Starch-based hydrogels for environmental applications: A review.

Water sources have become extremely scarce and contaminated by organic and inorganic industrial and agricultural pollutants as well as household wastes. Poisoning water resources by dyes and metals is a problem because contaminated water can leak into subsurface and surface sources, causing serious contamination and health problems. Therefore, developing wastewater treatment technologies is valuable. Today, hydrogels have attracted considerable attention owing to their broad applications. Hydrogels are polymeric network compositions with significant water-imbibing capacity. Hydrogels have potential applications in diverse fields such as biomedical, personal care products, pharmaceuticals, cosmetics, and biosensors. They can be prepared by using natural (biopolymers) and synthetic polymers. Synthetic polymer-based hydrogels obtained from petrochemicals are not environmentally benign; thus, abundant plant-based polysaccharides are found as more suitable compounds for making biodegradable hydrogels. Polysaccharides with many advantages such as non-toxicity, biodegradability, availability, inexpensiveness, etc. are widely employed for the preparation of environmentally friendly hydrogels. Polysaccharides-based hydrogels containing chitin, chitosan, gum, starch (St), etc. are employed to remove pollutants, metals, and dyes. Among these, St has attracted a lot of attention. St can be mixed with other compounds to make hydrogels, which remove dyes and metal ions to variable degrees of efficiency. Although St has numerous advantages, it suffers from drawbacks such as low stability, low water solubility, and fast degradability in water which limit its application as an environmental adsorbent. As an effective way to overcome these weaknesses, various modification approaches to form starch-based hydrogels (SBHs) employing different compounds have been reported. The preparation methods and applications of SBH adsorbents in organic dyes, hazardous materials, and toxic ions elimination from water resources have been comprehensively discussed in this review.

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.

Fermentation of Rubus dolichocarpus juice using Lactobacillus gasseri and Lacticaseibacillus casei and protecting phenolic compounds by Stevia extract during cold storage.

This study aimed to investigate the biological activities of Lactobacillus gasseri SM 05 (L. gasseri) and Lacticaseibacillus casei subsp. casei PTCC 1608 (L. casei) in the black raspberry (Rubus dolichocarpus) juice (BRJ) environment, and also the anti-adhesion activity against Salmonella typhimurium (S. typhimurium) in fermented black raspberry juice (FBRJ). Results showed significant anti-adhesion activity in Caco-2 epithelial cells. In the anti-adhesion process, lactic acid bacteria (LAB) improve intestinal health by preventing the adhesion of pathogens. Adding LAB to BRJ produces metabolites with bacteriocin properties. Major findings of this research include improved intestinal health, improved antidiabetic properties, inhibition of degradation of amino acids, and increase in the nutritional value of foods that have been subjected to heat processing by preventing Maillard inhibition, and inhibition of oxidation of foodstuff by increased antioxidant activity of BRJ. Both species of Lactobacillus effectively controlled the growth of S. typhimurium during BRJ fermentation. Moreover, in all tests, as well as Maillard's and α-amylase inhibition, L. gasseri was more effective than L. casei. The phenolic and flavonoid compounds increased significantly after fermentation by both LAB (p < 0.05). Adding Stevia extract to FBRJ and performing the HHP process showed convenient protection of phenolic compounds compared to heat processing.

Evaluation of the anti-inflammatory activity of fisetin-loaded nanoparticles in an in vitro model of osteoarthritis.

Cartilage lesions, especially osteoarthritis (OA), are a common health problem, causing pain and disability in various age groups, principally in older adults and athletes. One of the main challenges to be considered in cartilage tissue repair is the regeneration of cartilage tissue in an active inflammatory environment. Fisetin has various biological effects including anti-inflammatory, antioxidant, apoptotic, and antiproliferative activities. The only disadvantages of fisetin in the pharmaceutical field are its instability and low solubility in aqueous media. This study is aimed at preparing chitosan (CS)-based nanoparticles to yield fisetin with improved bioavailability features. Then, the effect of fisetin-loaded nanoparticles (FNPs) on inflammatory responses in interleukin-1ß (IL-1ß) pretreated human chondrocytes has also been investigated. FNPs presented an average size of 363.1 ± 17.2 nm and a zeta potential of + 17.7 ± 0.1 mV with encapsulation efficiency (EE) and loading capacity (LC) of 78.79 ± 7.7% and 37.46 ± 6.6%, respectively. The viability of human chondrocytes was not affected by blank nanoparticles (BNPs) up to a concentration of 2000 µg/mL. In addition, the hemolysis results clearly showed that FNPs did not damage the red blood cells (RBCs) and had good hemocompatibility within the range investigated. FNPs, similar to fisetin, were able to inhibit the inflammatory responses induced by IL-1ß such as the expression of interleukin-6 (IL-6) and tumor necrosis factor-α (TNF-α) while increasing the production of an anti-inflammatory cytokine such as interleukin-10 (IL-10). Overall, the in vitro evaluation results of the anti-inflammatory activity showed that FNPs can serve as delivery systems to transfer fisetin to treat inflammation in OA.

Synthesis of palladium nanoparticles stabilized on Schiff base-modified ZnO particles as a nanoscale catalyst for the phosphine-free Heck coupling reaction and 4-nitrophenol reduction.

Recently, the development of heterogeneous nanocatalytic systems using solid supports has been gaining importance due to some advantages such as easy handling, high thermal stability, high efficiency, reusability, and so on. Therefore, the design of catalyst supports for the preparation of stable heterogeneous catalytic systems is of great importance. In this work, Schiff base-modified ZnO particles have been developed (ZnO-Scb) as a novel support. A heterogeneous nanocatalyst system has then been prepared by immobilizing palladium nanoparticles (Pd NPs) on the ZnO-Scb surface as the support. The resulting palladium nanocatalyst (Pd-ZnO-Scb) structure has been characterized by different analytical techniques (FT-IR, XRD, TEM, FE-SEM, elemental mapping and EDS) and used to catalyze the Heck coupling reactions and 4-nitrophenol (4-NP) reduction. Test results revealed that Pd-ZnO-Scb could effectively couple various aryl halides with styrene in yields of up to 98% in short reaction times. Pd-ZnO-Scb was also efficiently used in the complete 4-NP reduction within 135 s at room temperature. Additionally, it was found that Pd-ZnO-Scb was more effective than other reported catalysts in the Heck coupling reaction. Moreover, the recycling tests indicated that Pd-ZnO-Scb could be easily isolated from the reaction medium and reused in seven consecutive catalytic runs while retaining its nanostructure.

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 a magnetic polystyrene-supported Cu(II)-containing heterocyclic complex as a magnetically separable and reusable catalyst for the preparation of N-sulfonyl-N-aryl tetrazoles.

In this work, a cost-effective, environmentally friendly, and convenient method for synthesizing a novel heterogeneous catalyst via modification of polystyrene using tetrazole-copper magnetic complex [Ps@Tet-Cu(II)@Fe3O4] has been successfully developed. The synthesized complex was analyzed using TEM (transmission electron microscopy), HRTEM (high resolution-transmission electron microscopy), STEM (scanning transmission electron microscopy), FFT (Fast Fourier transform), XRD (X-ray diffraction), FT-IR (Fourier transform-infrared spectroscopy), TG/DTG (Thermogravimetry and differential thermogravimetry), ICP-OES (Inductively coupled plasma-optical emission spectrometry), Vibrating sample magnetometer (VSM), EDS (energy dispersive X-ray spectroscopy), and elemental mapping. N-Sulfonyl-N-aryl tetrazoles were synthesized in high yields from N-sulfonyl-N-aryl cyanamides and sodium azide using Ps@Tet-Cu(II)@Fe3O4 nanocatalyst. The Ps@Tet-Cu(II)@Fe3O4 complex can be recycled and reused easily multiple times using an external magnet without significant loss of catalytic activity.

Nano-sized and microporous palladium catalyst supported on modified chitosan/cigarette butt composite for treatment of environmental contaminants.

This study reports a versatile process for the fabrication of a microporous heterogeneous palladium nanocatalyst on a novel spherical, biodegradable, and chemically/physically resistant catalyst support consisting of chitosan (CS) and cigarette waste-derived activated carbon (CAC). The physicochemical properties of the microporous Pd-CS-CAC nanocatalyst developed were successfully determined by FTIR, XRD, FE-SEM, TEM, BET, and EDS techniques. TEM studies showed that the average particle size of the synthesized Pd NPs was about 30 nm. The catalytic prowess of microporous Pd-CS-CAC was evaluated in the reduction/decolorization of various nitroarenes (2-nitroaniline (2-NA), 4-nitroaniline (4-NA), 4-nitrophenol (4-NP), and 4-nitro-o-phenylenediamine (4-NPD)) and organic dyes (methyl red (MR), methyl orange (MO), methylene blue (MB), congo red (CR), and rhodamine B (RhB)) in an aqueous medium in the presence of NaBH4 as the reducing agent at room temperature. The catalytic activities were studied by UV-Vis absorption spectroscopy of the supernatant at regular time intervals. The short reaction times, mild reaction conditions, high efficiency (100% conversion), easy separation, and excellent chemical stability of the catalyst due to its heterogeneity and reusability are the advantages of this method. The results of the tests showed that reduction/decolorization reactions were successfully carried out within 10-140 s due to the good catalytic ability of Pd-CS-CAC. Moreover, Pd-CS-CAC was reused for 5 consecutive times with no loss of the initial shape, size, and morphology, confirming that it was a sustainable and robust nanocatalyst.

Extraction and purification of α-pinene; a comprehensive review.

Extensive use of α-pinene in cosmetics, and medicine, especially for its antioxidant/antibacterial, and anti-cancer properties, and also as a flavoring agent, has made it a versatile product. α-Pinene (one of the two pinene isomers) is the most abundant terpene in nature. When extracting α-pinene from plants and, to a lesser extent, fruits, given that its purity is essential, purification methods should also be used as described in this study. Also, an attempt has been made to describe the extraction techniques of α-pinene, carried out by conventional and novel methods. Some disadvantages of conventional methods (such as hydrodistillation or solvent extraction) are being time consuming, low capacity per batch and being labor intensive and the requirement of trained operators. Most novel methods, such as supercritical fluid extraction and microwave-assisted extraction, can reduce the extraction time, cost, and energy compared to conventional methods, and, in fact, the extraction and preservation efficiency of α-pinene in these methods is higher than conventional methods. Although the above-mentioned extraction methods are effective, they still require rather long extraction times. In fact, advanced methods such as green and solvent-free ultrasonic-microwave-assisted extraction are much more efficient than microwave-assisted extraction and ultrasound-assisted extraction because the extraction efficiency and separation of α-pinene in these methods are higher; furthermore, no solvent consumption and maximum extraction efficiency are some crucial advantages of these techniques. However, the application of some novel methods, such as ultrasound-assisted extraction, in industry scale is still problematic because of their intricate design data.

Facile synthesis of Cu NPs@Fe3O4-lignosulfonate: Study of catalytic and antibacterial/antioxidant activities.

Environmental pollution is one of the important concerns for human health. There are different types of pollutants and techniques to eliminate them from the environment. We hereby report an efficient method for the remediation of environmental contaminants through the catalytic reduction of the selected pollutants. A green method has been developed for the immobilization of copper nanoparticles on magnetic lignosulfonate (Cu NPs@Fe3O4-LS) using the aqueous extract of Filago arvensis L. as a non-toxic reducing and stabilizing agent. The characterization of the prepared Cu NPs@Fe3O4-LS was achieved by vibrating sample magnetometer (VSM), Fourier-transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), high resolution TEM (HRTEM), X-ray diffraction (XRD), scanning TEM (STEM), thermogravimetry-differential thermal analysis (TG/DTA), fast Fourier transform (FFT), energy-dispersive X-ray spectroscopy (EDS), and X-ray photoelectron (XPS) analyses. The synthesized Cu NPs@Fe3O4-LS was applied as a magnetic and green catalyst in the reduction of congo red (CR), 4-nitrophenol (4-NP), and methylene blue (MB). The progress of the reduction reactions was monitored by UV-Vis spectroscopy. Finally, the biological properties of Cu NPs@Fe3O4-LS were investigated. The prepared catalyst demonstrated excellent catalytic efficiency in the reduction of CR, 4-NP, and MB in the presence of sodium borohydride (NaBH4) as the reducing agent. The appropriate magnetism of Cu NPs@Fe3O4-LS made its recovery very simple. The advantages of this process include a simple reaction set-up, high and catalytic antibacterial/antioxidant activities, short reaction time, environmentally friendliness, high stability, and easy separation of the catalyst. In addition, the prepared Cu NPs@Fe3O4-LS could be reused for four cycles with no significant decline in performance.

Lignosulfonate valorization into a Cu-containing magnetically recyclable photocatalyst for treating wastewater pollutants in aqueous media.

This study presents an eco-friendly and economical process for preparing a magnetic copper complex conjugated to modified calcium lignosulfonate (LS) through a diamine (Fe3O4@LS@naphthalene-1,5-diamine@copper complex; FLN-Cu) as a green and novel catalyst. The prepared catalyst was characterized by Fourier-transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), vibrating sample magnetometer (VSM), Brunauer-Emmett-Teller (BET), energy-dispersive X-ray spectroscopy (EDS), elemental mapping, inductively coupled plasma-optical emission spectrometry (ICP-OES) and field emission scanning electron microscopy (FESEM) techniques. The photocatalytic performance of the synthesized FLN-Cu catalyst was investigated by the degradation of aqueous solutions of dyes such as Rhodamine B (RhB), methylene blue (MB), and Congo red (CR) under UV irradiation. The dye degradation was followed by UV-Vis (ultraviolet-visible) spectrophotometry by measuring the changes in absorbance. The effects of different factors such as pH, contact time, photocatalyst dosage, and initial concentration of dye on the adsorption percentage were also investigated. Moreover, the catalyst showed high stability and could be readily separated from the reaction media using a magnet and reused five times without a remarkable loss of catalytic ability.

Micro- and nanotechnology in biomedical engineering for cartilage tissue regeneration in osteoarthritis.

Osteoarthritis, which typically arises from aging, traumatic injury, or obesity, is the most common form of arthritis, which usually leads to malfunction of the joints and requires medical interventions due to the poor self-healing capacity of articular cartilage. However, currently used medical treatment modalities have reported, at least in part, disappointing and frustrating results for patients with osteoarthritis. Recent progress in the design and fabrication of tissue-engineered microscale/nanoscale platforms, which arises from the convergence of stem cell research and nanotechnology methods, has shown promising results in the administration of new and efficient options for treating osteochondral lesions. This paper presents an overview of the recent advances in osteochondral tissue engineering resulting from the application of micro- and nanotechnology approaches in the structure of biomaterials, including biological and microscale/nanoscale topographical cues, microspheres, nanoparticles, nanofibers, and nanotubes.

Magnetic chitosan stabilized Cu(II)-tetrazole complex: an effective nanocatalyst for the synthesis of 3-imino-2-phenylisoindolin-1-one derivatives under ultrasound irradiation.

In the present research, a recyclable catalyst has been prepared via a simple approach using chitosan as a linear polysaccharide. This paper reports the synthesis of novel copper(II) complex of 5-phenyl-1H-tetrazole immobilized on magnetic chitosan (MCS@PhTet@Cu(II)) as an effective catalyst. Transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM), vibrating sample magnetometer (VSM), Fourier-transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDS), and inductively coupled plasma mass spectrometry (ICP-MS) techniques were applied for the characterization of the catalyst. The catalytic activity of MCS@PhTet@Cu(II) was evaluated in the ultrasound-assisted synthesis of 3-imino-2-phenylisoindolin-1-one derivatives via the reaction between benzoyl chloride and arylcyanamides in ethanol at ambient temperature. Utilizing a wide variety of arylcyanamides under mild conditions, no use of toxic organic solvents, moderate reaction time, high yields along with catalyst excellent reusability and easy separation of the products without any tedious separation techniques, made this method a novel and simple process. The resulting heterogeneous catalyst showed valuable advantages such as easier work-up, better stability, and greater separation ability using an external magnet. The catalyst showed high efficacy and recyclability even after five cycles with no significant loss of its efficacy. The present methodology provides a path for the preparation of structurally diverse heterocyclic compounds, which may exhibit important biological activity.

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.

Polydopamine-coated magnetic Spirulina nanocomposite for efficient magnetic dispersive solid-phase extraction of aflatoxins in pistachio.

An efficient adsorbent was synthesized and used in magnetic dispersive solid phase extraction (MDSPE) of aflatoxins B1, B2, G1, and G2 at trace levels in pistachio prior to analysis by HPLC equipped with a fluorescence detector. Spirulina (Sp) algae was first magnetized, followed by surface modification with dopamine (Dp). The adsorbent was characterized using FT-IR, XRD, FE-SEM, EDX, VSM, and BET analyses. The effects of different analytical parameters on the extraction performance were evaluated. Under optimal conditions, good limits of detection (LODs) and quantifications (LOQs) were achieved in the ranges of 0.02-0.07 and 0.06-0.21 ng g-1, respectively. The RSDs were 5.9, 6.3, 5.6, and 7.3% for AFB1, G1, B2, and G2, respectively. The proposed method was successfully used to determine AFs in pistachio samples and acceptable recoveries in the range of 72-95% were obtained.

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.

Progresses in chitin, chitosan, starch, cellulose, pectin, alginate, gelatin and gum based (nano)catalysts for the Heck coupling reactions: A review.

Heck cross-coupling reaction (HCR) is one of the few transition metal catalyzed CC bond-forming reactions, which has been considered as the most effective, direct, and atom economical synthetic method using various catalytic systems. Heck reaction is widely employed in numerous syntheses including preparation of pharmaceutical and biologically active compounds, agrochemicals, natural products, fine chemicals, etc. Commonly, Pd-based catalysts have been used in HCR. In recent decades, the application of biopolymers as natural and effective supports has received attention due to their being cost effective, abundance, and non-toxicity. In fact, recent studies demonstrated that biopolymer-based catalysts had high sorption capacities, chelating activities, versatility, and stability, which make them potentially applicable as green materials (supports) in HCR. These catalytic systems present high stability and recyclability after several cycles of reaction. This review aims at providing an overview of the current progresses made towards the application of various polysaccharide and gelatin-supported metal catalysts in HCR in recent years. Natural polymers such as starch, gum, pectin, chitin, chitosan, cellulose, alginate and gelatin have been used as natural supports for metal-based catalysts in HCR. Diverse aspects of the reactions, different methods of preparation and application of polysaccharide and gelatin-based catalysts and their reusability have been reviewed.

Polysaccharide-based (nano)materials for Cr(VI) removal.

Chromium is a potentially poisonous and carcinogenic species, which originates from human activities and various industries such as leather, steel, iron, and electroplating industries. Chromium is present in various oxidation states, among which hexavalent chromium (Cr(VI)) is highly toxic as a natural contaminant. Therefore, chromium, particularly Cr(VI), must be eliminated from the environment, soil, and water to overcome significant problems due to its accumulation in the environment. There are different approaches such as adsorption, ion exchange, photocatalytic reduction, etc. for removing Cr(VI) from the environment. By converting Cr(VI) to Cr(III), its toxicity is reduced. Cr(III) is essential for the human diet, even in small amounts. Today, biopolymers such as alginate, cellulose, gum, pectin, starch, chitin, and chitosan have received much attention for the removal of environmental pollutants. Biopolymers, particularly polysaccharides, are very useful compounds due to their OH and NH2 functional groups and some advantages such as biodegradability, biocompatibility, and accessibility. Therefore, they can be widely applied in catalytic applications and as efficient adsorbents for the removal of toxic compounds from the environment. This review briefly investigates the application of polysaccharide-based (nano)materials for efficient Cr(VI) removal from the environment using adsorption/reduction, photocatalytic, and chemical reduction mechanisms.