Surface-Enhanced Raman Scattering Using 2D Materials.

The use of surface-enhanced Raman scattering (SERS) as a technique for detecting small amounts of (bio)chemical analytes has become increasingly popular in various fields. While gold and silver nanostructures have been extensively studied as SERS substrates, the availability of other types of substrates is currently expanding the applications of this spectroscopic method. Recently, researchers have begun exploring two-dimensional (2D) materials (e. g., graphene-like nanostructures) as substrates for SERS analysis. These materials offer unique optical properties, a well-defined structure, and the ability to modify their surface chemistry. As a contribution to advance this field, this concept article highlights the significance of understanding the chemical mechanism that underlies the experimental Raman spectra of chemisorbed molecules onto 2D materials' surfaces. Therefore, the article discusses recent advancements in fabricating substrates using 2D layered materials and the synergic effects of using their metallic composites for SERS applications. Additionally, it provides a new perspective on using Raman imaging in developing 2D materials as analytical platforms for Raman spectroscopy, an exciting emerging research area with significant potential.

Removal of Rare Earth Elements from complex mixtures by using manganese ferrite nanoparticles: Optimization through surface response methodology.

The crucial role of Rare Earth Elements (REEs) in the development of hi-tech in addition to their limited availability have urged countries to develop sustainable alternatives to their conventional primary sources (ore mining). Sorption technologies using magnetic materials such as spinel ferrite nanoparticles provide efficient removal of REEs from contaminated solutions and ease of separation through application of an external magnetic field. However, there is still limited knowledge available regarding the optimal operational conditions in which to use these materials, especially in complex aqueous mixtures with different REEs. In this study, we have used Surface Response Methodology (SRM) applied to MnFe2O4 nanosorbents to identify their ideal sorption conditions of pH (4-8), REEs concentration (1-5 µM) and sorbent mass (20-180 mg L-1) in a mixture of nine REEs in water samples of distinct salinity (NaCl: 0-30 g L-1). Our results indicated that high pH favored REEs sorption because of the material's surface charge, which promoted interactions with REEs ions at pH 6-8. Yttrium was the least removed element, but total removal was achieved for lowest REEs concentration using 151 mg L-1 of sorbent. High removals were also obtained for the concentration of 5 µM (100 % removal, except for Y and La). Salinity did not impair sorption significantly (<10 %), which was owed to the high sorbent mass used in those assays. An increase in sorbent mass and initial REEs concentration also promoted faster kinetics. The spinel type MnFe2O4 nanoparticles showed great promise in a realistic application, which is the next proposed step in this line of research.

Surface-enhanced Raman scattering detection of thiram and ciprofloxacin using chitosan-silver coated paper substrates.

Fast detection of contaminants of emerging concern (CECs) in water resources is of great environmental interest. Ideally, sustainable materials should be used in water quality monitoring technologies implemented for such purposes. In this regard, the application of bio-based materials aimed at the fabrication of analytical platforms has become of great importance. This research merges both endeavors by exploring the application of chitosan-coated paper, decorated with silver nanoparticles (AgNPs), on surface-enhanced Raman scattering (SERS) spectroscopy studies of two distinct types of CECs dissolved in aqueous samples: an antibiotic (ciprofloxacin) and a pesticide (thiram). Our results indicate the superior SERS performance of biocoated substrates compared to their non-coated paper counterparts. The detection limits achieved for thiram and ciprofloxacin using the biocoated substrates were 0.024 ppm and 7.7 ppm, respectively. The efficient detection of both analytes is interpreted in terms of the role of the biopolymer in promoting AgNPs assemblies that result in local regions of enhanced SERS activity. Taking advantage of these observations, we use confocal Raman microscopy to obtain Raman images of the substrates using ciprofloxacin and thiram as molecular probes. We also demonstrate that these biobased substrates can be promising for on-site analysis when used in conjunction with portable Raman instruments.

Chemical Strategies for Dendritic Magneto-plasmonic Nanostructures Applied to Surface-Enhanced Raman Spectroscopy.

Invited for the cover of this issue is the group of Tito Trindade and colleagues at the University of Aveiro. The image depicts dendritic magneto-plasmonic substrates for surface-enhanced Raman scattering (SERS) detection. Read the full text of the article at 10.1002/chem.202202382.

Chemical Strategies for Dendritic Magneto-plasmonic Nanostructures Applied to Surface-Enhanced Raman Spectroscopy.

Chemical analyses in the field using surface-enhanced Raman scattering (SERS) protocols are expected to be part of several analytical procedures applied to water quality monitoring. To date, these endeavors have been supported by developments in SERS substrate nanofabrication, instrumentation portability, and the internet of things. Here, we report distinct chemical strategies for preparing magneto-plasmonic (Fe3 O4 : Au) colloids, which are relevant in the context of trace-level detection of water contaminants due to their inherent multifunctionality. The main objective of this research is to investigate the role of poly(amidoamine) dendrimers (PAMAMs) in the preparation of SERS substrates integrating both functionalities into single nanostructures. Three chemical routes were investigated to design magneto-plasmonic nanostructures that translate into different ways for assessing SERS detection by using distinct interfaces. Hence, a series of magneto-plasmonic colloids have been characterized and then assessed for their SERS activity by using a model pesticide (thiram) dissolved in aqueous samples.

Insightful vibrational imaging study on the hydration mechanism of carbamazepine.

Anhydrous carbamazepine (CBZ) is an anti-convulsant drug commonly used to treat epilepsy and relieve trigeminal neuralgia. The presence of the dihydrate form in commercial CBZ tablets can change the dissolution rate of the active pharmaceutical ingredient (API), thus decreasing its activity. The hydration transformation can occur during wet granulation or storage, within a few weeks, depending on the ambient conditions. This work aims to investigate the effect of relative humidity (RH) in the transition of pure anhydrous CBZ (CBZ III) into the hydrate form by using confocal Raman microscopy with cluster analysis (CA). Firstly, several tablets of pure CBZ III containing different amounts of CBZ DH (50%, 10%, 1%, 0.5%) were prepared and analyzed by Raman imaging with CA. Our results show that CBZ DH crystals can be detected in the CBZ III tablets, at as low a concentration as 0.5%, giving distinct Raman features for the analysed polymorphs. The stability of pure anhydrous (CBZ III) tablets was then monitored by Raman imaging at room temperature (20-22 °C) and different RH (6%, 60% and 89%). The Raman imaging with CA showed that the anhydrous CBZ tablets start to convert into the hydrate form after 48 h, and it completely changes after 120 hours (5 days) at RH 89%. The tablets exposed to RH 6% and 60% did not demonstrate the presence of CBZ DH after 1 week of exposure. The exposure time was extended for 9 months in the former, and no CBZ DH was observed. A comparative study using IR imaging was also performed, demonstrating the viability of these vibrational imaging techniques as valuable tools to monitor the hydration process of active pharmaceutical ingredients.

Magnetic Driven Nanocarriers for pH-Responsive Doxorubicin Release in Cancer Therapy.

Doxorubicin is one of the most widely used anti-cancer drugs, but side effects and selectivity problems create a demand for alternative drug delivery systems. Herein we describe a hybrid magnetic nanomaterial as a pH-dependent doxorubicin release carrier. This nanocarrier comprises magnetic iron oxide cores with a diameter of 10 nm, enveloped in a hybrid material made of siliceous shells and ĸ-carrageenan. The hybrid shells possess high drug loading capacity and a favorable drug release profile, while the iron oxide cores allows easy manipulation via an external magnetic field. The pH responsiveness was assessed in phosphate buffers at pH levels equivalent to those of blood (pH 7.4) and tumor microenvironment (pH 4.2 and 5). The nanoparticles have a loading capacity of up to 12.3 wt.% and a release profile of 80% in 5 h at acidic pH versus 25% at blood pH. In vitro drug delivery tests on human breast cancer and non-cancer cellular cultures have shown that, compared to the free drug, the loaded nanocarriers have comparable antiproliferative effect but a less intense cytotoxic effect, especially in the non-cancer cell line. The results show a clear potential for these new hybrid nanomaterials as alternative drug carriers for doxorubicin.

Remediation of arsenic from contaminated seawater using manganese spinel ferrite nanoparticles: Ecotoxicological evaluation in Mytilus galloprovincialis.

In the last decade different approaches have been applied for water remediation purposes, including the use of nanoparticles (NPs) to remove metals and metalloids from water. Although studies have been done on the toxic impacts of such NPs, very scarce information is available on the impacts of water after decontamination when discharged into aquatic environments. As such, in the present study we aimed to evaluate the ecotoxicological safety of seawater previously contaminated with arsenic (As) and remediated by using manganese-ferrite (MnFe2O4-NPs) NPs. For this, mussels Mytilus galloprovincialis were exposed for 28 days to different conditions, including clean seawater (control), As (1000 µg L-1) contaminated and remediated (As 70 µg L-1) seawater, water containing MnFe2O4- NPs (50 mg L-1) with and without the presence of As. At the end of exposure, concentrations of As in mussels tissues were quantified and biomarkers related to mussels' metabolism and oxidative stress status were evaluated. Results revealed that mussels exposed to water contaminated with As and to As + NPs accumulated significantly more As (between 62% and 76% more) than those exposed to remediated seawater. Regarding biomarkers, our findings demonstrated that in comparison to remediated seawater (conditions a, b, c) mussels exposed to contaminated seawater (conditions A, B, C) presented significantly lower metabolic activity, lower expenditure of energy reserves, activation of antioxidant and biotransformation defences, higher lipids and protein damages and greater AChE inhibition. Furthermore, organisms exposed to As, NPs or As + NPs revealed similar biochemical effects, both before and after water decontamination. In conclusion, the present study suggests that seawater previously contaminated with As and remediated by MnFe2O4-NPs presented significantly lower toxicity than As contaminated water, evidencing the potential use of these NPs to remediate seawater contaminated with As and its safety towards marine systems after discharges to these environments.

Trimethyl Chitosan/Siloxane-Hybrid Coated Fe3O4 Nanoparticles for the Uptake of Sulfamethoxazole from Water.

The presence of several organic contaminants in the environment and aquatic compartments has been a matter of great concern in the recent years. To tackle this problem, new sustainable and cost-effective technologies are needed. Herein we describe magnetic biosorbents prepared from trimethyl chitosan (TMC), which is a quaternary chitosan scarcely studied for environmental applications. Core@shell particles comprising a core of magnetite (Fe3O4) coated with TMC/siloxane hybrid shells (Fe3O4@SiO2/SiTMC) were successfully prepared using a simple one-step coating procedure. Adsorption tests were conducted to investigate the potential of the coated particles for the magnetically assisted removal of the antibiotic sulfamethoxazole (SMX) from aqueous solutions. It was found that TMC-based particles provide higher SMX adsorption capacity than the counterparts prepared using pristine chitosan. Therefore, the type of chemical modification introduced in the chitosan type precursors used in the surface coatings has a dominant effect on the sorption efficiency of the respective final magnetic nanosorbents.

Fluorescent Bioactive Corrole Grafted-Chitosan Films.

Transparent corrole grafted-chitosan films were prepared by chemical modification of chitosan with a corrole macrocycle, namely, 5,10,15-tris(pentafluorophenyl)corrole (TPFC), followed by solvent casting. The obtained films were characterized in terms of absorption spectra (UV-vis), FLIM (fluorescence lifetime imaging microscopy), structure (FTIR, XPS), thermal stability (TGA), thermomechanical properties (DMA), and antibacterial activity. The results showed that the chemical grafting of chitosan with corrole units did not affect its film-forming ability and that the grafting yield increased with the reaction time. The obtained transparent films presented fluorescence which increases with the amount of grafted corrole units. Additionally, all films showed bacteriostatic effect against S. aureus, as well as good thermomechanical properties and thermal stability. Considering these features, promising applications may be envisaged for these corrole-chitosan films, such as biosensors, bioimaging agents, and bioactive optical devices.

Biological synthesis of nanosized sulfide semiconductors: current status and future prospects.

There have been extensive and comprehensive reviews in the field of metal sulfide precipitation in the context of environmental remediation. However, these works have focused mainly on the removal of metals from aqueous solutions-usually, metal-contaminated effluents-with less emphasis on the precipitation process and on the end-products, frequently centering on metal removal efficiencies. Recently, there has been an increasing interest not only in the possible beneficial effects of these bioremediation strategies for metal-rich effluents but also on the formed precipitates. These metal sulfide materials are of special relevance in industry, due to their optical, electronic, and mechanical properties. Hence, identifying new routes for synthesizing these materials, as well as developing methodologies allowing for the control of the shape and size of particulates, is of environmental, economic, and practical importance. Multiple studies have shown proof-of-concept for the biological synthesis of inorganic metallic sulfide nanoparticles (NPs), resorting to varied organisms or cell components, though this information has scarcely been structured and compiled in a systematic manner. In this review, we overview the biological synthesis methodologies of nanosized metal sulfides and the advantages of these strategies when compared to more conventional chemical routes. Furthermore, we highlight the possibility of the use of numerous organisms for the synthesis of different metal sulfide NPs, with emphasis on sulfate-reducing bacteria (SRB). Finally, we put in perspective the potential of these methodologies in the emerging research areas of biohydrometallurgy and nanobiotechnology for the uptake of metals in the form of metal sulfide nanoparticles. A more complete understanding of the principles underlying the (bio)chemistry of formation of solids in these conditions may lead to the large-scale production of such metal sulfides, while simultaneously allowing an enhanced control over the size and shape of these biogenic nanomaterials.

Hybrid nanostructures for SERS: materials development and chemical detection.

This review focuses on recent developments in hybrid and nanostructured substrates for SERS (surface-enhanced Raman scattering) studies. Thus substrates composed of at least two distinct types of materials, in which one is a SERS active metal, are considered here aiming at their use as platforms for chemical detection in a variety of contexts. Fundamental aspects related to the SERS effect and plasmonic behaviour of nanometals are briefly introduced. The materials described include polymer nanocomposites containing metal nanoparticles and coupled inorganic nanophases. Chemical approaches to tailor the morphological features of these substrates in order to get high SERS activity are reviewed. Finally, some perspectives for practical applications in the context of chemical detection of analytes using such hybrid platforms are presented.

Biotechnologically obtained nanocomposites: A practical application for photodegradation of Safranin-T under UV-Vis and solar light.

This research was undertaken to determine the potential of biologically obtained ZnS-TiO2 nanocomposites to be used as catalysts in the photodegradation of organic pollutants, namely, Safranin-T. The photocatalysts were prepared by modifying the surface of commercial TiO2 particles with naturally produced ZnS, using sulfide species produced by sulfate-reducing bacteria and metal contaminated wastewaters. Comparative studies using powder X-ray diffraction (XRD) and scanning electron microscopy (SEM), prior and after photodegradation, were carried out in order to monitor possible structural and morphological changes on the particles. Adsorption properties and specific areas were determined by the Brunauer-Emmet-Teller (BET) method. The final solutions were characterized by UV-Vis and chemical oxygen demand (COD) content in order to determine Safranin-T concentration and toxicity. The influence of the catalyst amount, initial pH and dye concentration was also evaluated. Finally, the efficiency of the precipitates as catalysts in sunlight-mediated photodegradation was investigated, performing two scale experiments by using different volumes of dye-contaminated water (150 mL and 10 L). All tested composites showed potential to be used as photocatalysts for the degradation of Safranin-T, although the ZnS-TiO2_0.06 composite (0.06 g of TiO2 per 50 mL of the zinc solution) was the most effective. This substantiates the applicability of these biologically obtained materials as efficient photocatalysts for the degradation of organic pollutants, in laboratorial conditions and under direct sunlight.

Removal of chromium(III) from contaminated waters using cobalt ferrite: how safe is remediated water to aquatic wildlife?

The release of hazardous elements by industrial effluents to aquatic ecosystems is a potential threat to the environment. Chromium (Cr) is one of the elements whose levels in several freshwater ecosystems should be reduced to promote water reuse. In recent years, magnetic materials have gained increasing interest as sorbents because of their easy removal from treated water through magnetic separation. In this study, colloidal cobalt ferrite (CoFe2O4) particles were investigated as magnetic sorbents for chromium-aqueous chemical species. The oxidative stress responses of Mytilus galloprovincialis mussels exposed to 200 µg/L of Cr, resembling remediated water, were evaluated. More than 95% of Cr was removed from contaminated solutions by CoFe2O4 aqueous suspensions at pH 6 and pH 10. The kinetics of sorption experiments were examined using pseudo-1st order, pseudo-2nd order and Elovich models to evaluate which mathematical model has a better adjustment to the experimental data. The present study revealed that the levels of Cr that remained in remediated water induced limited biochemical changes in mussels, being considered safe for aquatic systems. Overall, the use of cobalt ferrite-based sorbents may constitute a promising approach to remediate contaminated water.

Green synthesis of covellite nanocrystals using biologically generated sulfide: potential for bioremediation systems.

This work describes the synthesis of CuS powders in high yield and via an environmentally friendly and straightforward process, under ambient conditions (temperature and pressure), by adding to aqueous copper (II) a nutrient solution containing biologically generated sulfide from sulfate-reducing bacteria (SRB). The powders obtained were composed of CuS (covellite) nanoparticles (NPs) exhibiting a spheroid morphology (<5 nm). The relevance of this method to obtain CuS supported solid substrates has been demonstrated by performing the synthesis in the presence of TiO2 and SiO2 submicron particles. We further extended the work carried out, which substantiates the potential of using biogenic sulfide for the production of covellite nanocrystals and composites, using the effluent of a bioremediation column. Hence, such process results in the synthesis of added value products obtained from metal rich effluents, such as metallurgical and industrial ones, or Acid Mine Drainage (AMD), when associated with bioremediation processes.

A comparative life cycle assessment of graphene nanoplatelets- and glass fibre-reinforced poly(propylene) composites for automotive applications.

The circulation of motor vehicles with an exhaust system is one of the leading causes of pollution. Due to the risk factor for human health and contribution to climate change, countries have been growing efforts to achieve a sustainable level of air quality and limit carbon dioxide (CO2) emissions in recent years. Hence, there has been significant interest in developing technological innovations such as alternative fuels and lighter thermoplastic composites for auto applications. Thermoplastic nanocomposites show substantial properties improvements, incorporating much lower nanofiller percentages than fibre-reinforced thermoplastic composites, allowing for a reduction in the weight of automotive parts (AP). For these motivations, this study presents a comparative life cycle assessment (LCA) of poly(propylene) (PP)-based graphene nanoplatelets (GnPs) nanocomposite and PP/glass fibre (GF) composite for automotive applications. The AP selected as the functional unit was the front end part of 1.5 tons weight car. The LCA included preparing raw materials, AP manufacturing, AP use, and AP end-of-life (EoL). Three different EoL scenarios were considered in this analysis. Several midpoint environmental impact indicators were evaluated. Overall, the results suggest that the different EoL scenarios do not affect the global environmental impact of both AP systems. The environmental impacts of the AP depend on the type of material. The AP of the PP-based GnPs nanocomposite exhibited a weight 28 % lower than the AP of the PP/GF composite. This lightweight resulted in energy and emissions savings, especially during the AP use stage, which was the stage with the most significant contribution in most environmental impact categories. Using nanocomposite reduced the AP environmental impact from 17 % to 75 %, depending on the impact category. The study suggested that substituting traditional composite with a new lighter nanocomposite can decrease the global environmental impacts caused by AP.

Environmental hazards of WELGRO® Cu+Zn: A nano-enabled fertilizer.

Nanoagrochemicals have the potential to revolutionize agriculture towards a precision farming system, able to reduce application rates and consequently their environmental footprint, while keeping efficacy. Several nanoagrochemicals (including nanopesticides (Npes) and nanofertilizers (Nfer)) are already commercialized but the environmental risk assessment of these advanced materials is often lacking. In the present study, we studied the commercial fertilizer WELGRO® Cu + Zn and assessed its ecotoxicity to the soil invertebrate species Enchytraeus crypticus (Oligochaeta), further comparing it to its individual active substances CuO and ZnO. To get a comprehensive picture of possible effects, we used four types of highly relevant tests in LUFA 2.2 soil: 1) avoidance behaviour (2 days), 2) reproduction (OECD standard, 28 d), 3) its extension (56 d), and 4) the full life cycle (FLC) (46 d) - this high level of hazard screening allows for increased interpretation. The results confirmed the nano-features of WELGRO® and a higher toxicity than the mixture of the individual components CuO + ZnO. E. crypticus avoided the soil spiked with WELGRO® and CuO + ZnO, this being the most sensitive endpoint - avoidance behaviour. Both WELGRO® and the active substances were little to non-toxic based on the OECD standard test. However, the toxicity dramatically increased in the tests focussing on longer-term sustainability measures, i.e., 56 days, ca. 170 for WELGRO®. This seems related to the nano-features of WELGRO®, e.g., slow release of ions from the nanoparticles throughout time. The FLCt results showed WELGRO® affected hatching and juveniles' survival, being these the most sensitive life stages. Hence, under actual real world field usage scenarios, i.e., based on the recommended application rates, nanoenabled WELGRO® can affect oligochaete populations like enchytraeids, both via the immediate avoidance behaviour and also via prolonged exposure periods.

Application of Nanoparticles in Cancer Treatment: A Concise Review.

Timely diagnosis and appropriate antitumoral treatments remain of utmost importance, since cancer remains a leading cause of death worldwide. Within this context, nanotechnology offers specific benefits in terms of cancer therapy by reducing its adverse effects and guiding drugs to selectively target cancer cells. In this comprehensive review, we have summarized the most relevant novel outcomes in the range of 2010-2023, covering the design and application of nanosystems for cancer therapy. We have established the general requirements for nanoparticles to be used in drug delivery and strategies for their uptake in tumor microenvironment and vasculature, including the reticuloendothelial system uptake and surface functionalization with protein corona. After a brief review of the classes of nanovectors, we have covered different classes of nanoparticles used in cancer therapies. First, the advances in the encapsulation of drugs (such as paclitaxel and fisetin) into nanoliposomes and nanoemulsions are described, as well as their relevance in current clinical trials. Then, polymeric nanoparticles are presented, namely the ones comprising poly lactic-co-glycolic acid, polyethylene glycol (and PEG dilemma) and dendrimers. The relevance of quantum dots in bioimaging is also covered, namely the systems with zinc sulfide and indium phosphide. Afterwards, we have reviewed gold nanoparticles (spheres and anisotropic) and their application in plasmon-induced photothermal therapy. The clinical relevance of iron oxide nanoparticles, such as magnetite and maghemite, has been analyzed in different fields, namely for magnetic resonance imaging, immunotherapy, hyperthermia, and drug delivery. Lastly, we have covered the recent advances in the systems using carbon nanomaterials, namely graphene oxide, carbon nanotubes, fullerenes, and carbon dots. Finally, we have compared the strategies of passive and active targeting of nanoparticles and their relevance in cancer theranostics. This review aims to be a (nano)mark on the ongoing journey towards realizing the remarkable potential of different nanoparticles in the realm of cancer therapeutics.

Corrigendum: Colloidal nanomaterials for water quality improvement and monitoring.

[This corrects the article DOI: 10.3389/fchem.2022.1011186.].

A single-source route for the synthesis of metal oxide nanoparticles using vegetable oil solvents.

We report a general method for the synthesis of metal oxide colloidal nanocrystals in sunflower oil using single-source precursors. In this research, iron oxide nanocrystals have been synthesized and characterized though this method can be extended to the synthesis of other common metal oxides such as ZnO and also to other types of vegetable oils as solvents. Using this method, nanoparticles with average diameters of 7 nm and 3 nm were obtained respectively for iron oxide and zinc oxide. The magnetic iron oxide phase was identified using powder XRD, surface enhanced Raman spectroscopy and magnetic measurements as maghemite as the main component. The magnetic measurements demonstrate the superparamagnetic behavior of the iron oxide nanoparticles. This synthetic approach is an interesting way to synthesize metal oxide nanocrystals in eco-friendly solvents of natural origin.