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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.

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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.

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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.

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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.

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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.

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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.

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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.

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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).

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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.

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