EuIII and TbIII upconversion intermediated by interparticle energy transfer in functionalized NaLnF4 nanoparticles.

Lanthanide (LnIII)-doped sodium gadolinium tetrafluoride (NaGdF4) nanoparticles have been excelled as attractive upconversion systems for anti-counterfeiting or energy conversion for instance, with a special interest in the visible upconversion of EuIII and TbIII. The core@shell architecture has enabled the bright upconversion of EuIII and TbIII in this matrix by interfacial energy transfer sensibilized by the TmIII/YbIII pair. Another approach to enable EuIII and TbIII upconversion could be the interparticle energy transfer (IPET) between LnIII-doped sensitizer and acceptor nanoparticles. Yet, the low molar absorptivity of the LnIII through 4f ↔ 4f electronic transitions and the large distance between the nanoparticles are shortcomings that should decrease the energy transfer efficiency. On the other hand, it is feasible to predict that the association of organic ligands displaying large molar absorptivity on the acceptor nanoparticle surface could help to overcome the absorption limitation. Inspired by this exciting possibility, herein, we present the EuIII/TbIII upconversion intermediated by IPET between the donor TmIII, YbIII-doped NaGdF4 nanoparticle and the acceptor LnIII-doped NaGdF4 (Ln = Eu and/or Tb) nanoparticles functionalized with a series organic ligands on the surface (tta- = thenoyltrifluoroacetonate, acac- = acetylacetonate, or 3,5-bbza- = 3,5-dibromebenzoate). Either in solid state or in suspension, upon excitation at 980 nm, visible EuIII/TbIII upconversion could be observed. This emission comes from the absorption of the TmIII, YbIII pair in the donor nanoparticle, followed by IPET from the TmIII excited levels to the ligand singlet/triplet states on the acceptor nanoparticle surface, ligand-to-EuIII/TbIII energy transfer, and upconversion emission. Spectroscopic evidences from the analysis of the donor level lifetimes indicate the contribution of non-radiative energy transfer for the IPET mechanism; the radiative mechanism also contributes for the IPET. Moreover, the design herein introduced enables the development of luminescence temperature probes with relative thermal sensitivity as high as 1.67% K-1 at 373 K. Therefore, this new upconversion pathway opens an avenue of possibilities in an uncharted territory to tune the visible upconversion of LnIII ions.

Synergy of shaped-induced enhanced Raman scattering to improve surface-enhanced Raman scattering signal in the thiram molecule detection.

Herein, we explore the combined effect of Shaped-Induced Enhanced Raman Scattering (SIERS) and Surface-Enhanced Raman Scattering (SERS) for detecting thiram molecules. We fabricated V-shaped microchannels on a silicon (100) substrate through a standard lithography and etching process. The analysis of SIERS@SERS was performed for Si-V substrates modified with AuNRs with different thiram concentrations, 10-7 to 10-10 mol/L. The spectra were collected for different regions of the Si-V substrates, i.e., in the inside, edge, between (flat top), and far from Si-V (coffee-ring AuNRs aggregation) to assess the performance of Si-V microchannels obtained. The IDMAP statistical projection reveals a higher silhouette coefficient of 0.91 for the inside of Si-V, indicating a more excellent spectral reproducibility with closer relative intensities. The device platform used in this study stands out as a robust option for commercial sensors, demonstrating exceptional sensitivity in detecting a diverse range of molecules, even at low concentrations.

The microwave-assisted synthesis of silica nanoparticles and their applications in a soy plant culture.

A rapid and environmentally friendly synthesis of thermodynamically stable silica nanoparticles (SiO2-NPs) from heating via microwave irradiation (MW) compared to conductive heating is presented, as well as their evaluations in a soy plant culture. The parameters of time and microwave power were evaluated for the optimization of the heating program. Characterization of the produced nanomaterials was obtained from the dynamic light scattering (DLS) and zeta potential analyses, and the morphology of the SiO2-NPs was obtained by transmission electron microcopy (TEM) images. From the proposed synthesis, stable, monodisperse, and amorphous SiO2-NPs were obtained. Average sizes reported by DLS and TEM techniques were equal to 11.6 nm and 13.8 nm, respectively. The water-stable suspension of SiO2-NPs shows a zeta potential of -31.80 mV, and the homogeneously spheroidal morphology observed by TEM corroborates with the low polydispersity values (0.300). Additionally, the TEM with fast Fourier transform (FFT), demonstrates the amorphous characteristic of the nanoparticles. The MW-based synthesis is 30 times faster, utilizes 4-fold less reagents, and is ca. 18-fold cheaper than conventional synthesis through conductive heating. After the synthesis, the SiO2-NPs were added to the soil used for the cultivation of soybeans, and the homeostasis for Cu, Ni, and Zn was evaluated through the determination of their total contents by inductively coupled plasma mass spectrometry (ICP-MS) in soy leaves and also through bioimages obtained using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Although the results corroborate through both techniques, they also show the influence of these nanoparticles on the elemental distribution of the leaf surface with altered homeostasis of such elements from both transgenic crops compared to the control group.

Bifunctional Temperature and Oxygen Dual Probe Based on Anthracene and Europium Complex Luminescence.

In this work, we synthesized a polydimethylsiloxane membrane containing two emitter groups chemically attached to the membrane structure. For this, we attached the anthracene group and the [Eu(bzac)3] complex as blue and red emitters, respectively, in the matrix via hydrosilylation reactions. The synthesized membrane can be used as a bifunctional temperature and oxygen ratiometric optical probe by analyzing the effects that temperature changes and oxygen levels produce on the ratio of anthracene and europium(III) emission components. As a temperature probe, the system is operational in the 203-323 K range, with an observed maximum relative sensitivity of 2.06% K-1 at 290 K and temperature uncertainties below 0.1 K over all the operational range. As an oxygen probe, we evaluated the ratiometric response at 25, 30, 35, and 40 °C. These results show an interesting approach to obtaining bifunctional ratiometric optical probes and also suggest the presence of an anthracene → europium(III) energy transfer, even though there is no chemical bonding between species.

Silicon Microchannel-Driven Raman Scattering Enhancement to Improve Gold Nanorod Functions as a SERS Substrate toward Single-Molecule Detection.

The investigation of enhanced Raman signal effects and the preparation of high-quality, reliable surface-enhanced Raman scattering (SERS) substrates is still a hot topic in the SERS field. Herein, we report an effect based on the shape-induced enhanced Raman scattering (SIERS) to improve the action of gold nanorods (AuNRs) as a SERS substrate. Scattered electric field simulations reveal that bare V-shaped Si substrates exhibit spatially distributed interference patterns from the incident radiation used in the Raman experiment, resulting in constructive interference for an enhanced Raman signal. Experimental data show a 4.29 increase in Raman signal intensity for bare V-shaped Si microchannels when compared with flat Si substrates. The combination of V-shaped microchannels and uniform aggregates of AuNRs is the key feature to achieve detections in ultra-low concentrations, enabling reproducible SERS substrates having high performance and sensitivity. Besides SIERS effects, the geometric design of V-shaped microchannels also enables a "trap" to the molecule confinement and builds up an excellent electromagnetic field distribution by AuNR aggregates. The statistical projection of SERS spectra combined with the SIERS effect displayed a silhouette coefficient of 0.83, indicating attomolar (10-18 mol L-1) detection with the V-shaped Si microchannel.

Aptasensor based on a flower-shaped silver magnetic nanocomposite enables the sensitive and label-free detection of troponin I (cTnI) by SERS.

Acute myocardial infarction (AMI) is nowadays the leading death cause worldwide. For that reason, the early diagnosis of AMI is of central importance to reduce the risk of death. In this sense, aptamer-based sensors for surface-enhanced Raman spectroscopy (SERS aptasensors) emerged as an interesting alternative for future high-performance diagnostic tools. SERS aptasensors combine the fast, precise, and sensitive nature of SERS measurements with the selectivity of aptamers for specific biological targets. Herein, we report an efficient SERS aptasensor for the detection of cardiac troponin I (cTnI), a gold-standard biomarker for AMI. Our SERS platform comprises a magnetite core with an intermediate silica shell, and a flower-shaped silver layer (Fe3O4@SiO2@Ag) to confer excellent plasmonic properties and ease of collection by magnetism. The branched silver structure combined with magnetic aggregation offers a high near-field amplification to superior SERS performance. Additionally, a tailored DNA aptamer with high specificity for cTnI was anchored to the silver surface to produce the aptasensor with increased sensing capability towards cTnI. With our SERS aptasensor, a cTnI concentration as low as 10 ng ml-1 (10-11 mol l-1) could be detected. This value is ten times lower than the upper threshold of the typical concentration range of cTnI of AMI patients. Hence, our SERS aptasensor holds great promise to be explored in AMI diagnosis.

Raman spectroscopy-in situ characterization of reversibly intercalated oxygen vacancies in α-MoO3.

This work reports on the in situ strategy to reversibly generate or suppress oxygen vacancies on α-MoO3 which were probed by Raman spectroscopy. Reversible changes in two features of the α-MoO3 Raman spectrum could be correlated to the generation of oxygen vacancies: displacement of the T b band frequency and the intensity decrease of the symmetrical stretching (ν s) band. These two features could be used to qualitatively describe oxygen vacancies. Raman results also indicate that oxygen vacancies are located in the interlayer region of the α-MoO3 lattice. This observation is corroborated by in situ X-ray diffraction, which also indicates the absence of nonstoichiometric phase transitions.

Investigation of citric acid-assisted sol-gel synthesis coupled to the self-propagating combustion method for preparing bioactive glass with high structural homogeneity.

In this research, the mechanism of an efficient strategy for the synthesis of 58S bioglass with high structural homogeneity by a citric acid assisted sol-gel route was investigated. This is an interesting approach to prepare bioactive glass via the sol-gel method with application potential in bone tissue engineering and also for the development of new biomedical devices. Herein, 58S bioglass was synthesized by two routes: conventional sol-gel method (CSG) and citric acid assisted sol-gel route coupled to the self-propagating combustion method (SPC). The effects of citric acid on the temperature required for 58S vitreous consolidation, long- and short-range ordering were investigated by several analysis techniques. Results suggested that citric acid molecules serve as an effective molecular template formed by molecular network raised from intermolecular forces, especially the hydrogen bonds, resulting from the chemical interactions between the COOH and hydroxyl groups (water, ethanol, POH, SiOH). In this scenario, citric acid controls the phase segregation during the drying and combustion steps of the gel in the SPC method by establishing chemical interactions (hydrogen bonds) with the superficial silanol groups present on the small-sized silica nanoparticles present in the sol governing their growth. Besides these mentioned features, the self-propagating combustion behavior exhibited by the nitrate-citrate in the SPC xerogel during the combustion step allowed the removal of the organic load and the consolidation of the vitreous structure at a temperature considerably lower than the sample obtained by the CSG method. Consequently, the SPC method leads to the formation of a glass structure with high homogeneity for the 58S, whereas the conventional sol-gel method produces a matrix enriched with calcium phosphate crystalline nuclei - glass-ceramic.

Analysis of the effects of mesoporous silica particles SBA-15 and SBA-16 in Streptococcus pneumoniae transformation process.

Streptococcus pneumoniae are natural competent bacteria which requires the presence of a pheromone-like molecule to do the transformation process. This study verified the influence of mesoporous silica (SBA-15 and SBA-16) on the transformation process in S. pneumoniae using a donor DNA obtained from a mutant strain of this microorganism (Sp360∆luxS). The results showed that mesoporous silica SBA-15 and SBA-16 particles doubled the transformation ratio frequency compared with negative control (without nanoparticles) in using SBA-15 (ratio 1.81 ± 0.04) and SBA-16 (ratio 2.18 ± 0.22). We demonstrated the how mesoporous silica nanoparticles were able to increase the pneumococcus transformations, which could possibly lead to the acquisition of virulence factor genes and resistance of antibiotics.

Comprehensive in vitro and in vivo studies of novel melt-derived Nb-substituted 45S5 bioglass reveal its enhanced bioactive properties for bone healing.

The present work presents and discusses the results of a comprehensive study on the bioactive properties of Nb-substituted silicate glass derived from 45S5 bioglass. In vitro and in vivo experiments were performed. We undertook three different types of in vitro analyses: (i) investigation of the kinetics of chemical reactivity and the bioactivity of Nb-substituted glass in simulated body fluid (SBF) by 31P MASNMR spectroscopy, (ii) determination of ionic leaching profiles in buffered solution by inductively coupled plasma optical emission spectrometry (ICP-OES), and (iii) assessment of the compatibility and osteogenic differentiation of human embryonic stem cells (hESCs) treated with dissolution products of different compositions of Nb-substituted glass. The results revealed that Nb-substituted glass is not toxic to hESCs. Moreover, adding up to 1.3 mol% of Nb2O5 to 45S5 bioglass significantly enhanced its osteogenic capacity. For the in vivo experiments, trial glass rods were implanted into circular defects in rat tibia in order to evaluate their biocompatibility and bioactivity. Results showed all Nb-containing glass was biocompatible and that the addition of 1.3 mol% of Nb2O5, replacing phosphorous, increases the osteostimulation of bioglass. Therefore, these results support the assertion that Nb-substituted glass is suitable for biomedical applications.

Proof of concept for a passive sampler for monitoring of gaseous elemental mercury in artisanal gold mining.

Mercury emissions from artisanal gold mining operations occurring in roughly 80 developing countries are a major workplace health hazard for millions of people as well as the largest contributor to global mercury pollution. There are no portable, cheap, and rapid methods able to inform workers or health practitioners of mercury exposure on site in remote locations. In this work, a proof of concept for a miniaturized mercury sampler, prepared by the direct reduction of gold into the porous nanostructures of Vycor glass (PVG), is introduced. Mercury retention on the PVG/Au sampler induces significant color changes, due to the formation of Au-Hg amalgam that affects the surface plasmon resonance characteristics of the material. The color change can potentially be quantified by the analysis of pictures obtained with a cell phone camera rapidly and onsite. Laboratory experiments showed the viability of using PVG/Au as passive sampler for monitoring of Hg°. PVG/Au samplers were then deployed in an artisanal and small-scale gold mining (ASGM) operations in Burkina Faso and it was able to indicate personal mercury exposures. The amount of mercury quantified in the samplers for all miners was higher than the current personal exposure limit set by the US Occupational Safety & Health Administration (OSHA).

The importance of evaluating the real metal concentration in nanoparticles post-synthesis for their applications: A case-study using silver nanoparticles.

To determine whether the effect observed in a study is related to the nanoparticle only or to their synergic effect with the "free" metal ions, the real concentration of silver (104±8 and 100±2 mg L(-1)) after AgNP synthesis is obtained through ICP-MS and ICP OES in the solution after the AgNP synthesis and in different fractions after centrifugation (at 8100 g for 40 min). From the resuspension of the AgNP contained in the solution (AgNP-total) after synthesis (AgNP-res), concentrations of 49±3 and 51±3 mg L(-1) are found and concentrations of 50±7 and 47±2 mg L(-1) in the supernatant (Ag-sup) are found using ICP-MS and ICP OES respectively. The characterization of AgNP-total, AgNP-res and Ag-sup is performed by HRTEM and UV-vis, corroborating the results in terms of Ag determination, and indicates that half of the total silver concentration is in the AgNP form and that the other half is in the "free" silver form. The results of the stability test of the NPs indicate a 7% decrease in Ag as NP three months after its synthesis.

Selective synthesis of silver nanoparticles onto potassium hexaniobate: structural organisation with bactericidal properties.

Silver-based nanocomposites are known to act as biocides against a series of microorganisms and are largely studied as an alternative to substitute conventional antibiotics that show decreasing efficacy. In this work, an eco-friendly method to synthesize silver nanoparticles assembled on the surface of hexaniobate crystals is reported. By means of ion exchange, K(+) ions of layered potassium hexaniobate were partially substituted by Ag(+) ions and the resulting material was exposed to UV light. The irradiation allowed the reduction of silver ions with consequent formation of silver nanoparticles located only on the hexaniobate surface, whereas Ag(+) ions located in the interlayer space remained in the ionic form. Increasing UV-light exposure times allowed controlling of the silver nanoparticle size. The antibacterial effects of the pristine potassium hexaniobate and of silver-containing hexaniobate samples were tested against Escherichia coli (E. coli). The antibacterial efficacy was determined to be related to the presence of silver in hexaniobate. An increasing activity against E. coli was observed with the decrease in silver nanoparticles size, suggesting that silver nanoparticles of distinct sizes interact differently with bacterial cell walls.

Determination of Judd-Ofelt intensity parameters of pure samarium(III) complexes.

This work reports an alternative aproach to obtain the Judd-Ofelt intensity parameters of Sm(III) complexes with the general formula: [Sm(tta)(3)(L)(n)], with L = H(2)O, triphenylphosphine oxide (tppo), 2,2'-bipyridine (bipy) and 1,10-phenantroline (phen); n = 2 for H(2)O and tppo and n = 1 for phen and bipy, using the absorption spectra of rare earth complexes where the powders are dispersed in KBr pellets. This approach can be applied to other complexes of rare earth ions that have spin allowed transitions and it is validated by comparing the emission spectra of the complexes with those dispersed in KBr pellets.