Magnetic studies of ultrafine CoFe2O4 nanoparticles with different molecular surface coatings.

Surface functionalized ultrafine CoFe2O4 nanoparticles (NPs), with mean diameter ∼5 nm, were investigated by means of DC magnetization and AC susceptibility over the temperature range of 4-400 K. All NPs present the same CoFe2O4 core, with different molecular surface coatings, increasing gradually the number of carbon atoms in the coating layer: glycine (C2H5NO2), alanine (C3H7NO2), aminobutanoic acid (C4H9NO2), aminohexanoic acid (C6H13NO2), and aminododecanoic acid (C12H25NO2). Samples were intentionally fabricated in order to modulate the core-core magnetic dipolar interaction, as the thickness of the coating layer increases with the number of carbon atoms in the coating molecule. The magnetic data of the uncoated CoFe2O4 NPs were also collected for comparison. All investigated CoFe2O4 NPs (coated and uncoated) are in a magnetically blocked state at room temperature as evidenced by ZFC/FC measurements and the presence of hysteresis with ∼700 Oe coercivity. Low temperature magnetization scans show slightly constricted hysteresis loops with coercivity decreasing systematically with a decreasing number of carbon atoms in the coating molecule, possibly resulting from differences in magnetic dipole coupling between NPs. Large thermomagnetic irreversibility, slow monotonic increase in the FC magnetization and non-saturation of the magnetization give evidence for the cluster glass (CG) nature in the CoFe2O4 NPs. The out of phase part (χ'') of AC susceptibility for all samples shows a clear frequency dependent hump which was analyzed to distinguish superparamagnetic (SPM), cluster glass (CG) and spin glass (SG) behavior by using Néel-Arrhenius, Vogel-Fulcher, and power law fittings. These analyses rule out the SPM state and suggest the presence of significant inter-cluster dipolar interaction, giving rise to CG cooperative freezing in the high-temperature region. In the low-temperature range, however, the disordered spins on the nanoparticle's surface play an important role in the formation of the SG-like state, as evidenced by Arrott plots and temperature dependency of dM/dH in the initial magnetization curves. In summary, the magnetic measurements showed that undercooling the system evolves from a SPM state of weakly interacting spin clusters, through the CG state induced by strong dipolar interaction, to the SG state resulting from the frustration of the disordered surface spins.

Single-Atom Gadolinium Anchored on Graphene Quantum Dots as a Magnetic Resonance Signal Amplifier.

A single-atom metal doped on carbonaceous nanomaterials has attracted increasing attention due to its potential applications as high-performance catalysts. However, few studies focus on the applications of such nanomaterials as nanotheranostics for simultaneous bioimaging and cancer therapy. Herein, it is pioneeringly demonstrated that the single-atom Gd anchored onto graphene quantum dots (SAGd-GQDs), with dendrite-like morphology, was successfully prepared. More importantly, the as-fabricated SAGd-GQDs exhibits a robustly enhanced longitudinal relaxivity (r1 = 86.08 mM-1 s-1) at a low Gd3+ concentration of 2 µmol kg-1, which is 25 times higher than the commercial Gd-DTPA (r1 = 3.44 mM-1 s-1). In vitro and in vivo studies suggest that the obtained SAGd-GQDs is a highly potent and contrast agent to obtain high-definition MRI, thereby opening up more opportunities for future precise clinical theranostics.

Nanostrategies to Develop Current Antiviral Vaccines.

Infectious diseases are a worldwide concern. They are responsible for increasing the mortality rate and causing economic and social problems. Viral epidemics and pandemics, such as the COVID-19 pandemic, force the scientific community to consider molecules with antiviral activity. A number of viral infections still do not have a vaccine or efficient treatment and it is imperative to search for vaccines to control these infections. In this context, nanotechnology in association with the design of vaccines has presented an option for virus control. Nanovaccines have displayed an impressive immune response using a low dosage. This review aims to describe the advances and update the data in studies using nanovaccines and their immunomodulatory effect against human viruses.

Nanocapsules for the co-delivery of selol and doxorubicin to breast adenocarcinoma 4T1 cells in vitro.

Nanocapsules (NCS-DOX) with an oily core of selol and a shell of poly(methyl vinyl ether-co-maleic anhydride) covalently conjugated to doxorubicin were developed. These nanocapsules are spherical, with an average hydrodynamic diameter of about 170 nm, and with negative zeta potential. NCS-DOX effectively co-delivered the selol and the doxorubicin into 4T1 cells and changed the intracellular distribution of DOX from the nuclei to the mitochondria. Moreover, a significantly increased cytotoxicity against 4T1 cells was observed, which is suggestive of additive or synergic effect of selol and doxorubicin. In conclusion, PVM/MA nanocapsules are suitable platforms to co-deliver drugs into cancer cells.

Magnetic nanohydrogel obtained by miniemulsion polymerization of poly(acrylic acid) grafted onto derivatized dextran.

This study describes the synthesis of magnetic nanohydrogels by miniemulsion polymerization technique. Dextran was derivatized by the glycidyl methacrylate to anchor vinyl groups on polysaccharides backbone, allowing its use as a macromonomer for miniemulsion polymerization, as confirmed by proton nuclear magnetic resonance spectroscopy (13C NMR). Magnetite nanoparticles were synthesized by coprecipitation, followed by air oxidation to maghemite. The results of X-ray diffractometry (XRD), Raman and transmission electron microscopy (TEM) analysis showed that maghemite nanoparticles were obtained with a diameter of 5.27nm. The entrapment of iron oxide nanoparticles in a dextran nanohydrogel matrix was confirmed by thermogravimetric analysis (TGA), scanning transmission electron microscopy (STEM) and Zeta potential data. The magnetic nanohydrogels presented superparamagnetic behavior and were colloidal stable in physiological during 30days. Our findings suggest that the synthesized magnetic nanohydrogel are potential candidates for use in drug delivery systems due to its physicochemical and magnetic properties.

Genotoxic and histopathological biomarkers for assessing the effects of magnetic exfoliated vermiculite and exfoliated vermiculite in Danio rerio.

Magnetic exfoliated vermiculite is a synthetic nanocomposite that quickly and efficiently absorbs organic compounds such as oil from water bodies. It was developed primarily to mitigate pollution, but the possible adverse impacts of its application have not yet been evaluated. In this context, the acute toxicity of magnetic exfoliated vermiculite and exfoliated vermiculite was herein assessed by genotoxic and histopathological biomarkers in zebrafish (Danio rerio). DNA fragmentation was statistically significant for all groups exposed to the magnetic exfoliated vermiculite and for fish exposed to the highest concentration (200mg/L) of exfoliated vermiculite, whereas the micronucleus frequency, nuclear abnormalities and histopathological alterations were not statistically significant for the fish exposed to these materials. In the intestinal lumen, epithelial cells and goblet cells, we found the presence of magnetic exfoliated vermiculite and exfoliated vermiculite, but no alterations or presence of the materials-test in the gills or liver were observed. Our findings suggest that the use of magnetic exfoliated vermiculite and exfoliated vermiculite during standard ecotoxicological assays caused DNA damage in D. rerio, whose alterations may be likely to be repaired, indicating that the magnetic nanoparticles have the ability to promote genotoxic damage, such as DNA fragmentation, but not mutagenic effects.

Spatial distribution of some trace and major elements in sediments of the Cávado estuary (Esposende, Portugal).

For the first time, the occurrence and spatial distribution of several elements, including some toxic metals, have been investigated in sediments of the estuary of the Cávado River (Esposende, Portugal). The pseudo total concentrations of Al, As, Cd, Co, Cr, Cu, Fe, Mg, Mn, Ni, Pb, Sn, V and Zn in sediments collected at 24 sites covering the tidal part of the estuary were determined. According to the concentrations measured, the Cávado estuary can be considered as non-contaminated. For most of the elements, the concentrations tended to be higher upstream. Only a moderate enrichment in Cr and Ni was detected in a few sites. An important decrease in concentration was observed for the most toxic metals compared to historical data reported in the literature. Several hotspots were identified, but even in those cases the amount of metals stored in the sediments does not represent a toxicological threat to living organisms.

Interferences of surfactants during determination of chlorophenols by acetylation coupled to headspace-solid phase microextraction-gas chromatography with an electron capture detector.

The micellar extraction (ME) of chlorophenols (CPs) from solid samples is rapid and avoids the use of organic solvents. The cationic surfactant cetyltrimethylammonium bromide (CTAB) is a powerful agent for ME of CPs. However, CTAB will be an important interference when the extracts are subsequently analyzed by direct solid phase microextraction (SPME) without a previous derivatization step. Therefore, CTAB is usually replaced by the nonionic surfactant polyoxyethylene-10-lauryl ether (POLE), which causes less interference but is less efficient in extracting CPs. In order to assess to what extent the derivatization of CPs with headspace (HS) sampling would be able to reduce surfactant interferences, CPs were measured in the presence of CTAB or POLE using acetylation and HS-SPME coupled to GC with an electron capture detector. Experiments were carried out both in water and in a 0.1 g/mL solution of NaCl (salting out agent). Acetylation and HS-SPME strongly decreased the interference of CTAB for CP determination. Therefore, the application of CTAB followed by SPME determination for an efficient ME of CPs from solid samples should be reconsidered since using CTAB with HS-SPME after acetylation proved to be a potential tool for CP determination in those matrixes after method optimization.

Pentachlorophenol toxicity to a mixture of Microcystis aeruginosa and Chlorella vulgaris cultures.

Pentachlorophenol (PCP) is a priority pollutant due to its persistence and high toxicity. For the first time, PCP effects were investigated at laboratory scale on co-cultures of two ubiquitous freshwater phytoplankton species: the cyanobacterium Microcystis aeruginosa and the microalgae Chlorella vulgaris. The cells were exposed to environmental levels of PCP for 10 days in Fraquil culture medium, at nominal concentrations from 0.1 to 10,000 µg L(-1). Growth was assessed by area under growth curve (cell count vs. time). The phytoplankton community structure can be changed as a consequence of a PCP contamination. Low µg L(-1) levels of PCP are advantageous to M. aeruginosa. This is the first report of the promoting effect of PCP on the growth of aquatic cyanobacteria, using mixtures with microalgae. As a result of the direct toxic effects of high PCP concentrations on M. aeruginosa, C. vulgaris cell count increased given that in biological controls M. aeruginosa inhibited the C. vulgaris growth. At 16.7 mg L(-1), PCP already had direct toxic effects also on the microalga. The pH of culture medium tended to decrease with increasing PCP concentrations, which was mostly related to the growth inhibition of cyanobacterium caused by PCP. The PCP concentration was stable in the co-cultures, which differed from what has been observed in monocultures of the same two species. Short-term laboratory assays with two phytoplankton species gives important information on the species interactions, namely possible direct and indirect effects of a toxicant, and must be considered in ecotoxicity studies regarding environmental extrapolations.

Stability of chlorophenols and their acetylated derivatives in water: sample storage procedures.

The determination of chlorophenols (CPs) in water samples is a subject of increasing interest. Reduction of sample storage space and the stability of CPs when present at very low levels are still problems that deserve research. The stability of CPs at ng/L levels at different temperatures and in the presence or absence of sodium carbonate and acetic anhydride was studied for up to 39 days. Stable and reproducible CP concentrations for about a month of storage in both river and wastewater were achieved in two storage conditions as follows: at -18 degrees C with addition of 10% sodium chloride; and at 4 degrees C with addition of both 10% sodium chloride and 10 mglmL sodium carbonate. These sample treatments are good alternatives to the immobilization of CPs on SPE cartridges in terms of both analyte stability and saving of storage space.

Cyanobacterium Microcystis aeruginosa response to pentachlorophenol and comparison with that of the microalga Chlorella vulgaris.

Pentachlorophenol (PCP) effects on a strain of the cyanobacterium Microcystis aeruginosa were investigated at laboratory scale. This is the first systematic ecotoxicity study of the effects of PCP on an aquatic cyanobacterium. The microalga Chlorella vulgaris was studied in the same conditions as the cyanobacterium, in order to compare the PCP toxicity and its removal by the species. The cells were exposed to environmental levels of PCP during 10 days, in Fraquil culture medium, at nominal concentrations from 0.01 to 1000 µg L(-1), to the cyanobacterium, and 0.01 to 5000 µg L(-1), to the microalga. Growth was assessed by area under growth curve (AUC, optical density vs time) and chlorophyll a content (chla). The toxicity profiles of the two species were very different. The calculated effective concentrations EC20 and EC50 were much lower to M. aeruginosa, and its growth inhibition expressed by chla was concentration-dependent while by AUC was not concentration-dependent. The cells might continue to divide even with lower levels of chla. The number of C. vulgaris cells decreased with the PCP concentration without major impact on the chla. The effect of PCP on M. aeruginosa is hormetic: every concentration studied was toxic except 1 µg L(-1), which promoted its growth. The legal limit of PCP set by the European Union for surface waters (1 µg L(-1)) should be reconsidered since a toxic cyanobacteria bloom might occur. The study of the removal of PCP from the culture medium by the two species is an additional novelty of this work. M. aeruginosa could remove part of the PCP from the medium, at concentrations where toxic effects were observed, while C. vulgaris stabilized it.

A top-down synthesis route to ultrasmall multifunctional Gd-based silica nanoparticles for theranostic applications.

New, ultrasmall nanoparticles with sizes below 5 nm have been obtained. These small rigid platforms (SRP) are composed of a polysiloxane matrix with DOTAGA (1,4,7,10-tetraazacyclododecane-1-glutaric anhydride-4,7,10-triacetic acid)-Gd(3+) chelates on their surface. They have been synthesised by an original top-down process: 1) formation of a gadolinium oxide Gd2O3 core, 2) encapsulation in a polysiloxane shell grafted with DOTAGA ligands, 3) dissolution of the gadolinium oxide core due to chelation of Gd(3+) by DOTAGA ligands and 4) polysiloxane fragmentation. These nanoparticles have been fully characterised using photon correlation spectroscopy (PCS), transmission electron microscopy (TEM), a superconducting quantum interference device (SQUID) and electron paramagnetic resonance (EPR) to demonstrate the dissolution of the oxide core and by inductively coupled plasma mass spectrometry (ICP-MS), mass spectrometry, fluorescence spectroscopy, (29)Si solid-state NMR, (1)H NMR and diffusion ordered spectroscopy (DOSY) to determine the nanoparticle composition. Relaxivity measurements gave a longitudinal relaxivity r1 of 11.9 s(-1) mM(-1) per Gd at 60 MHz. Finally, potentiometric titrations showed that Gd(3+) is strongly chelated to DOTAGA (complexation constant logß110 =24.78) and cellular tests confirmed the that nanoconstructs had a very low toxicity. Moreover, SRPs are excreted from the body by renal clearance. Their efficiency as contrast agents for MRI has been proved and they are promising candidates as sensitising agents for image-guided radiotherapy.

Extraction and preconcentration techniques for chromatographic determination of chlorophenols in environmental and food samples.

Methods for chlorophenols (CPs) determination (with low limits of detection) that can be applied to real environmental samples (waters, sediments, soils, biological tissues) and food are reviewed. Special emphasis is given to sampling, storage conditions and the application of preconcentration techniques for the determination of CPs using chromatographic methods. Solid phase extraction, solid phase microextraction, stir bar sorptive extraction, liquid phase microextraction, dispersive liquid-liquid microextraction, liquid-liquid-liquid microextraction and purge and trap methods are considered. Methods for microwave and ultrasonic extraction of CPs from solid matrices are also focused.

A noninvasive, remote and precise method for temperature and concentration estimation using magnetic nanoparticles.

This study describes an approach for remote measuring of on-site temperature and particle concentration using magnetic nanoparticles (MNPs) via simulation and also experimentally. The sensor model indicates that under different applied magnetic fields, the magnetization equation of the MNPs can be discretized to give a higher-order nonlinear equation in two variables that consequently separates information regarding temperature and particle concentration. As a result, on-site tissue temperature or nanoparticle concentration can be determined using remote detection of the magnetization. In order to address key issues in the higher-order equation we propose a new solution method of the first-order model from the perspective of the generalized inverse matrix. Simulations for solving the equation, as well as to optimize the solution of higher equations, were carried out. In the final section we describe a prototype experiment used to investigate the measurement of the temperature in which we used a superconducting magnetometer and commercial MNPs. The overall error after nine repeated measurements was found to be less than 0.57 K within 310-350 K, with a corresponding root mean square of less than 0.55 K. A linear relationship was also found between the estimated concentration of MNPs and the sample's mass.

A headspace SPME-GC-ECD method suitable for determination of chlorophenols in water samples.

A headspace solid phase microextraction coupled to gas chromatography with electron capture detector (HS-SPME-GC-ECD) method was optimized for the determination of seven chlorophenols (CPs) with different levels of chlorination. This is the first time that HS-SPME-GC-ECD with acetylation of the analytes is used for the simultaneous determination of CPs in water samples. The influence of fibre type, derivatization conditions, salt addition, temperature and time of extraction and temperature of desorption was checked. Possible sources of contamination and analyte losses were considered. The best results were obtained with the polydimethylsiloxane/divinylbenzene fibre, derivatization by acetylation using 100 µL of acetic anhydride and 0.1 g of anhydrous sodium carbonate per 10 mL of sample, salt addition of 100 g L(-1) sodium chloride, extraction at 70 °C for 60 min and desorption in the GC injector at 260 °C for 6 min. The limits of detection (LOD) for monochlorophenols were 12 and 122 ng L(-1) for 2-chlorophenol and 4-chlorophenol, respectively. For polychlorinated CPs, the LODs were lower than 6 ng L(-1), values similar to the existing methods that use SPME with derivatization for CPs determination in water samples. The method is suitable for the determination of CPs in most environmental aqueous samples. Repeatability and reproducibility were less than 16.8% and 11.7%, respectively. The optimized method was successfully applied for the analysis of waters with complex matrices such as river and estuarine water samples.