Institut des Molécules et Matériaux du Mans

Experimental results obtained in different laboratories world-wide by researchers using surface-enhanced Raman scattering (SERS) can differ significantly. We, an international team of scientists with long-standing expertise in SERS, address this issue from our perspective by presenting considerations on reliable and quantitative SERS. The central idea of this joint effort is to highlight key parameters and pitfalls that are often encountered in the literature. To that end, we provide here a series of recommendations on: a) the characterization of solid and colloidal SERS substrates by correlative electron and optical microscopy and spectroscopy, b) on the determination of the SERS enhancement factor (EF), including suitable Raman reporter/probe molecules, and finally on c) good analytical practice. We hope that both newcomers and specialists will benefit from these recommendations to increase the inter-laboratory comparability of experimental SERS results and further establish SERS as an analytical tool.

Superparamagnetic ferrite nanoparticles (MFe2O4, where M = Fe, Co, Mn) were synthesized through a novel one-step aqueous coprecipitation method based on the use of a new type of alkaline agent: the alkanolamines isopropanolamine and diisopropanolamine. The role played by the bases on the particles’ size, chemical composition, and magnetic properties was investigated and compared directly with the effect of the traditional inorganic base NaOH. The novel MFe2O4 nanomaterials exhibited high colloidal stability, particle sizes in the range of 4–12 nm, and superparamagnetic properties. More remarkably, they presented smaller particle sizes (up to 6 times) and enhanced saturation magnetization (up to 1.3 times) relative to those prepared with NaOH. Furthermore, the nanomaterials exhibited improved magnetic properties when compared with nanoferrites of similar size synthesized by coprecipitation with other bases or by other methods reported in the literature. The alkanolamines were responsible for these achievements by acting both as alkaline agents and as complexing agents that controlled the particle size during the synthesis process and improved the spin rearrangement at the surface (thinner magnetic “dead” layers). These results open new horizons for the design of water-dispersible MFe2O4 nanoparticles with tuned properties through a versatile and easily scalable coprecipitation route.

(MRSA). 23 of these complexes have not been reported for their antimicrobial properties before. This work reveals the vast diversity that metal-containing compounds can bring to antimicrobial research. It is important to raise awareness of these types of compounds for the design of truly novel antibiotics with potential for combatting antimicrobial resistance.

Providing an adequate quantity and quality of food for the escalating human population under changing climatic conditions is currently a great challenge. In outdoor cultures, sunlight provides energy (through photosynthesis) for photosynthetic organisms. They also use light quality to sense and respond to their environment. To increase the production capacity, controlled growing systems using artificial lighting have been taken into consideration. Recent development of light-emitting diode (LED) technologies presents an enormous potential for improving plant growth and making systems more sustainable. This review uses selected examples to show how LED can mimic natural light to ensure the growth and development of photosynthetic organisms, and how changes in intensity and wavelength can manipulate the plant metabolism with the aim to produce functionalized foods.

Our understanding of the fate and distribution of micro- and nano- plastics in the marine environment is limited by the intrinsic difficulties of the techniques currently used for the detection, quantification, and chemical identification of small particles in liquid (light scattering, vibrational spectroscopies, and optical and electron microscopies). Here we introduce Raman Tweezers (RTs), namely optical tweezers combined with Raman spectroscopy, as an analytical tool for the study of micro- and nanoplastics in seawater. We show optical trapping and chemical identification of sub-20 μm plastics, down to the 50 nm range. Analysis at the single particle level allows us to unambiguously discriminate plastics from organic matter and mineral sediments, overcoming the capacities of standard Raman spectroscopy in liquid, intrinsically limited to ensemble measurements. Being a microscopy technique, RTs also permits one to assess the size and shapes of particles (beads, fragments, and fibers), with spatial resolution only limited by diffraction. Applications are shown on both model particles and naturally aged environmental samples, made of common plastic pollutants, including polyethylene, polypropylene, nylon, and polystyrene, also in the presence of a thin eco-corona. Coupled to suitable extraction and concentration protocols, RTs have the potential to strongly impact future research on micro and nanoplastics environmental pollution, and enable the understanding of the fragmentation processes on a multiscale level of aged polymers.

Iron oxide nanoparticles (NPs) with average sizes in the range 4–28 nm have been obtained by varying different synthesis parameters of the thermal decomposition of an iron precursor (iron stearate) in the presence of surfactants in high boiling solvents. The synthesis parameters affect the NPs nucleation and growth steps, by modifying the stability of iron stearate on which depend the monomer formation and concentration, in agreement with the LaMer model. The monomer formation, which is reaction time and/or temperature dependent, is thus found to vary mainly as a function of the nature of solvents and ligands. The structural and magnetic characterizations of NPs with sizes in the range 5–20 nm confirm that the composition of NPs evolves from the maghemite for small sizes (typically <8 nm) up to a core of rather stoichiometric magnetite surrounded by an oxidized shell for large sizes (>12 nm) via a perturbed oxidized state for intermediate sizes. The values of saturation magnetization lower than those of bulk magnetite and maghemite were found to be related to this composition evolution and to the presence of oxidation defects, surface spin canting and volume spin canting as a function of NPs diameter. Small NPs presented mainly a surface spin canting. NPs with large sizes display Ms which depends on their oxidized shell thickness, defects and surface spin canting. NPs with intermediate sizes display a surface and in particular a volume spin canting due to a disordered structure induced by a perturbed oxidation state in these NPs.

The isoxazolidine ring represents one of the privileged structures in medicinal chemistry, and there have been an increasing number of studies on isoxazolidine and isoxazolidine-containing compounds. Optimization of the 1,3-dipolar cycloaddition (1,3-DC), original methods including electrophilic or palladium-mediated cyclization of unsaturated hydroxylamine, has been developed to obtain isoxazolidines. Novel reactions involving the isoxazolidine ring have been highlighted to accomplish total synthesis or to obtain bioactive compounds, one of the most significant examples being probably the thermic ring contraction applied to the total synthesis of (±)-Gelsemoxonine. The unique isoxazolidine scaffold also exhibits an impressive potential as a mimic of nucleosides, carbohydrates, PNA, amino acids, and steroid analogs. This review aims to be a comprehensive and general summary of the different isoxazolidine syntheses, their use as starting building blocks for the preparation of natural compounds, and their main biological activities.

Two porous iron trimesates, namely, commercial Basolite F300 (Fe(BTC); BTC = 1,3,5-benzenetricarboxylate) with unknown structure and synthetic MIL-100(Fe) (MIL stands for Material of Institut Lavoisier) of well-defined crystalline structure, have been compared as heterogeneous catalysts for four different reactions. It was found that while for catalytic processes requiring strong Lewis acid sites, Fe(BTC) performs better, MIL-100(Fe) is the preferred catalyst for oxidation reactions. These catalytic results have been rationalized by a combined in situ infrared and 57Fe Mössbauer spectroscopic characterization. It is proposed that the presence of extra Brønsted acid sites on the Fe(BTC) and the easier redox behavior of the MIL-100(Fe) could explain these comparative catalytic performances. The results illustrate the importance of structural defects (presence of weak Brønsted acid sites) and structural stability (MIL-100(Fe) is stable upon annealing at 280 °C despite Fe3+-to-Fe2+ reduction) on the catalytic activity of these two solids, depending on the reaction type.

Through the photosynthetic activity, microalgae process more than 25% of annual inorganic carbon dissolved in oceans into carbohydrates that ultimately, serve to feed the other levels of the trophic networks. Besides, microalgae synthesize bioactive molecules such as pigments and lipids that exhibit health properties. In addition, abiotic stresses, such as high irradiance, nutrient starvation, UV irradiation, trigger metabolic reorientations ending with the production of other bioactive compounds such as ω-3 fatty acids or carotenoids. Traditionally, these compounds are acquired through the dietary alimentation. The increasing, and often unsatisfied, demand for compounds from natural sources, combined with the decrease of the halieutic resources, forces the search for alternative resources for these bioactive components. Microalgae possess this strong potential. For instance, the diatom Odontella aurita is already commercialized as dietary complement and compete with fish oil for human nutrition. In this contribution, the microalga world is briefly presented. Then, the different types of biologically active molecules identified in microalgae are presented together with their potential use. Due to space limitation, only the biological activities of lipids and pigments are described in details. The contribution ends with a description of the possibilities to play with the environmental constrains to increase the productivity of biologically active molecules by microalgae and by a description of the progresses made in the field of alga culturing.

Marine plastic pollution is a major environmental issue. Given their ubiquitous nature and small dimensions, ingestion of microplastic (MP) and nanoplastic (NP) particles and their subsequent impact on marine life are a growing concern worldwide. Transfers along the trophic chain, including possible translocation, for which the hazards are less understood, are also a major preoccupation. Effects of MP ingestion have been studied on animals through laboratory exposure, showing impacts on feeding activity, reserve depletion and inflammatory responses, with consequences for fitness, notably reproduction. However, most experimental studies have used doses of manufactured virgin microspheres that may not be environmentally realistic. As for most ecotoxicological issues, the environmental relevance of laboratory exposure experiments has recently been debated. Here we review constraints and priorities for conducting experimental exposures of marine wildlife to microplastics based on the literature, feedback from peer reviewers and knowledge gained from our experience. Priorities are suggested taking into account the complexity of microplastics in terms of (i) aggregation status, surface properties and interactions with organic and inorganic materials, (ii) diversity of encountered particles types and concentrations, (iii) particle bioavailability and distribution in experimental tanks to achieve reproducibility and repeatability in estimating effects, and (iv) strict experimental procedures to verify the existence of genuine translocation. Relevant integrative approaches encompass a wide spectrum of methods from -omics to ecophysiological approaches, including modelling, are discussed to provide novel insights on the impacts of MP/NP on marine ecosystems from a long-term perspective. Knowledge obtained in this way would inform stakeholders in such a way as to help them mitigate impacts of the micro- and nano-plastic legacy.

The search for novel compounds of marine origin has increased in the last decades for their application in various areas such as pharmaceutical, human or animal nutrition, cosmetics or bioenergy. In this context of blue technology development, microalgae are of particular interest due to their immense biodiversity and their relatively simple growth needs. In this review, we discuss about the promising use of microalgae and microalgal compounds as sources of natural antibiotics against human pathogens but also about their potential to limit microbial infections in aquaculture. An alternative to conventional antibiotics is needed as the microbial resistance to these drugs is increasing in humans and animals. Furthermore, using natural antibiotics for livestock could meet the consumer demand to avoid chemicals in food, would support a sustainable aquaculture and present the advantage of being environmentally friendly. Using natural and renewable microalgal compounds is still in its early days, but considering the important research development and rapid improvement in culture, extraction and purification processes, the valorization of microalgae will surely extend in the future.

Alternative materials to platinum-based catalysts are required to produce molecular hydrogen from water at low overpotentials. Transition-metal chalcogenide catalysts have attracted significant interest over the past few years because of their activity toward proton reduction and their relative abundance compared with platinum. We report the synthesis and characterization of a new type of iron sulfide (FeS, pyrrhotite) nanoparticles prepared via a solvothermal route. This material can achieve electrocatalysis for molecular hydrogen evolution with no structural decomposition or activity decrease for at least 6 days at a mild overpotential in neutral water at room temperature.

Undoped ZnO and Zn0.97−xAl0.03MnxO (x = 0, 1, 2 and 3%) nanopowders (NPs) were synthesized by co-precipitation method. They were characterized by X-ray diffraction (XRD), Fourier transformed infrared (FTIR), Raman, UV–visible, photoluminescence (PL) and impedance spectroscopies. All samples exhibit a single phase wurtzite type. The average crystallite size lying between 22 and 42 nm was found to increase for all doped ZnO samples. The optical transmission in the visible region was improved due to doping. The optical band gap is in the range of 3–3.4 eV and was found to decrease up to 2% of Mn content but slightly increases with further doping. All PL spectra exhibit two emission peaks in UV and visible regions. The deconvolution of the visible emission peak reveals different emissions for all samples. An additional yellow emission is noticed for (Al + Mn) ZnO doped samples suggesting that the incorporation of aluminum and manganese in the zinc oxide host lattice enhances luminescence properties of ZnO. The ac conductivity (σac) was found to follow Jonscher’s power law and was improved with doping. Cole-Cole plots of all samples were suitably fitted to a circuit consisting in a parallel combination of a resistance and a constant phase element (CPE). Keywords: ZnO nanopowder, Doping, XRD, Optical properties, Conductivity

Click and drug: A combination of orthogonal click reactions is employed for the preparation of functional iron oxide nanoparticles (IONPs) that show unprecedented hyperthermia-induced drug release through a magnetically stimulated retro-Diels–Alder (rDA) process. Magnetic stimulation induces sufficient local energy in close proximity to the cycloadduct to initiate the rDA process.

The impact of a microplastic (MPs) mixture composed of polyethylene (PE) and polypropylene (PP) plastic particles, prepared from commercially available products, was evaluated in blue mussels Mytilus spp. exposed to three environmentally relevant concentrations: 0.008µg Lˉ¹ (low), 10 µg Lˉ¹ (medium) and 100 µg Lˉ¹ (high). Organisms were exposed for 10 days followed by 10 days of depuration in clean seawater under controlled laboratory conditions. The evaluation of MP effects on mussel clearance rate, tissue structure, antioxidant defences, immune and digestive parameters, and DNA integrity were investigated while the identification of plastic particles in mussel tissues (gills, digestive gland, and remaining tissues), and biodeposits (faeces and pseudofaeces) was performed using infrared microscopy (µFT-IR). Results showed the presence of MPs only in the digestive gland of mussels exposed to the highest tested concentration of MPs with a mean of 0,75 particle/mussel (after the 10 days of exposure). In biodeposits, PE and PP particles were detected following exposure to all tested concentrations confirming the ingestion of MPs by the organisms. A differential response of antioxidant enzyme activities between digestive gland and gills was observed. Significant increases in superoxide dismutase (SOD) and catalase (CAT) activities were measured in the digestive gland of mussels exposed to the low (0.008µg Lˉ¹) and medium (10 µg Lˉ¹) concentrations of MPs and in the gills from mussels exposed to the highest concentration (100 µg Lˉ¹) of MPs that could be indicative of a change in the redox balance. Moreover, an increase in acid phosphatase activity was measured in hemolymph of mussels exposed to 0.008 and 10 µg Lˉ¹ concentrations. No significant difference was observed in the clearance rate, and histopathological parameters between control and exposed mussels. This study brings new insights on the potential sublethal impacts of MPs at environmentally relevant concentrations in marine bivalves.

importance in the development of many new technologies, andare impacting various key points of modern life, that is, energyproduction and storage, microelectronics and photonics,catalysis, automotive, building, etc. Many research fields andapplications are indeed concerned by a better knowledge of therelationships occurring between the structure of suchcompounds and some pertinent physical properties. ThisReview deals with the structural chemistry of solid-stateinorganic fluorides and oxide-fluorides, mostly transitionmetal-based, including rare-earth elements. Such a Review hasnot been published for a long time.1 Articles that recentlyappeared on inorganic fluorinated compounds were mostlyfocused on material science characteristics: morphology, surfacefunctionalization, nanostructuration of the materials andapplications, rather than on the description of characteristicstructural features.2−5 Detailed reviews focused on rare earthbasedinorganic fluorides have also appeared some yearsago...

Fucoxanthin is a well-known carotenoid of the xanthophyll family, mainly produced by marine organisms such as the macroalgae of the fucus genus or microalgae such as Phaeodactylum tricornutum. Fucoxanthin has antioxidant and anti-inflammatory properties but also several anticancer effects. Fucoxanthin induces cell growth arrest, apoptosis, and/or autophagy in several cancer cell lines as well as in animal models of cancer. Fucoxanthin treatment leads to the inhibition of metastasis-related migration, invasion, epithelial–mesenchymal transition, and angiogenesis. Fucoxanthin also affects the DNA repair pathways, which could be involved in the resistance phenotype of tumor cells. Moreover, combined treatments of fucoxanthin, or its metabolite fucoxanthinol, with usual anticancer treatments can support conventional therapeutic strategies by reducing drug resistance. This review focuses on the current knowledge of fucoxanthin with its potential anticancer properties, showing that fucoxanthin could be a promising compound for cancer therapy by acting on most of the classical hallmarks of tumor cells.

A mixed cation MIL-53(Cr-Fe) MOF has been obtained by direct synthesis. Multiple experimental techniques have demonstrated the presence of a genuine mixed phase, leading to a breathing behaviour different from either of the single cation analogues.

A versatile method based on Raman microscopy was developed to follow the degradation of iron carboxylate Metal Organic Framework (MOF) nano- or micro-particles in simulated body fluid (phosphate buffer). The analysis of both the morphology and chemical composition of individual particles, including observation at different regions on the same particle, evidenced the formation of a sharp erosion front during particle degradation. Interestingly, this front separated an intact non eroded crystalline core from an amorphous shell made of an inorganic network. According to Mössbauer spectrometry investigations, the shell consists essentially of iron phosphates. Noteworthy, neither drug loading nor surface modification affected the integrity of the tridimensional MOF network. These findings could be of interest in the further development of next generations of MOF drug carriers.

Diatoms are responsible for up to 40% of the carbon fixation in our oceans. The fixed carbon is moved through carbon metabolism towards the synthesis of organic molecules that are consumed through interlocking foodwebs, and this process is strongly impacted by the abiotic environment. However, it has become evident that diatoms can be used as 'platform' organisms for the production of high valuable bio-products such as lipids, pigments and carbohydrates where stress conditions can be used to direct carbon metabolism towards the commercial production of these compounds. In the first section of this review, some aspects of carbon metabolism in diatoms and how it is impacted by environmental factors are briefly described. The second section is focused on the biosynthesis of lipids and in particular omega-3 long-chain polyunsaturated fatty acids and how low temperature stress impacts on the production of these compounds. In a third section, we review the recent advances in bioengineering for lipid production. Finally, we discuss new perspectives for designing strains for the sustainable production of high-value lipids.This article is part of the themed issue 'The peculiar carbon metabolism in diatoms'.