPs) deployed the laser ablation method in air; Ag NPs are deposited on the bentonite via the magnetic stirring method. The structural and morphological characterization of the as-prepared bentonite/Ag nanocomposite (denoted as B/Ag30, 30 min being the laser ablation time) is accomplished using different methods. Additionally, the catalytic assessment of the ensued composite exhibited excellent catalytic reduction/degradation activity for common aqueous pollutants namely methyl orange (MO), congo red (CR) and 4-nitrophenol (4-NP) utilizing NaBH4 as reductant. Furthermore, the recycling tests displayed the high stability/reusability of B/Ag30 nanocomposite for at least 4 runs with retention of catalytic prowess.

Biowaste- and nature-derived (nano)materials: Biosynthesis, stability and environmental applications.

Due to the environmental pollution issues and the supply of drinking/clean water, removal of both inorganic and organic (particularly dyes, nitroarenes, and heavy metals) to non-dangerous products and useful compounds are very important transformations. The deployment of sustainable and eco-friendly nanomaterials with exceptional structural and unique features such as high efficiency and stability/recyclability, high surface/volume ratio, low-cost production routes has become a priority; nonetheless, numerous significant challenges/restrictions still remained unresolved. The immobilization of green synthesized metal nanoparticles (NPs) on the natural materials and biowaste generated templates have been analyzed widely as a greener approach due to their environmentally friendly preparation methods, earth-abundance, cost-effectiveness with low energy consumption, biocompatibility, as well as adjustability in various cases of biomolecules as bioreducing agents. Natural and biowaste materials are widely considered as important sources to fabricate greener and biosynthesized types of metal, metal oxide, and metal sulfide nanomaterials using plant extracts. Integrating green synthesized nanoparticles with various biotemplates offers new practical composites for mitigating environmental challenges. In this review, degradation of dyes, reduction of toxic nitrophenols, absorption of heavy metals, and other hazardous/toxic environmental pollutants from contaminated water bodies using biowaste- and nature-derived nanomaterials are highlighted.

Modified chitosan-zeolite supported Pd nanoparticles: A reusable catalyst for the synthesis of 5-substituted-1H-tetrazoles from aryl halides.

A novel heterogeneous catalyst has been developed using chitosan-zeolite supported Pd nanoparticles (PdNPs@CS-Zeo) and used in an efficient synthesis of 5-substituted-1H-tetrazoles from aryl halides with high yields for relatively short reaction times with an easy work-up procedure. In this method, highly effective and reusable PdNPs@CS-Zeo catalyst was used in the reaction of various aryl iodides/bromides with K4[Fe(CN)6] as a non-toxic cyanide source to catalyze the [2 + 3] cycloaddition of the corresponding aryl nitriles with NaN3 in the sequential one-pot preparation of 5-substituted-1H-tetrazoles. The synthesized PdNPs@CS-Zeo nanocatalyst was characterized using XRD, FTIR, TEM, HRTEM, XPS, Raman, TG-DTG, ICP-OES, BET, and EDS mapping. Additionally, the nanocatalyst could be effectively separated by filtration and reused for multiple times without significant decrease of catalytic activity.

Lignin-derived (nano)materials for environmental pollution remediation: Current challenges and future perspectives.

The supply of affordable drinking and sufficiently clean water for human consumption is one of the world's foremost environmental problems and a large number of scientific research works are addressing this issue Various hazardous/toxic environmental contaminants in water bodies, both inorganic and organic (specifically heavy metals and dyes), have become a serious global problem. Nowadays, extensive efforts have been made to search for novel, cost effective and practical biosorbents derived from biomass resources with special attention to value added, biomass-based renewable materials. Lignin and (nano)material adorned lignin derived entities can proficiently and cost effectively remove organic/inorganic contaminants from aqueous media. As low cost of preparation is crucial for their wide applications in water/wastewater treatment (particularly industrial water), future investigations must be devoted to refining and processing the economic viability of low cost, green lignin-derived (nano)materials. Production of functionalized lignin, lignin supported metal/metal oxide nanocomposites or hydrogels is one of the effective approaches in (nano)technology. This review outlines recent research progresses, trends/challenges and future prospects about lignin-derived (nano)materials and their sustainable applications in wastewater treatment/purification, specifically focusing on adsorption and/or catalytic reduction/(photo)degradation of a variety of pollutants.

Carbon-based nanomaterials for targeted cancer nanotherapy: recent trends and future prospects.

Carbon-based nanomaterials are becoming attractive materials due to their unique structural dimensions and promising mechanical, electrical, thermal, optical and chemical characteristics. Carbon nanotubes, graphene, graphene oxide, carbon and graphene quantum dots have numerous applications in diverse areas, including biosensing, drug/gene delivery, tissue engineering, imaging, regenerative medicine, diagnosis, and cancer therapy. Cancer remains one of the major health problems all over the world, and several therapeutic approaches are focussed on designing targeted anticancer drug delivery nanosystems by applying benign and less hazardous resources with high biocompatibility, ease of functionalization, remarkable targeted therapy issues, and low adverse effects. This review highlights the recent development on these carbon based-nanomaterials in the field of targeted cancer therapy and discusses their possible and promising diagnostic and therapeutic applications for the treatment of cancers.

Carbon-based sustainable nanomaterials for water treatment: State-of-art and future perspectives.

The supply of safe drinking and clean water is becoming increasingly challenging proposition throughout the world. The deployment of environmentally sustainable nanomaterials with unique advantages namely high efficiency and selectivity, earth-abundance, recyclability, low-cost of production processes, and stability, has been a priority although several important challenges and constraints still remained unresolved. Carbon nanomaterials namely activated carbon, multi-walled- and single-walled carbon nanotubes, have been developed and applied as adsorbents for wastewater treatment and purification; graphene and graphene oxide-based nanomaterials as well as carbon and graphene quantum dots-derived nanomaterials have shown significant promise for water and wastewater treatment and purification, especially, for industrial- and pharmaceutical-laden wastes. This review encompasses advanced carbonaceous nanomaterials and methodologies that are deployed for the elimination of contaminants and ionic metals in aqueous media, and as novel nanosorbents for wastewater, drinking and ground water treatment. Additionally, recent trends and challenges pertaining to the sustainable carbon and graphene quantum dots-derived nanomaterials and their appliances for treating and purifying wastewater are highlighted.

Starch, cellulose, pectin, gum, alginate, chitin and chitosan derived (nano)materials for sustainable water treatment: A review.

Natural biopolymers, polymeric organic molecules produced by living organisms and/or renewable resources, are considered greener, sustainable, and eco-friendly materials. Natural polysaccharides comprising cellulose, chitin/chitosan, starch, gum, alginate, and pectin are sustainable materials owing to their outstanding structural features, abundant availability, and nontoxicity, ease of modification, biocompatibility, and promissing potentials. Plentiful polysaccharides have been utilized for making assorted (nano)catalysts in recent years; fabrication of polysaccharides-supported metal/metal oxide (nano)materials is one of the effective strategies in nanotechnology. Water is one of the world's foremost environmental stress concerns. Nanomaterial-adorned polysaccharides-based entities have functioned as novel and more efficient (nano)catalysts or sorbents in eliminating an array of aqueous pollutants and contaminants, including ionic metals and organic/inorganic pollutants from wastewater. This review encompasses recent advancements, trends and challenges for natural biopolymers assembled from renewable resources for exploitation in the production of starch, cellulose, pectin, gum, alginate, chitin and chitosan-derived (nano)materials.

Green-synthesized nanocatalysts and nanomaterials for water treatment: Current challenges and future perspectives.

Numerous hazardous environmental pollutants in water bodies, both organic and inorganic, have become a critical global issue. As greener and bio-synthesized versions of nanoparticles exhibit significant promise for wastewater treatment, this review discusses trends and future prospects exploiting the sustainable applications of green-synthesized nanocatalysts and nanomaterials for the removal of contaminants and metal ions from aqueous solutions. Recent trends and challenges about these nanocatalysts and nanomaterials and their potential applications in wastewater treatment and water purification are highlighted including toxicity and biosafety issues. This review delineates the pros and cons and critical issues pertaining to the deployment of these nanomaterials endowed with their superior surface area, mechanical properties, significant chemical reactivity, and cost-effectiveness with low energy consumption, for removal of hazardous materials and contaminants from water; comprehensive coverage of these materials for industrial wastewater remediation, and their recovery is underscored by recent advancements in nanofabrication, encompassing intelligent and smart nanomaterials.

Lignin, lipid, protein, hyaluronic acid, starch, cellulose, gum, pectin, alginate and chitosan-based nanomaterials for cancer nanotherapy: Challenges and opportunities.

Although nanotechnology-driven drug delivery systems are relatively new, they are rapidly evolving since the nanomaterials are deployed as effective means of diagnosis and delivery of assorted therapeutic agents to targeted intracellular sites in a controlled release manner. Nanomedicine and nanoparticulate drug delivery systems are rapidly developing as they play crucial roles in the development of therapeutic strategies for various types of cancer and malignancy. Nevertheless, high costs, associated toxicity and production of complexities are some of the critical barriers for their applications. Green nanomedicines have continually been improved as one of the viable approaches towards tumor drug delivery, thus making a notable impact on which considerably affect cancer treatment. In this regard, the utilization of natural and renewable feedstocks as a starting point for the fabrication of nanosystems can considerably contribute to the development of green nanomedicines. Nanostructures and biopolymers derived from natural and biorenewable resources such as proteins, lipids, lignin, hyaluronic acid, starch, cellulose, gum, pectin, alginate, and chitosan play vital roles in the development of cancer nanotherapy, imaging and management. This review uncovers recent investigations on diverse nanoarchitectures fabricated from natural and renewable feedstocks for the controlled/sustained and targeted drug/gene delivery systems against cancers including an outlook on some of the scientific challenges and opportunities in this field. Various important natural biopolymers and nanomaterials for cancer nanotherapy are covered and the scientific challenges and opportunities in this field are reviewed.

Pd-based nanoparticles: Plant-assisted biosynthesis, characterization, mechanism, stability, catalytic and antimicrobial activities.

Among various metal nanoparticles, palladium nanoparticles (Pd NPs) are one of the most important and fascinating nanomaterials. An important concern about the preparation of Pd NPs is the formation of toxic by-products, dangerous wastes and harmful pollutants. The best solution to exclude and/or minimize these toxic substances is plant mediated biosynthesis of Pd NPs. Biogenic Pd-based NPs from plant extracts have been identified as valuable nanocatalysts in various catalytic reactions because of their excellent activities and selectivity. They have captured the attention of researchers owing to their economical, sustainable, green and eco-friendly nature. This review attempts to cover the recent progresses in the fabrication, characterization and broad applications of biogenic Pd NPs in environmental and catalytic systems. In addition, the stability of biosynthesized Pd NPs and mechanism of their formation are investigated.

Trimetallic Nanoparticles: Greener Synthesis and Their Applications.

Nanoparticles (NPs) and multifunctional nano-sized materials have significant applications in diverse fields, namely catalysis, sensors, optics, solar energy conversion, cancer therapy/diagnosis, and bioimaging. Trimetallic NPs have found unique catalytic, active food packaging, biomedical, antimicrobial, and sensing applications; they preserve an ever-superior level of catalytic activities and selectivity compared to monometallic and bimetallic nanomaterials. Due to these important applications, a variety of preparation routes, including hydrothermal, microemulsion, selective catalytic reduction, co-precipitation, and microwave-assisted methodologies have been reported for the syntheses of these nanomaterials. As the fabrication of nanomaterials using physicochemical methods often have hazardous and toxic impacts on the environment, there is a vital need to design innovative and well-organized eco-friendly, sustainable, and greener synthetic protocols for their assembly, by applying safer, renewable, and inexpensive materials. In this review, noteworthy recent advancements relating to the applications of trimetallic NPs and nanocomposites comprising these NPs are underscored as well as their eco-friendly and sustainable synthetic preparative options.

Nanomaterials and Nanotechnology-Associated Innovations against Viral Infections with a Focus on Coronaviruses.

Viral infections have recently emerged not only as a health threat to people but rapidly became the cause of universal fatality on a large scale. Nanomaterials comprising functionalized nanoparticles (NPs) and quantum dots and nanotechnology-associated innovative detection methods, vaccine design, and nanodrug production have shown immense promise for interfacing with pathogenic viruses and restricting their entrance into cells. These viruses have been scrutinized using rapid diagnostic detection and therapeutic interventional options against the caused infections including vaccine development for prevention and control. Coronaviruses, namely SARS-CoV, MERS-CoV, and SARS-CoV-2, have endangered human life, and the COVID-19 (caused by SARS-CoV-2) outbreak has become a perilous challenge to public health globally with huge accompanying morbidity rates. Thus, it is imperative to expedite the drug and vaccine development efforts that would help mitigate this pandemic. In this regard, smart and innovative nano-based technologies and approaches encompassing applications of green nanomedicine, bio-inspired methods, multifunctional bioengineered nanomaterials, and biomimetic drug delivery systems/carriers can help resolve the critical issues regarding detection, prevention, and treatment of viral infections. This perspective review expounds recent nanoscience advancements for the detection and treatment of viral infections with focus on coronaviruses and encompasses nano-based formulations and delivery platforms, nanovaccines, and promising methods for clinical diagnosis, especially regarding SARS-CoV-2.

Upgraded Valorization of Biowaste: Laser-Assisted Synthesis of Pd/Calcium Lignosulfonate Nanocomposite for Hydrogen Storage and Environmental Remediation.

Laser ablation in liquid (LAL), one of the promising pathways to produce nanoparticles, is used herein for the modification of the abundant biowaste, calcium lignosulfonate (CLS), adorning it with palladium nanoparticles (Pd NPs). The ensuing Pd/CLS nanocomposite, fabricated via a simple stirring method, is deployed for hydrogen storage and environmental cleanup studies; a hydrogen storage capacity of about 5.8 C g-1 confirmed that Pd NPs serve as active sites for the adsorption of hydrogen. Additionally, the novel, sustainable, and reusable nanocomposite also exhibits superior catalytic activity toward the reduction of hexavalent chromium [Cr(VI)], 4-nitrophenol (4-NP), and methylene blue (MB) in an aqueous solution in a short time; the synthesized nanocatalyst could be reused for at least eight successive runs.

Laser-assisted preparation of Pd nanoparticles on carbon cloth for the degradation of environmental pollutants in aqueous medium.

Laser ablation in liquid (LAL), one of the attractive methods for fabrication of nanoparticles, was used for the modification of carbon cloth (CC) by deposition of palladium nanoparticles (Pd NPs); a simple stirring method was deployed to deposit Pd NPs on the CC surface. Characterization techniques viz X-ray diffraction (XRD), Fourier transform infrared (FT-IR), scanning electron microscope (SEM), energy-dispersive X-ray spectrometry (EDS) and inductively coupled plasma atomic emission spectroscopy (ICP-AES) were applied to study the surface of the ensuing samples which confirmed that LAL technique managed to fabricate and deposit the Pd NPs on the surface of CC. In addition, the catalytic prowess of the carbon cloth-Pd NPs (CC/Pd NPs) was investigated in the NaBH4- or HCOOH-assisted reduction of assorted environmental pollutants in aqueous medium namely hexavalent chromium [Cr(VI)], 4-nitrophenol (4-NP), congo red (CR) and methylene blue (MB). The CC/Pd NPs system has advantages such as high stability/sustainability, high catalytic performance and easy reusability.

A catalyst-free and expeditious general synthesis of N-benzyl-N-arylcyanamides under ultrasound irradiation at room temperature.

A hitherto unknown, novel and direct approach to the efficient synthesis of N-benzyl-N-arylcyanamides is described via N-benzylation of a variety of arylcyanamides with benzyl bromide under ultrasound irradiation condition at room temperature; assorted N-benzyl-N-arylcyanamides are expeditiously accessible in excellent yields. The salient features of this approach include a very simple and clean reaction, higher yields obtained under mild conditions in an environmentally benign protocol. Additionally, easy isolation of the desired products without any tedious purification renders the present protocol a suitable alternative to desirable organic disubstituted cyanamides.

Synthesis of 1-Substituted 1H-1,2,3,4-Tetrazoles Using Biosynthesized Ag/Sodium Borosilicate Nanocomposite.

An expedient solvent-free methodology has been developed to produce 1-substituted 1H-1,2,3,4-tetrazoles using sodium borosilicate glass-supported silver nanoparticles (Ag NPs) as a novel heterogeneous catalyst. A cost-efficient, facile, and greener method was deployed for the creation of Ag/sodium borosilicate nanocomposite (ASBN) catalyst by using Aleurites moluccana leaf extract as a stabilizing and reducing agent. The ASBN catalyst was identified using the latest microscopic and spectroscopic techniques such as FT-IR, TEM, FESEM, XRD, EDS, and elemental mapping. The deployment of this new catalyst enables the preparation of assorted 1-substituted tetrazoles in good to high yields via an easy work-up procedure in a relatively short reaction time under environmentally friendly conditions without using harmful and toxic reducing agents. The ASBN catalyst can be recycled and reused multiple times without meaningful loss of activity. To extend the application of the ASBN, the performance of the quantitative structure-activity relationships model was investigated for protein binding and toxicity hazard considerations.

Green synthesis of Ag/Fe(3)O(4) nanocomposite using Euphorbia peplus Linn leaf extract and evaluation of its catalytic activity.

In this work, the Ag/Fe3O4 nanocomposite was prepared by Euphorbia peplus Linn (L.) leaf extract as a suitable reducing source and stabilizing agent. The green synthesized nanocomposite was characterized using X-ray diffraction analysis (XRD), field emission scanning electron microscope (FESEM), transmission electron microscopy (TEM) images, energy-dispersive X-ray spectroscopy (EDS) and FT-IR spectroscopy. TEM analysis of Ag/Fe3O4 nanocomposite showed the spherical shape nanoparticles (NPs) with an average size of 5-10nm. The Ag/Fe3O4 nanocomposite then was used as a magnetically recoverable catalyst for the [2+3] cycloaddition of arylcyanamides and sodium azide in high yields and short reaction times without formation of hydrazoic acid (HN3). Also it can be easily recovered via applying of external magnetic field and reused several times without significant loss of activity.