A Novel Nanoporous Adsorbent for Pesticides Obtained from Biogenic Calcium Carbonate Derived from Waste Crab Shells.

A novel nanoporous adsorbent was obtained through the thermal treatment and chemical wash of the wasted crab shells (BC1) and characterized by various techniques. The structure of BC1 at the end of the treatments comprised a mixture of calcite and amorphous CaCO3, as evidenced by X-ray diffraction and Fourier transform infrared absorption. The BET surface area, BET pore volume, and pore diameter were 250.33 m2 g-1, 0.4 cm3 g-1, and <70 nm, respectively. The point of zero charge of BC1 was determined to be around pH 9. The prepared adsorbent was tested for its adsorption efficacy towards the neonicotinoid pesticide acetamiprid. The influence of pH (2-10), temperature (20-45 °C), adsorbent dose (0.2-1.2 g L-1), contact time (5-60 min), and initial pesticide concentration (10-60 mg L-1) on the adsorption process of acetamiprid on BC1 was studied. The adsorption capacity of BC1 was 17.8 mg g-1 under optimum conditions (i.e., 20 mg L-1 initial acetamiprid concentration, pH 8, 1 g L-1 adsorbent dose, 25 °C, and 15 min contact time). The equilibrium data obtained from the adsorption experiment fitted well with the Langmuir isotherm model. We developed an effective nanoporous adsorbent for the recycling of crab shells which can be applied on site with minimal laboratory infrastructure according to local needs.

Enhanced Stability of Dopamine Delivery via Hydrogel with Integrated Graphene.

The synthesis of graphene-based materials for drug delivery represents an area of active research, and the use of graphene in drug delivery systems is promising due to its unique properties. Thus, in the present work, we discuss the potential of few-layer graphene in a hydrogel system for dopamine release. The hydrogels are frequently used for these systems for their special physico-chemical properties, which can ensure that the drug is effectively released in time. However, the release from such structures is mostly determined by diffusion alone, and to overcome this restriction, the hydrogel can be "improved" with nanoscale fillers like graphene. The release kinetics of the composite obtained were analyzed to better understand how the use of graphene, instead of the more common graphene oxide (GO) and reduced graphene oxide (rGO), affects the characteristics of the system. Thus, the systems developed in this study consist of three main components: biopolymer, graphene, and dopamine. The hydrogels with graphene were prepared by combining two different solutions, one with polyacrylic acid and agarose and one with graphene prepared by the exfoliation method with microwave irradiation. The drug delivery systems were developed by adding dopamine to the obtained hydrogels. After 24 h of release, the presence of dopamine was observed, demonstrating that the system developed can slow down the drug's degradation because of the interactions with the graphene nanoplates and the polymer matrix.

Correlation of Elemental Transfer, Bioactive Compounds and Antioxidant Activity on Lactuca sativa L. Grown in Soil with Functionalized CNT and HMs.

While heavy metals (HM) have been considered in recent decades to be the most common and problematic pollutants, the expansion of the list of pollutants due to the active use of carbon nanotubes (CNT) raises new questions about the benefit and harm of HM released to nature individually or fixed on CNT walls. A pot experiment was conducted to compare the effect of two classes of potential pollutants-metal salts of Pb, Mn, Cu, Zn, Cd, and Ni; and functionalized CNTs with COOH, MnO2, Fe3O4, and MnO2-Fe3O4-applied in soil, on the elemental transfer, the bioactive compounds accumulation, and the antioxidant activity in lettuce. While CNTs mainly increased the elemental transfer from soil to leaves, HM salts strongly obstructed it. In the presence of CNTs, the antioxidant activity in lettuce leaves correlated with the transfer of elements from soil to root and from root to leaves. The excess of HMs in soil induced a greater variation of the polyphenols quantity and antioxidant activity than the excess of CNTs. It might be assumed that lettuce perceived HMs as a more aggressive stressor than CNTs and more strongly activated the defense mechanism, showing the reduction of the element transfer and enhancing of total polyphenol production and antioxidant activity.

Antioxidant, Anti-Inflammatory Effects and Ability to Stimulate Wound Healing of a Common-Plantain Extract in Alginate Gel Formulations.

Our study aimed to investigate the biological effects of a common-plantain (Plantago major L.) extract, encapsulated in alginate, on dermal human fibroblast cultures in vitro, in view of its potential use as a wound healing adjuvant therapy. Common-plantain extracts were obtained by infusion and ultrasound extraction, and their total polyphenolic content and antioxidant capacity were determined by spectrophotometry. The best extract, which was obtained by infusion, was further encapsulated in sodium alginate in two different formulations. Fourier Transform Infrared Spectroscopy (FTIR) was used to demonstrate the existing interactions in the obtained common-plantain extract in the alginate formulations. The encapsulation efficiency was evaluated based on the total polyphenol content. These alginate gel formulations were further used in vitro to determine their biocompatibility and antioxidant and anti-inflammatory effects by spectrophotometry and ELISA, as well as their ability to stimulate fibroblast migration (scratch test assay) at different time points. In addition, the collagen 1 and 3 levels were determined by Western blot analysis. The data showed that the microencapsulated plantain extract formulations induced an antioxidant, anti-inflammatory effect, enhanced collagen production and increased wound closure in the first 8 h of their application. These results are encouraging for the use of this alginate plantain extract formulation as an adjuvant for skin wound healing.

The Effect of Functionalized Multiwall Carbon Nanotubes with Fe and Mn Oxides on Lactuca sativa L.

The aim of this work was to evaluate the effect of six nanomaterials, namely CNT-COOH, CNT-MnO2, CNT-Fe3O4, CNT-MnO2-Fe3O4, MnO2, and Fe3O4 on lettuceTo determine the impact of nanomaterials on lettuce, the results obtained were compared with those for the control plant, grown in the same conditions of light, temperature, and humidity but without the addition of nanomaterial. The study found that the content of bioactive compounds and the antioxidant capacity varied in the treated plants compared to the control ones, depending on the nanomaterial. The use of CNTs functionalized with metal oxides increases the elemental concentration of lettuce leaves for the majority of the elements. On the contrary, metal oxide nanoparticles and CNT functionalized with carboxyl groups induce a decrease in the concentration of many elements. Soil amending with MnO2 affects the content of more than ten elements in leaves. Simultaneous application of CNT and MnO2 stimulates the elemental translocation of all elements from roots to leaves, but the simultaneous use of CNT and Fe3O4 leads to the most intense translocation compared to the control other than Mo.

Biosynthesis of Nanoparticles Using Plant Extracts and Essential Oils.

Plant extracts and essential oils have a wide variety of molecules with potential application in different fields such as medicine, the food industry, and cosmetics. Furthermore, these plant derivatives are widely interested in human and animal health, including potent antitumor, antifungal, anti-inflammatory, and bactericidal activity. Given this diversity, different methodologies were needed to optimize the extraction, purification, and characterization of each class of biomolecules. In addition, these plant products can still be used in the synthesis of nanomaterials to reduce the undesirable effects of conventional synthesis routes based on hazardous/toxic chemical reagents and associate the properties of nanomaterials with those present in extracts and essential oils. Vegetable oils and extracts are chemically complex, and although they are already used in the synthesis of nanomaterials, limited studies have examined which molecules are effectively acting in the synthesis and stabilization of these nanostructures. Similarly, few studies have investigated whether the molecules coating the nanomaterials derived from these extracts and essential oils would bring benefits or somehow reduce their potential activity. This synergistic effect presents a promising field to be further explored. Thus, in this review article, we conducted a comprehensive review addressing the main groups of molecules present in plant extracts and essential oils, their extraction capacity, and available methodologies for their characterization. Moreover, we highlighted the potential of these plant products in the synthesis of different metallic nanomaterials and their antimicrobial capacity. Furthermore, we correlated the extract's role in antimicrobial activity, considering the potential synergy between molecules from the plant product and the different metallic forms associated with nanomaterials.

A Multi-Method Approach for Impact Assessment of Some Heavy Metals on Lactuca sativa L.

Heavy metals represent a large category of pollutants. Heavy metals are the focus of researchers around the world, mainly due to their harmful effects on plants. In this paper, the influence of copper, cadmium, manganese, nickel, zinc and lead, present in soil in different concentrations (below the permissible limit, the maximum permissible concentration and a concentration higher than the maximum permissible limit) on lettuce (Lactuca sativa L.) was evaluated. For this purpose, the authors analyzed the variation of photosynthetic pigments, total polyphenols, antioxidant activity and the elemental content in the studied plants. The experimental results showed that the variation of the content of biologically active compounds, elemental content and the antioxidant activity in the plants grown in contaminated soil, compared to the control plants, depends on the type and concentration of the metal added to the soil. The biggest decrease was recorded for plants grown in soil treated with Ni I (-42.38%) for chlorophyll a, Zn II (-32.92%) for chlorophyll b, Ni I (-40.46%) for carotenoids, Pb I (-40.95%) for polyphenols and Cu III (-29.42%) for DPPH. On the other hand, the largest increase regarding the amount of biologically active compounds was registered for Mn I (88.24%) in the case of the chlorophyll a, Mn I (65.56%) for chlorophyll b, Pb I (116.03%) for carotenoids, Ni III (1351.23%) for polyphenols and Ni III (1149.35%) for DPPH.

The Antibacterial Properties of Nanocomposites Based on Carbon Nanotubes and Metal Oxides Functionalized with Azithromycin and Ciprofloxacin.

Different microorganisms are present in nature, some of which are assumed to be hazardous to the human body. It is crucial to control their continuing growth to improve human life. Nanomaterial surface functionalization represents a current topic in continuous evolution that supports the development of new materials with multiple applications in biology, medicine, and the environment. This study focused on the antibacterial activity of different nanocomposites based on functionalized multi-walled carbon nanotubes against four common bacterial strains. Two metal oxides (CuO and NiO) and two antibiotics (azithromycin and ciprofloxacin) were selected for the present study to obtain the following nanocomposites: MWCNT-COOH/Antibiotic, MWCNT-COOH/Fe3O4/Antibiotic, and MWCNT-COOH/Fe3O4/MO/Antibiotic. The present study included two Gram-positive bacteria (Staphylococcus aureus and Enterococcus faecalis) and two Gram-negative bacteria (Escherichia coli and Pseudomonas aeruginosa). Ciprofloxacin (Cip) functionalized materials (MWCNT-COOH/Fe3O4/Cip) were most efficient against all tested bacterial strains; therefore, we conclude that Cu and Ni reduce the effects of Cip. The obtained results indicate that the nanocomposites functionalized with Cip are more effective against selected bacteria strains compared to azithromycin (Azi) functionalized nanocomposites. The current work determined the antibacterial activities of different nanocomposites and gave fresh insights into their manufacture for future research regarding environmental depollution.

Synthesis and Characterization of MWCNT-COOH/Fe3O4 and CNT-COOH/Fe3O4/NiO Nanocomposites: Assessment of Adsorption and Photocatalytic Performance.

In this study the adsorption and photodegradation capabilities of modified multi-walled carbon nanotubes (MWCNTs), using tartrazine as a model pollutant, is demonstrated. MWCNT-COOH/Fe3O4 and MWCNT-COOH/Fe3O4/NiO nanocomposites were prepared by precipitation of metal oxides in the presence of MWCNTs. Their properties were examined by X-ray diffraction in powder (XRD), Fourier-transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), scanning electron microscopy (SEM), Raman spectroscopy, synchrotron-based Scanning PhotoElectron Microscopy (SPEM), and Brunauer-Emmett-Teller (BET) analysis. It was found that the optimal adsorption conditions were pH 4 for MWCNT-COOH/Fe3O4 and pH 3 for MWCNT-COOH/Fe3O4/NiO, temperature 25 °C, adsorbent dose 1 g L-1, initial concentration of tartrazine 5 mg L-1 for MWCNT-COOH/Fe3O4 and 10 mg L-1 for MWCNT-COOH/Fe3O4/NiO and contact time 5 min for MWCNT-COOH/Fe3O4/NiO and 15 min for MWCNT-COOH/Fe3O4. Moreover, the predominant degradation process was elucidated simultaneously, with and without simulated sunlight irradiation, using thermal lens spectrometry (TLS) and UV-Vis absorption spectrophotometry. The results indicated the prevalence of the photodegradation mechanism over adsorption from the beginning of the degradation process.

The Effect of Copper Salts on Bioactive Compounds and Ultrastructure of Wheat Plants.

Abiotic stress agents, among them metal stress, can cause oxidative damage to plant cells. In defense, plants can increase the production of secondary metabolites in order to mitigate the harmful effects caused by them. The purpose of this work was to evaluate the effect of two types of copper salts (CuSO4 and Cu(NO3)2), added in two different amounts in soil (150 mg/kg, respectively 300 mg/kg), on assimilating pigments, total polyphenols, antioxidant activity and the elemental composition of wheat. The obtained results were compared with those from control plants grown in the same conditions but without copper salts. The amount of assimilating pigments, total polyphenols, and antioxidant activity respectively increases or decreases in the plants treated with copper salts compared to the control depending on the stage of development of the plant. No significant damage induced in the leaves of the wheat plants treated with the selected salts was observed following the TEM analysis. In six-week-old plants it was observed by EDX analysis that the salts are transformed into nanoparticles. The bioactive compounds, elemental composition and their interaction is influenced by concentration of metal's salt, type of salt and exposure period.

Efficient Extraction of Total Polyphenols from Apple and Investigation of Its SPF Properties.

The purpose of this study was to evaluate the sun protection factor (SPF) of cosmetic emulsions with the addition of hydroalcoholic apple extract. First, the total polyphenolic content, the antioxidant activity and SPF properties of the extracts obtained by sonication and refluxing were evaluated. The two extraction methods were improved using the central composite design. For cosmetic emulsion that contained a different concentration of apple extract (10-40%), a SPF value between 0.51 and 0.90 was obtained. The most efficient apple extract was obtained by reflux using 50% ethanol and a 60 min extraction time. The concentrated extract was incorporated in a cosmetic emulsion whose SPF maximum was 0.90. Accordingly, due to photoprotective properties, the apple extract can be a candidate for use in cosmetic formulations.

The Effect of TiO2 Nanoparticles on the Composition and Ultrastructure of Wheat.

The present work aims to follow the influence of TiO2 nanoparticles (TiO2 NPs) on bioactive compounds, the elemental content of wheat, and on wheat leaves' ultrastructure. Synthesized nanoparticles were characterized by X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, and transmission electron microscopy (TEM). The concentration of phenolic compounds, assimilation pigments, antioxidant capacity, elemental content, as well as the ultrastructural changes that may occur in the wheat plants grown in the presence or absence of TiO2 NPs were evaluated. In plants grown in the presence of TiO2 NPs, the amount of assimilating pigments and total polyphenols decreased compared to the control sample, while the antioxidant activity of plants grown in amended soil was higher than those grown in control soil. Following ultrastructural analysis, no significant changes were observed in the leaves of TiO2-treated plants. Application of TiO2 NPs to soil caused a significant reaction of the plant to stress conditions. This was revealed by the increase of antioxidant capacity and the decrease of chlorophyll, total polyphenols, and carotenoids. Besides, the application of TiO2 NPs led to significant positive (K, Zn, Br, and Mo) and negative (Na, Mn, Fe, As, Sr, Sb, and Ba) variation of content.

The Impact Assessment of CuO Nanoparticles on the Composition and Ultrastructure of Triticum aestivum L.

In the present study, the effects of copper oxide nanoparticles (CuO NPs) on bioactive compounds, the ultrastructural modifications which can occur, and elemental content of wheat were investigated. Changes in the wheat plants grown in presence or absence of CuO NPs were estimated. The application of CuO NPs decreased the amounts of chlorophylls and carotenoids and increased the amounts of polyphenols and antioxidant capacity. Ultrastructural analysis showed that the plants treated with CuO NPs were negatively affected. Soil amending completely inhibited the accumulation of seventeen elements, while K, Br, Al, and Zn were accumulated and Cl, Na, Ba, and Sr content decreased in wheat samples, regardless of the type of NPs applied. The application of chemically obtained NPs induced the most significant changes, completely blocking the assimilation of Fe, Mo, As, Sb, and Sm, and favoring much higher accumulation of Br than biogenic NPs. The decrease in chlorophylls and carotenoids is correlated with increase in antioxidant capacity, and occurs with increase of Mo, Al, Mg, K, Zn, and Ca content. The behavior of total polyphenols is correlated with Br content, and antagonist to Al behavior. From the point of view of bioactive compounds, the most affected plants were those that grew in the presence of CuO-NP-cel, while from the point of view of elementary analysis, the most affected plants were those grown in the presence of CuO-NP. By corroborating the obtained results, it was found that the CuO NPs have a negative effect on wheat plants.

Evaluation of CNT-COOH/MnO2/Fe3O4 nanocomposite for ibuprofen and paracetamol removal from aqueous solutions.

The nanocomposite CNT-COOH/MnO2/Fe3O4 was synthesized and characterized by different techniques, namely X-ray diffraction, Fourier-transform infrared spectroscopy, transmission electron microscopy, scanning electron microscopy, energy dispersive spectroscopy, thermogravimetric analysis, Brunauer-Emmett-Teller analysis, magnetic measurement, point of zero charge and hydrophobicity index. Analyzes revealed the groups -COOH, MnO2 and Fe3O4 attached to the carbon nanotubes, the acidic character of the obtained nanocomposite and its stability. The surface area for the obtained nanocomposite was 114.2 m2 g-1. The prepared nanocomposite was used for adsorption of ibuprofen and paracetamol from aqueous solution. Isotherm, kinetic and thermodynamic parameters were determined for predicting the ibuprofen and paracetamol adsorption on synthetized nanocomposite. The equilibrium data obtained from adsorption were well represented by Langmuir model and kinetics data were well fitted by the pseudo-second order model. The maximum adsorption capacity obtained for ibuprofen and paracetamol was 103.093 mg g-1, 80.645 mg g-1 respectively. The thermodynamic analysis showed that the adsorption process for both pollutants was spontaneous and endothermic. The synthetized nanocomposite can be a suitable new absorbent for ibuprofen and paracetamol removal from aqueous solutions due to its high adsorbing capacity and it can be separated by an external magnetic field.