Using Hybrid PDI-Fe3O4 Nanoparticles for Capturing Aliphatic Alcohols: Halogen Bonding vs. Lone Pair-π Interactions.

In this study, Fe3O4 nanoparticles (FeNPs) decorated with halogenated perylene diimides (PDIs) have been used for capturing VOCs (volatile organic compounds) through noncovalent binding. Concretely, we have used tetrachlorinated/brominated PDIs as well as a nonhalogenated PDI as a reference system. On the other hand, methanol, ethanol, propanol, and butanol were used as VOCs. Experimental studies along with theoretical calculations (the BP86-D3/def2-TZVPP level of theory) pointed to two possible and likely competitive binding modes (lone pair-π through the π-acidic surface of the PDI and a halogen bond via the σ-holes at the Cl/Br atoms). More in detail, thermal desorption (TD) experiments showed an increase in the VOC retention capacity upon increasing the length of the alkyl chain, suggesting a preference for the interaction with the PDI aromatic surface. In addition, the tetrachlorinated derivative showed larger VOC retention times compared to the tetrabrominated analog. These results were complemented by several state-of-the-art computational tools, such as the electrostatic surface potential analysis, the Quantum Theory of Atoms in Molecules (QTAIM), as well as the noncovalent interaction plot (NCIplot) visual index, which were helpful to rationalize the role of each interaction in the VOC···PDI recognition phenomena.

Highin vitroactivity of gold and silver nanoparticles from Solanum mammosum L. against SARS-CoV-2 surrogate Phi6 and viral model PhiX174.

The search for new strategies to curb the spread of the SARS-CoV-2 coronavirus, which causes COVID-19, has become a global priority. Various nanomaterials have been proposed as ideal candidates to inactivate the virus; however, because of the high level of biosecurity required for their use, alternative models should be determined. This study aimed to compare the effects of two types of nanomaterials gold (AuNPs) and silver nanoparticles (AgNPs), recognized for their antiviral activity and affinity with the coronavirus spike protein using PhiX174 and enveloped Phi6 bacteriophages as models. To reduce the toxicity of nanoparticles, a species known for its intermediate antiviral activity,Solanum mammosumL. (Sm), was used. NPs prepared with sodium borohydride (NaBH4) functioned as the control. Antiviral activity against PhiX174 and Phi6 was analyzed using its seed, fruit, leaves, and essential oil; the leaves were the most effective on Phi6. Using the aqueous extract of the leaves, AuNPs-Sm of 5.34 ± 2.25 nm and AgNPs-Sm of 15.92 ± 8.03 nm, measured by transmission electron microscopy, were obtained. When comparing NPs with precursors, both gold(III) acetate and silver nitrate were more toxic than their respective NPs (99.99% at 1 mg ml-1). The AuNPs-Sm were less toxic, reaching 99.30% viral inactivation at 1 mg ml-1, unlike the AgNPs-Sm, which reached 99.94% at 0.01 mg ml-1. In addition, cell toxicity was tested in human adenocarcinoma alveolar basal epithelial cells (A549) and human foreskin fibroblasts. Gallic acid was the main component identified in the leaf extract using high performance liquid chromatography with diode array detection (HPLC-DAD). The FT-IR spectra showed the presence of a large proportion of polyphenolic compounds, and the antioxidant analysis confirmed the antiradical activity. The control NPs showed less antiviral activity than the AuNPs-Sm and AgNPs-Sm, which was statistically significant; this demonstrates that both theS. mammosumextract and its corresponding NPs have a greater antiviral effect on the surrogate Phi bacteriophage, which is an appropriate model for studying SARS-CoV-2.

Fertility and Iron Bioaccumulation in Drosophila melanogaster Fed with Magnetite Nanoparticles Using a Validated Method.

Research on nanomaterial exposure-related health risks is still quite limited; this includes standardizing methods for measuring metals in living organisms. Thus, this study validated an atomic absorption spectrophotometry method to determine fertility and bioaccumulated iron content in Drosophila melanogaster flies after feeding them magnetite nanoparticles (Fe3O4NPs) dosed in a culture medium (100, 250, 500, and 1000 mg kg-1). Some NPs were also coated with chitosan to compare iron assimilation. Considering both accuracy and precision, results showed the method was optimal for concentrations greater than 20 mg L-1. Recovery values were considered optimum within the 95-105% range. Regarding fertility, offspring for each coated and non-coated NPs concentration decreased in relation to the control group. Flies exposed to 100 mg L-1 of coated NPs presented the lowest fertility level and highest bioaccumulation factor. Despite an association between iron bioaccumulation and NPs concentration, the 500 mg L-1 dose of coated and non-coated NPs showed similar iron concentrations to those of the control group. Thus, Drosophila flies' fertility decreased after NPs exposure, while iron bioaccumulation was related to NPs concentration and coating. We determined this method can overcome sample limitations and biological matrix-associated heterogeneity, thus allowing for bioaccumulated iron detection regardless of exposure to coated or non-coated magnetite NPs, meaning this protocol could be applicable with any type of iron NPs.

Effective Elimination and Biodegradation of Polycyclic Aromatic Hydrocarbons from Seawater through the Formation of Magnetic Microfibres.

Supramolecular aggregates formed between polycyclic aromatic hydrocarbons and either naphthalene or perylene-derived diimides have been anchored in magnetite magnetic nanoparticles. The high affinity and stability of these aggregates allow them to capture and confine these extremely carcinogenic contaminants in a reduced space. In some cases, the high cohesion of these aggregates leads to the formation of magnetic microfibres of several microns in length, which can be isolated from the solution by the direct action of a magnet. Here we show a practical application of bioremediation aimed at the environmental decontamination of naphthalene, a very profuse contaminant, based on the uptake, sequestration, and acceleration of the biodegradation of the formed supramolecular aggregate, by the direct action of a bacterium of the lineage Roseobacter (biocompatible with nanostructured receptors and very widespread in marine environments) without providing more toxicity to the environment.

A Very Highly Efficient Magnetic Nanomaterial for the Removal of PAHs from Aqueous Media.

Two new hybrid magnetic recyclable nanomaterials are developed. These new materials are based on bisimide perylene dopamine or bisimide perylene 3-aminopropyltriethoxysilane and iron oxide nanoparticles. One of them, the bisimide perylene dopamine, has proven to be very efficient in the removal, by magneto filtration, of 15 carcinogenic polycyclic aromatic compounds (PAHs), especially naphthalene, acenaphthene, anthracene, phenanthrene, and fluorene. These compounds are known to be common contaminants of drinking and underground water. This nanomaterial presents a high dispersivity and stability in an aqueous media, and it is capable of forming supramolecular fluorescent magnetic nanofibers with benzo-alpha-pyrene or benzo[k]fluoranthene, BKF. This strong association is due to hydrophobic forces and the π-π interaction, between the bisimide perylene motif and the polycyclic aromatic compounds. The resilience of this material is tested in different media. No good results are obtained in ethanol, acetone, or acetonitrile, but an 85% recovery is achieved using toluene or hexane. Once washed, nanoparticles are shown to retain their ability to continue capturing PAHs.

Adsorption and Quantification of Volatile Organic Compounds (VOCs) by using Hybrid Magnetic Nanoparticles.

The ability of Fe3 O4 magnetic nanoparticles decorated with perylene bisimides to adsorb aromatic volatile organic compounds (VOCs) is reported. We have used DFT-D3 calculations to anticipate the strong ability of the electron-poor perylene bisimide to form noncovalent complexes with electron-rich aromatic rings belonging to the VOC family. Subsequently, we synthesized a hybrid magnetic nanomaterial based on bisimide perylene dopamine and iron oxide nanoparticles. This material was used to fill a sorbent tube to study its ability to adsorb aromatic VOCs. We connected two tubes in series filled with the hybrid nanoparticles. The analysis of the front and back tubes was performed by thermal desorption (TD) coupled with capillary gas chromatography (GC)/flame ionization detector (FID). Adsorption values (defined as %VOCs found in the back tube) were determined for a series of aromatic VOCs and compared with the DFT binding energies. The tubes can be desorbed and reutilized more than 200 times without losing their properties.

One-Pot Environmentally Friendly Synthesis of Nanomaterials Based on Phytate-Coated Fe3O4 Nanoparticles for Efficient Removal of the Radioactive Metal Ions 90Sr, 90Y and (UO2)2+ from Water.

We report the fast (three minutes) synthesis of green nanoparticles based on nanoparticles coated with the natural organic receptor phytate for the recognition and capture of 90Sr, 90Y, and (UO2)2+. The new material shows excellent retention for (UO2)2+, 97%; these values were 73% and 100% for 90Sr and 90Y, respectively. Recovery of the three radioactive metal ions occurs through a non-competitive process. The new hybrid material is harmless, easy to prepare, and immobilizes these radioactive contaminants in water with great efficiency.

Raltitrexed-Modified Gold and Silver Nanoparticles for Targeted Cancer Therapy: Cytotoxicity Behavior In Vitro on A549 and HCT-116 Human Cancer Cells.

Two different raltitrexed gold and silver nanoparticles for the delivery of an antitumoral drug into cancer cells were synthesized and characterized. A cysteine linker was used for the covalent bonding of raltitrexed to the surface of nanoparticles. To evaluate the efficacy of the antifolate-derivative nanoparticles, their cytotoxicity was assayed in vitro with A549 human lung adenocarcinoma and HCT-116 colorectal carcinoma human cells. Modified nanoparticles are a biocompatible material, and administration of silver raltitrexed nanoparticles strongly inhibited the viability of the cancer cells; gold raltitrexed nanoparticles do not show any type of cytotoxic effect. The results suggest that silver raltitrexed nanoparticles could be a potential delivery system for certain cancer cells.

Silver nanoparticles as a potential treatment against SARS-CoV-2: A review.

Several human coronaviruses (HCoVs) are distinguished by the ability to generate epidemics or pandemics, with their corresponding diseases characterized by severe respiratory illness, such as that which occurs in severe acute respiratory syndrome (SARS-CoV), Middle East respiratory syndrome (MERS-CoV), and, today, in SARS-CoV-2, an outbreak that has struck explosively and uncontrollably beginning in December 2019 and has claimed the lives of more than 1.9 M people worldwide as of January 2021. The development of vaccines has taken one year, which is why it is necessary to investigate whether some already-existing alternatives that have been successfully developed in recent years can mitigate the pandemic's advance. Silver nanoparticles (AgNPs) have proved effective in antiviral action. Thus, in this review, several in vitro and in vivo studies of the effect of AgNPs on viruses that cause respiratory diseases are analyzed and discussed to promote an understanding of the possible interaction of AgNPs with SARS-CoV-2. The study focuses on several in vivo toxicological studies of AgNPs and a dose extrapolation to humans to determine the chief avenue of exposure. It can be concluded that the use of AgNPs as a possible treatment for SARS-CoV-2 could be viable, based on comparing the virus' behavior to that of similar viruses in in vivo studies, and that the suggested route of administration in terms of least degree of adverse effects is inhalation. This article is categorized under: Nanotechnology Approaches to Biology > Nanoscale Systems in Biology Therapeutic Approaches and Drug Discovery > Nanomedicine for Respiratory Disease Toxicology and Regulatory Issues in Nanomedicine > Toxicology of Nanomaterials.

Determination of Antioxidant Activity by Oxygen Radical Absorbance Capacity (ORAC-FL), Cellular Antioxidant Activity (CAA), Electrochemical and Microbiological Analyses of Silver Nanoparticles Using the Aqueous Leaf Extract of Solanum mammosum L.

PURPOSE: The importance of studying polyphenolic compounds as natural antioxidants has encouraged the search for new methods of analysis that are quick and simple. The synthesis of silver nanoparticles (AgNPs) using plant extracts has been presented as an alternative to determine the total polyphenolic content and its antioxidant activity. METHODS: In this study, aqueous leaf extract of Solanum mammosum, a species of plant endemic to South America, was used to produce AgNPs. The technique of oxygen radical absorption capacity using fluorescein (ORAC-FL) was used to measure antioxidant activity. The oxidation of the 2´,7´-dichlorodihydrofluorescein diacetate (DCFH2-DA) as fluorescent probe was used to measure cellular antioxidant activity (CAA). Electrochemical behavior was also examined using differential pulse voltammetry (DPV) and cyclic voltammetry (CV). Total polyphenolic content (TPH) was analyzed using the Folin-Ciocalteu method, and the major polyphenolic compound was analyzed by high performance liquid chromatography with diode array detector (HPLC/DAD). Finally, a microbial analysis was conducted using Escherichia coli and Bacillus sp. RESULTS: The average size of nanoparticles was 5.2 ± 2.3 nm measured by high-resolution transmission electron microscopy (HR-TEM). The antioxidant activity measured by ORAC-FL in the extract and nanoparticles were 3944 ± 112 and 637.5 ± 14.8 µM ET/g of sample, respectively. Cellular antioxidant activity was 14.7 ± 0.2 for the aqueous extract and 12.5 ± 0.2 for the nanoparticles. The electrochemical index (EI) was 402 µA/V for the extract and 324 µA/V for the nanoparticles. Total polyphenolic content was 826.6 ± 20.9 and 139.7 ± 20.9 mg EGA/100 g of sample. Gallic acid was the main polyphenolic compound present in the leaf extract. Microbiological analysis revealed that although leaf extract was not toxic for Escherichia coli and Bacillus sp., minor toxic activity for AgNPs was detected for both strains. CONCLUSION: It is concluded that the aqueous extract of the leaves of S. mammosum contains nontoxic antioxidant compounds capable of producing AgNPs. The methods using AgNPs can be used as a fast analytical tool to monitor the presence of water-soluble polyphenolic compounds from plant origin. Analysis and detection of new antioxidants from plant extracts may be potentially applicable in biomedicine.

Introducing Selectivity on Carbonaceous Material: Removing Noble Salts, Au3+, and Ag+ from Aqueous Media by Nanodiamonds Functionalized with Squaramides.

Nanodiamonds coated with dopamine-squaramide compounds have been prepared by a calcination/esterification synthetic process, which improves the efficiency of this carbonaceous material with respect to non-functionalized nanodiamonds. The modified nanodiamonds show excellent selective coordination of Ag+ and Au3+ cations in a Cd2+, Co2+, Cr3+, Cu2+, Pb2+, and Zn2+ mixture in water. The coordination capacity of the carbonyl squaramide groups with the silver and gold cation is based on purely electrostatic cation-dipole interactions. Overall, it is demonstrated that the conjunction between the nanodiamonds and the organic receptor improves the selectivity of the material toward noble cations.

Synthesis of Silver Nanoparticles Using Aqueous Leaf Extract of Mimosa albida (Mimosoideae): Characterization and Antioxidant Activity.

The search for sensitive and rapid analytical techniques for the determination of natural antioxidants is an area in constant growth due, among other aspects, to the complexity of plant matrices. In this study, silver nanoparticles prepared with the aqueous extract of Mimosa albida leaves were used to assess their polyphenolic content and antioxidant capacity. Silver nanoparticles were characterized by different techniques. As a result, nanoparticles of 6.5 ± 3.1 nm were obtained. The total phenolic content in the extract was 1320.4 ± 17.6 mg of gallic acid equivalents GAE. 100 g-1 and in the nanoparticles 257.3 ± 5.1 mg GAE. 100 g-1. From the phenolic profile analyzed by ultra high-performance liquid chromatography (UPLC) with a diode-array detector (DAD), the presence of apigenin and luteolin in the plant extract is postulated. The antioxidant capacity measured by oxygen radical absorbance capacity ORAC-fluorescein assay was 86917 ± 6287 and 7563 ± 967 µmol ET g-1 in the extract and nanoparticles respectively. Electrochemical analysis by cyclic voltammetry (CV) confirmed the effective reduction capacity of the Mimosa albida leaves extract to reduce Ag ions to AgNPs and differential pulse voltammetry (DPV) suggested the presence of two main reducing agents in the extract. From this study, it was concluded that the aqueous extract of Mimosa albida contains reducing agents capable of synthesizing silver nanoparticles, which can be used in the phytochemical industry.

Green synthesis of silver nanoparticles using Solanum mammosum L. (Solanaceae) fruit extract and their larvicidal activity against Aedes aegypti L. (Diptera: Culicidae).

The family of mosquitoes (Diptera: Culicidae) contains several species of major public health relevance due to their role as vectors of human disease. One of these species, Aedes aegypti, is responsible for the transmission of some of the most important vector-borne viruses affecting humankind, including dengue fever, chikungunya and Zika. Traditionally, control of Ae. aegypti and other arthropod species has relied on the use of a relatively small diversity of chemical insecticides. However, widespread and intensive use of these substances has caused significant adverse environmental effects and has contributed to the appearance of pesticide-resistant populations in an increasing number of locations around the world, thereby dramatically reducing their efficiency. Therefore, it becomes urgent to develop novel alternative tools for vector control. In that context, our study aimed at evaluating the insecticidal activity against Ae. aegypti of aqueous extracts obtained from the fruits of Solanum mammosum L., as well as silver nanoparticles synthesized using aqueous extracts from this plant species (SmAgNPs). To perform the test, third instar Ae. aegypti larvae were exposed to increasing concentrations of plant extract and SmAgNPs for 24 h. Our results suggest that both the aqueous extract and SmAgNPs were toxic to the larvae, with SmAgNPs displaying a much higher level of toxicity than the extract alone, as reflected in their LC50 values (0.06 ppm vs 1631.27 ppm, respectively). These results suggest that both S. mammosum extracts and SmAgNPs exhibit noteworthy larvicidal activity, and should be further explored as potential source of alternative tools in the fight against insect vectors of human disease.

Influence of the aromatic surface on the capacity of adsorption of VOCs by magnetite supported organic-inorganic hybrids.

It has been recently evidenced that hybrid magnetic nanomaterials based on perylene diimide (PDI) dopamine and iron oxide nanoparticles are useful for the adsorption and determination of volatile organic compounds (VOCs). However, NDI compounds are expensive and difficult to handle compared to smaller size diimides. Therefore, in this manuscript a combined experimental and theoretical investigation is reported including the analysis of the effect of changing the aromatic surface on the ability of these magnetite supported organic-inorganic hybrid nanoparticles (NPs) to adsorb several aromatic and non-aromatic VOCs. In particular, two new hybrid Fe3O4NPs are synthesized and characterized where the size of organic PDI dopamine linker is progressively reduced to naphthalene diimide (NDI) and pyromellitic diimide (PMDI). These materials were utilized to fill two sorbent tubes in series. Thermal desorption (TD) combined with capillary gas chromatography (GC)/flame detector (FID) was used to analyze both front and back tubes. Adsorption values (defined as % VOCs found in the front tube) were determined for a series of VOCs. The binding energies (DFT-D3 calculations) of VOC-Fe3O4NP complexes were also computed to correlate the electron-accepting ability of the arylene diimide (PDI, NDI or PMDI) with the adsorption capacity of the different tubes. The prepared hybrids can be easily separated magnetically and showed great reusability.

MP2 study of the dual sigma/pi-anion-binding affinity of fluorinated phthallic acid anhydrides.

Several complexes of fluorine-substituted phthallic acid anhydrides with chloride anion have been optimized at the RI-MP2(full)/6-31++G** level of theory. The presence of fluorine atoms attached to the aromatic ring increases the acidity of the aromatic hydrogen atoms. The dual sigma/pi-binding affinity of title compounds have been studied by means of ab initio and molecular interaction potential with polarization (MIPp) calculations and Bader's theory of "atoms-in-molecules".

Removal of Au3+ and Ag+ from aqueous media with magnetic nanoparticles functionalized with squaramide derivatives.

New magnetic hybrid nanoparticles of Fe3O4 coated with organosulfur-squaramide compounds are prepared. The modified-nanoparticles show a good coordination for Ag+ and Hg2+ cations in water, and present a high affinity for Au3+ ions. The behaviour of the squaramide-coated nanoparticles differs significantly from that previously reported for nanoparticles used as Au3+ scavengers. In the presence of organosulfur-squaramide, the Au3+ salt is reduced to gold nanoparticles that are deposited upon Fe3O4 nanoparticles. For the first time, the coordination capacity of the carbonyl squaramide groups with the gold cation, based on purely electrostatic cation-dipole interactions, is proved.

Detection of chemical warfare simulants by phosphorylation of a coumarin oximate.

The detection of chemical warfare simulants is attained by the PET mechanism that gives an "off-on" fluorescent response with a half-life of approximately 50 ms upon phosphorylation of a reactive oximate functionality; the X-ray crystal structure of the oximate was also obtained and is discussed.

Preparation, solid-state characterization, and computational study of a crown ether attached to a squaramide.

[structure: see text] Crystals of a disecondary squaramide covalently linked to a crown ether presents a great variety of inter- and intramolecular nonbonded interactions including C-H/pi contacts, C-H...O and N-H...O hydrogen bonds, and pi-pi stacking between squaramide rings. Latter interaction, the stacking between squaramide rings, can be considered as an experimental evidence for the proposed aromaticity of squaramide when it is forming hydrogen bonds, either as acceptor or donor.

Rational design, synthesis, and application of a new receptor for the molecular recognition of tricarboxylate salts in aqueous media.

A rational design of a tripodal receptor for the molecular recognition of tricarboxylate salts in aqueous media, based on squaramide, has been performed using high-level DFT calculations (RI-BP86/SVP level of theory) in solution using the COSMO treatment, including some preliminary ab initio calculations at the higher RI-MP2/TZVP level of theory, comparing the ability of squaramide to bind carboxylate salts with two widely used guanidinium salts. The tripodal receptor has been synthesized using a new methodology that has been recently reported by some of us, and its capability of recognizing several mono-, di-, and tricarboxylate salts has been studied experimentally by means of microcalorimetry experiments in a very high competitive media, H(2)O:EtOH 1:3. These experiments give enthalpic and entropic data, which are unfortunately scarce in the literature of molecular recognition of anions. Finally, a fluorimetric ensemble of the receptor with fluorescein has been found to be useful for the fluorimetric determination of zinc citrate in a commercial toothpaste using competition assays.