Airborne environmental fine particles induce intense inflammatory response regardless of the absence of heavy metal elements.

Airborne environmental particles (EP) more commonly referred as particulate matter (PM) are an illustrative marker of air pollution that is associated with adverse effects on human health. Considering, PM is a complex mixture, not only in terms of its chemical composition, but also in the range of particle size, it is difficult to identify which attribute contributes more for the toxicity. Currently, there is no report about the immunotoxicological effects caused by PM with reduced content of heavy metals. This study intends to address this gap and provides a detailed characterization and immunotoxicity evaluation of PM collected in an urban area with heavy traffic congestion. Environmental particles were separated by different sizes though a sucrose gradient. This method allowed to achieve 4 sized fractions: EP f 15 % with a mean diameter of 284 nm ± 1.86 nm, EP f 25 % with a mean diameter of 461 nm ± 1.72 nm, EP f 35 % with a mean diameter of 1845 nm ± 251 nm and EP f 45 % with a mean diameter of 2204 nm ± 310 nm. Only the fractions with the smallest sizes (EP f 15 % and EP f 25 %) were subsequently studied. The chemical composition of both fractions was not substantially different, and the dominant elements were C, O, Ca and K. Only EP f 25 % showed to have a small amount of Fe. Therefore, the heavy metal elements were eliminated through centrifugation. Essentially, we found that the EP f 15 % was more cytotoxic in RAW 264.7 cells than EP f 25 %, which indicates the smaller size as the motive for the higher toxicity. In addition, both fractions of EP presented a good internalization in macrophages after 2 h exposure and induced the production of reactive oxygen species in a concentration-dependent manner. Moreover, EP f 15 % and EP f 25 % led to a strong secretion of proinflammatory cytokines (TNF-α and IL-6) in human peripheral blood mononuclear cells (hPBMCs) in the 3 concentrations tested. The inflammatory response observed was independent of the presence of heavy metals and endotoxins, since these last were suppressed by using polymyxin B sulfate. This report emphasizes the importance of an adequate physicochemical characterization and adequate controls in the experiments to achieve a right interpretation of the biological effects caused by PM.

Highly fluorescent and superparamagnetic nanosystem for biomedical applications.

This work reports on highly fluorescent and superparamagnetic bimodal nanoparticles (BNPs) obtained by a simple and efficient method as probes for fluorescence analysis and/or contrast agents for MRI. These promising BNPs with small dimensions (ca. 17 nm) consist of superparamagnetic iron oxide nanoparticles (SPIONs) covalently bound with CdTe quantum dots (ca. 3 nm). The chemical structure of the magnetic part of BNPs is predominantly magnetite, with minor goethite and maghemite contributions, as shown by Mössbauer spectroscopy, which is compatible with the x-ray diffraction data. Their size evaluation by different techniques showed that the SPION derivatization process, in order to produce the BNPs, does not lead to a large size increase. The BNPs saturation magnetization, when corrected for the organic content of the sample, is ca. 68 emu g-1, which is only slightly reduced relative to the bare nanoparticles. This indicates that the SPION surface functionalization does not change considerably the magnetic properties. The BNP aqueous suspensions presented stability, high fluorescence, high relaxivity ratio (r 2/r 1 equal to 25) and labeled efficiently HeLa cells as can be seen by fluorescence analysis. These BNP properties point to their applications as fluorescent probes as well as negative T 2-weighted MRI contrast agents. Moreover, their potential magnetic response could also be used for fast bioseparation applications.

Synthesis of Highly Luminescent Silica-Coated Upconversion Nanoparticles from Lanthanide Oxides or Nitrates Using Co-Precipitation and Sol-Gel Methods.

Upconversion nanoparticles (UCNPs) are under consideration for their use as bioimaging probes with enhanced optical performance for real time follow-up under non-invasive conditions. Photostable and core-shell NaYF4:Yb3+, Er3+-SiO2 UCNPs obtained by a novel and simple co-precipitation method from lanthanide nitrates or oxides were herein synthesized for the first time. The sol-gel Stöber method followed by oven or supercritical gel drying was used to confer biocompatible surface properties to UCNPs by the formation of an ultrathin silica coating. Upconversion (UC) spectra were studied to evaluate the fluorescence of UCNPs upon red/near infrared (NIR) irradiation. ζ-potential measurements, TEM analyses, XRD patterns and long-term physicochemical stability were also assessed and confirmed that the UCNPs co-precipitation synthesis is a shape- and phase-controlling approach. The bio- and hemocompatibility of the UCNPs formulation with the highest fluorescence intensity was evaluated with murine fibroblasts and human blood, respectively, and provided excellent results that endorse the efficacy of the silica gel coating. The herein synthesized UCNPs can be regarded as efficient fluorescent probes for bioimaging purposes with the high luminescence, physicochemical stability and biocompatibility required for biomedical applications.

Experimental and modeling study of ZnO:Ni nanoparticles for near-infrared light emitting diodes.

This work is devoted to the synthesis and study of the different properties of ZnO nanoparticles (NPs) doped with the Ni element. We have used a simple co-precipitation technique for the synthesis of our samples and various structural, morphological and optical techniques for their analysis. Energy-Dispersive X-ray spectroscopy (EDX) confirms the stoichiometry of the samples. The X-Ray Diffraction (XRD) patterns reveal the hexagonal wurtzite phase of polycrystalline ZnO with a P63mc space group. Debye Scherrer and Williamson-Hall methods show that the average size of crystallites is around 40 nm. Transmission electron microscopy (TEM) images confirm the XRD results. The optical spectrum of Zn0.95Ni0.5O shows the presence of near-band-edge (NBE) ultraviolet emission. The absorption defect bands appearing near the blue-green region and near infrared emission are attributed to the Ni2+ intra-3d luminescence. The electronic structure of the Ni2+ doped ZnO NPs confirms the T d site symmetry of Ni2+ in the ZnO host crystal and leads to a perfect correlation between calculated and experimental energy levels.

Evaluation of the Photocatalytic Activity of Distinctive-Shaped ZnO Nanocrystals Synthesized Using Latex of Different Plants Native to the Amazon Rainforest.

ZnO nanocrystals with three different morphologies have been synthesized via a simple sol-gel-based method using Brosimum parinarioides (bitter Amapá) and Parahancornia amapa (sweet Amapá) latex as chelating agents. X-ray diffraction (XRD) and electron diffraction patterns (SAED) patterns showed the ZnO nanocrystals were a pure hexagonal wurtzite phase of ZnO. XRD-based spherical harmonics predictions and HRTEM images depicted that the nanocrystallites constitute pitanga-like (~15.8 nm), teetotum-like (~16.8 nm), and cambuci-like (~22.2 nm) shapes for the samples synthesized using bitter Amapá, sweet Amapá, and bitter/sweet Amapá chelating agent, respectively. The band gap luminescence was observed at ~2.67-2.79 eV along with several structural defect-related, blue emissions at 468-474 nm (VO, VZn, Zni), green emissions positioned at 513.89-515.89 (h-VO+), and orange emission at 600.78 nm (VO+-VO++). The best MB dye removal efficiency (85%) was mainly ascribed to the unique shape and oxygen vacancy defects found in the teetotum-like ZnO nanocrystals. Thus, the bitter Amapá and sweet Amapá latex are effective chelating agents for synthesizing distinctive-shaped ZnO nanocrystals with highly defective and remarkable photocatalytic activity.

Supercritically dried superparamagnetic mesoporous silica nanoparticles for cancer theranostics.

Mesoporous silica nanoparticles with a superparamagnetic iron oxide core were prepared in this work, in order to obtain multifunctional platforms with adequate features for cancer theranostics. Three different core-shell nanocomplexes were obtained: IO-OAm/mSiO2, IO-APTES/mSiO2 and IO/SiO2/mSiO2. In the case of IO-OAm/mSiO2 and IO-APTES/mSiO2, iron oxide (IO) was obtained by thermal decomposition, having in this case a coating of oleylamine (OAm) that was in the second formulation exchanged by (3-aminopropyl)triethoxysilane ligand (APTES). Regarding the IO/SiO2/mSiO2 formulation, iron oxide was synthesized by microemulsion. The mesoporous silica shell (mSiO2) on the IO nanoparticles was obtained by sol-gel and the final materials were dried by supercritical fluids drying. VSM confirmed the superparamagnetic behaviour of the nanoparticles, leading to MS of 4.0, 1.8 and 10.2 emu·g-1, for IO-OAm/mSiO2, IO-APTES/mSiO2 and IO/SiO2/mSiO2, respectively. NMR relaxometry has shown the potential of these nanoparticles to be used as T2 contrast agents, with r2 values as high as 63.93 s-1·mM-1 Fe. The three types of nanoparticles exhibited loading contents of epirubicin of ~3% and drug release percentages of 19% for IO-OAm/mSiO2, 24% for IO-APTES/mSiO2 and 31% for IO/SiO2/mSiO2. The cytotoxicity of drug-loaded and non-loaded most promising nanoparticles was assessed, showing high potential of these platforms for application as anticancer drug carriers.

Biofunctionalized magnetic hydrogel nanospheres of magnetite and kappa-carrageenan.

Magnetic hydrogel kappa-carrageenan nanospheres were successfully prepared via water-in-oil (w/o) microemulsions combined with thermally induced gelation of the polysaccharide. The size of the nanospheres (an average diameter of about 50 and 75 nm) was modulated by varying the concentration of surfactant. The nanospheres contained superparamagnetic magnetite nanoparticles (average diameter 8 nm), previously prepared by co-precipitation within the biopolymer. Carboxyl groups, at a concentration of about 4 mmol g(-1), were successfully grafted at the surface of these magnetic nanospheres via carboxymethylation of the kappa-carrageenan. The carboxylated nanospheres were shown to be thermo-sensitive in the 37-45 degrees C temperature range, indicating their potential as thermally controlled delivery systems for drugs and/or magnetic particles at physiological temperatures. Finally, preliminary results have been obtained for IgG antibody conjugation of the carboxylated nanospheres and the potential of these systems for bio-applications is discussed.

Development of a biocompatible magnetic nanofluid by incorporating SPIONs in Amazonian oils.

Higher quality magnetic nanoparticles are needed for use as magnetic nanoprobe in medical imaging techniques and cancer therapy. Moreover, the phytochemistry benefits of some Amazonian essential oils have sparked great interest for medical treatments. In this work, a magnetic nanoprobe was developed, allying the biocompatibility and superparamagnetism of iron oxide nanoparticles (SPIONs) with benefits associated with Amazonian oils from Copaiba and Andiroba trees. SPIONs were obtained by two thermal decomposition procedures and different amounts of precursors (iron acetylacetonates). Their characterization was accomplished by Fourier transform infrared spectroscopy, thermogravimetric analysis, transmission electron microscopy (TEM), X-ray diffraction (XRD), Mössbauer spectroscopy and magnetization. The obtained nanoparticles composition and magnetic properties were not affected by the relative proportion of iron(II) and iron(III) in the precursor system. However, when changing the reducing and stabilizing agents the coating layer shows different compositions/relative weight - the more promising SPIONs have a coating mainly composed by oleylamine and an iron oxide:coating wt% ratio of 55:45. Nanoparticles size distributions were very narrow and centred in the average size of 6-7nm. Cellular assays confirmed the biocompatibility of SPIONs and their effective internalization in human colon cancer cells. Mössbauer/XRD results indicated maghemite as their main iron oxide phase, but traces of magnetite proved to be present. Magnetization saturations of 57emu/g at 5K and 42emu/g at 300K were achieved. With incorporation of SPIONs into Copaiba and Andiroba essential oils, these values show a 4-fold decrease, but the supermagnetic behaviour is preserved providing the effective formation of a nanofluid.

Distinct microbial populations are tightly linked to the profile of dissolved iron in the methanic sediments of the Helgoland mud area, North Sea.

Iron reduction in subseafloor sulfate-depleted and methane-rich marine sediments is currently a subject of interest in subsurface geomicrobiology. While iron reduction and microorganisms involved have been well studied in marine surface sediments, little is known about microorganisms responsible for iron reduction in deep methanic sediments. Here, we used quantitative PCR-based 16S rRNA gene copy numbers and pyrosequencing-based relative abundances of bacteria and archaea to investigate covariance between distinct microbial populations and specific geochemical profiles in the top 5 m of sediment cores from the Helgoland mud area, North Sea. We found that gene copy numbers of bacteria and archaea were specifically higher around the peak of dissolved iron in the methanic zone (250-350 cm). The higher copy numbers at these depths were also reflected by the relative sequence abundances of members of the candidate division JS1, methanogenic and Methanohalobium/ANME-3 related archaea. The distribution of these populations was strongly correlated to the profile of pore-water Fe(2+) while that of Desulfobacteraceae corresponded to the pore-water sulfate profile. Furthermore, specific JS1 populations also strongly co-varied with the distribution of Methanosaetaceae in the methanic zone. Our data suggest that the interplay among JS1 bacteria, methanogenic archaea and Methanohalobium/ANME-3-related archaea may be important for iron reduction and methane cycling in deep methanic sediments of the Helgoland mud area and perhaps in other methane-rich depositional environments.

In situ synthesis of magnetite nanoparticles in carrageenan gels.

Magnetite nanoparticles have been successfully synthesized in the presence of carrageenan polysaccharides using an in situ coprecipitation method. Iron coordination to the sulfate groups of the polysaccharide was confirmed by FTIR. The polysaccharide type (kappa, iota, or lambda) and concentration have been varied and their effects on particle morphology and chemical stability of the resultant nanocomposite investigated. The presence of carrageenan induces the formation of smaller particles, compared to those formed in the absence of polymer, and their average size depends on the nature and concentration of the polysaccharide used. The chemical stability of magnetite nanoparticles toward oxidation was also seen to depend on biopolymer type with magnetite formed in iota-carrageenan showing the highest chemical stability. A general tendency toward lower stability is observed as the polysaccharide concentration is increased. It is suggested that magnetite chemical stability in the carrageenan composites is determined by a fine balance between particle size and gel strength, the latter determining oxygen diffusion rates through the medium.