Luminescence properties of neodymium, samarium, and europium niobate and tantalate thin films.

Thin films of lanthanide orthoniobate LnNbO4 (LnNO) and orthotantalate LnTaO4 (LnTO), (Ln = Nd, Sm, Eu) were fabricated using the sol-gel method with subsequent spin-coating on the PbZrO3 /Al2 O3 substrate and annealing at 1000°C. X-ray diffraction patterns showed monoclinic M-LnNbO4 or M´-LnTaO4 , which coexists with the orthorhombic or tetragonal phase. X-ray photoelectron spectroscopy demonstrated the presence of Nd3+ , Sm3+ /Sm2+ and Eu3+ /Eu2+ ions. The luminescence properties of polymorphic films were investigated. Excitation spectra of PbZrO3 interlayer represented broad bands at 410 and 550 nm that were assigned to charge transfer bands (CTB). In all films, the CTB broad band at ~275 nm related to charge transfer transition of Ln3+ →O2- and NbO4 3- or TaO4 3- groups. In excitation spectra, 4 I9/2 →4 G5/2 (Nd3+ ), 6 H5/2 →6 P3/2 (Sm3+ ) and 7 F0 →5 L6 (Eu3+ ) transitions (at 585, 402 and 395 nm), respectively were found to be more intense than any other Ln3+ transition. The emission spectra showed narrow and intense bands at 1065, 600, and 614 nm that were ascribed to Nd3+ , Sm3+ , and Eu3+ 4f-f intraconfigurational transitions 4 F3/2 →4 I11/2 , 4 G5/2 →6 H7/2 , and 5 D0 →7 F2 , respectively. The excellent luminescence properties of films make them new potential groups for visible and/or near-infrared applications such as sensors and imaging equipment.

Silver nanoparticle incorporation into flexible polyamide 12 membranes.

To meet the demands of the market and society, the development of structured polymeric materials for application in the medical field is constantly increasing. Over the last decades, metallic silver nanoparticles have been explored due to their antimicrobial action. Here, we aimed to incorporate metallic silver nanoparticles into polymeric pieces obtained by additive manufacture via a chemical route involving silver nitrate and sodium borohydride. Polyamide 12 membranes were obtained by selective laser sintering, which was followed by washing, pretreatment, and functionalization with the alkoxides tetraethylorthosilicate and 3-aminopropyl tetraethoxysilane. For nanoparticle preparation and incorporation, a chemical route was tested under different conditions. The samples were characterized by techniques, such as X-ray diffraction, ultraviolet-visible spectroscopy, and infrared vibrational spectroscopy. Nanoparticle formation and incorporation into the polyamide 12 membranes were demonstrated by the absorbance band at 420 nm, which indicated that the particles measured between 10 and 50 nm in size; by the X-ray diffraction peaks at 2θ = 38, 44, and 64°, which are typical of crystalline silver; and by vibrational spectroscopy, which evidenced that the nanoparticles interacted with the polyamide 12 nitrogen groups. Polyamide 12 membranes containing metallic silver nanoparticles have promising biomedical applications as antimicrobial wound dressings associated with drug carriers.

Antitumor activity of solamargine in mouse melanoma model: relevance to clinical safety.

Melanoma is the most aggressive type of skin cancer, and thus it is important to develop new drugs for its treatment. The present study aimed to examine the antitumor effects of solamargine a major alkaloid heteroside present in Solanum lycocarpum fruit. In addition solamargine was incorporated into nanoparticles (NP) of yttrium vanadate functionalized with 3-chloropropyltrimethoxysilane (YVO4:Eu3+:CPTES:SM) to determine antitumor activity. The anti-melanoma assessment was performed using a syngeneic mouse melanoma model B16F10 cell line. In addition, systemic toxicity, nephrotoxic, and genotoxic parameters were assessed. Solamargine, at doses of 5 or 10 mg/kg/day administered subcutaneously to male C57BL/6 mice for 5 days, decreased tumor size and frequency of mitoses in tumor tissue, indicative of a decrease in cell proliferation. Treatments with YVO4:Eu3+:CPTES:SM significantly reduced the number of mitoses in tumor tissue, associated with no change in tumor size. There were no apparent signs of systemic toxicity, nephrotoxicity, and genotoxicity initiated by treatments either with solamargine alone or plant alkaloid incorporated into NP. The animals treated with YVO4:Eu3+:CPTES:SM exhibited significant increase in spleen weight accompanied by no apparent histological changes in all tissues examined. In addition, animals treated with solamargine (10 mg/kg/day) and YVO4:Eu3+:CPTES:SM demonstrated significant reduction in hepatic DNA damage which was induced by tumor growth. Therefore, data suggest that solamargine may be considered a promising candidate in cancer therapy with no apparent toxic effects.

Incorporation of indomethacin into a mesoporous silica nanoparticle enhances the anti-inflammatory effect Indomethacin into a mesoporous silica.

PURPOSE: We evaluated the analgesic, anti-inflammatory and toxicological effects of indomethacin incorporated into mesoporous silica nanoparticles (IND+NP). METHODS: Nociception was evaluated by the formalin assay. The anti-inflammatory potential was assessed by cell migration and paw edema assays, modulation of nitric oxide and cytokines (IL-6, IL-10 and TNF-α) by macrophages production. Toxicity was evaluated in peritoneal macrophages and by the locomotion assay and assessment of gastric injuries, presence of occult blood and hepatic and renal markers. RESULTS: IND+NP reduced nociception during phases 1 by 53% and 2 by 79% of the formalin assay and the influx of peritoneal cells by 94%, indicating an analgesic and anti-inflammatory effect more efficiently than indomethacin alone. Indomethacin, but not IND+NP, caused macroscopic gastric injuries, the presence of fecal occult blood, and an increase of ALT levels. In the paw edema assay, IND+NP reduced edema by 21%. IND+NP has no effect on the LPS-induced production of nitric oxide, IL-6, IL-10 and TNF-α on no cytotoxic concentrations. CONCLUSIONS: The incorporation of indomethacin into mesoporous silica nanoparticles effectively increased the activity of the drug observed in the formalin and cell migration assays and prevented the gastric and hepatic damage associated with its use.

NIR Luminescence Enhancement of YVO4:Nd Phosphor for Biological Application.

This work reports two systematic studies related to yttrium vanadate (YVO4) phosphors. The first evaluates how the annealing temperature and V5+/Y3+ molar ratio determine the emergence of a single YVO4 tetragonal phase, whereas the second concerns the optimal Nd3+ concentration to improve the infrared emission properties for bio-labelling applications. The YVO4:Nd phosphors were synthesized by adapting the non-hydrolytic sol-gel route. For the first study, samples containing different V5+/Y3+ molar ratios (1.02, 1.48, 1.71, or 3.13) were obtained. For the second study, YVO4:Nd phosphors containing different Nd3+ concentrations (1.0, 3.0, 5.0, or 10.0% in mol) were prepared. X-ray diffractometry and RAMAN spectroscopy results revealed that, regardless of the heat-treatment temperature, the V5+/Y3+ molar ratio of 1.48 was the best composition to avoid undesired phases like Y2O3 and V2O5. Photoluminescence results indicated that the sample containing 3.0% in mol of Nd3+ and annealed at 1000 °C presented the best infrared emission properties. This sample displayed an intense broad band in the ultraviolet region, which was ascribed to the VO43- charge transfer band, as well as several bands in the visible and infrared regions, which were attributed to the Nd3+ intraconfigurational f-f transitions. Regardless of the excitation wavelength (ultraviolet, visible, or near-infrared), the mean radiative lifetime was about 12.00 µs. The prepared phosphors presented absorption and emission bands in the biological window (BW) regions, which are located between 750 and 900 nm and between 1000 and 1300 nm, so they are candidates for applications in medical imaging and diagnoses.

Anti-Melanoma Activity of Indomethacin Incorporated into Mesoporous Silica Nanoparticles.

Melanoma is the deadliest type of skin cancer. Treatments that directly address tumor survival are required. Indomethacin (IND) is a well-known drug used worldwide. Although widely used as a therapeutic agent, IND has undesirable gastrointestinal effects. PURPOSE: To investigate the antitumor efficacy of IND incorporated into mesoporous silica nanoparticles (MSNPs+IND), as well as its toxic potential in a syngeneic murine B16 melanoma model. METHODS: Antitumor activity was evaluated by measuring tumor size and weight and by histopathological analysis. Possible molecular signaling pathways involved in the antitumor activity were analyzed by Western blot in liver tissue and by immunohistochemistry in tumor tissue. The potential toxicity was evaluated by determining body and organ weights and by biochemical and genotoxic analysis. RESULTS: MSNPs+IND treatments inhibited tumor growth by up to 70.09% and decreased the frequency of mitosis in tumor tissues, which was up to 37.95% lower compared to the IND groups. In hepatic tissue, COX-2 levels decreased significantly after treatment with MSNPs+IND and IND. Additionally, MSNPs+IND and IND increased the levels of cleaved caspase-3 (156.25% and 137.50%, respectively), inducing tumor cell apoptosis. Genotoxicity was limited to the group treated with the higher concentration of IND, while MSNPs prevented IND-induced genotoxicity. CONCLUSIONS: MSNPs may be promising for future applications in cancer therapy.

Effect of ytterbium amount on LaNbO4:Tm3+,Yb3+ nanoparticles for bio-labelling applications.

PURPOSE: This work investigates how Yb3+ concentration affects the luminescent properties of LaNbO4 nanoparticles for medical imaging applications. Due to the highly transparent optical window for organic tissues in the near infrared region (650-1000 nm), upconversion fluorescence allows near infrared wavelengths to penetrate deeply into tissues, which is useful in biomedical areas such as biodetection, activated phototherapy, and screening. MATERIALS/METHOD: Upconversion nanoparticles based on LaNbO4 doped with Tm3+ and Yb3+ were prepared by the one-step industrial process called Spray Pyrolysis. Samples with different Tm3+:Yb3+ molar ratios (1:4, 1:8 and 1:16) were obtained. RESULTS: The X-ray powder diffractograms of all the samples displayed the typical peaks of a crystalline material (tetragonal phase). Emission bands emerged in the blue, red, and near infrared regions, and they corresponded to the Tm3+1G4 → 3H6 (475 nm), 1G4 → 3F4 (650 nm), 3F2,3 â†’ 3H6 (690 nm), and 3H4 → 3H6 (803 nm) transitions, which indicated a two-photon absorption process. As for bio-labelling application, the results indicated that Yb3+ concentration was directly related to signal intensity. CONCLUSIONS: The intensity of positive conversion emissions depends directly on Yb3+ concentration. The bio-labelling tests pointed to the potential application of these materials. The sample containing the highest amount of Yb3+ provided better results and was easier to detect than the standard sample.

Non-hydrolytic Sol-Gel Route: a Powerful Process to Develop UV-Vis-IR Luminescent YVO4 Phosphors.

The spectroscopic properties of lanthanide ions stem from absorption and emission radiation in the solar spectrum range, which promotes numerous applications in areas such as white light emission, bio-imaging, biological markers, and photovoltaic cells, among others. To intensify these properties, several matrixes have been studied, particularly the yttrium vanadate matrix due to its structural, mechanic, and physicochemical properties. The non-hydrolytic sol-gel process is a versatile way to prepare inorganic oxides doped with lanthanide ions. In this work, we describe the synthesis of yttrium vanadate matrixes doped with Eu3+, Er3+, and/or Yb3+ ions (containing 1% lanthanide ions with respect to Y3+ (molar ratio)) by the non-hydrolytic sol-gel, annealed at 800 °C for 4 h, and their characterization by X-ray diffraction and photoluminescence spectroscopy. The X-ray diffraction patterns display the peaks corresponding to the yttrium vanadate tetragonal phase. Laser excitation at 980 nm elicits Er3+ emission bands in the green and red regions and Eu3+ emission at 620 nm. Laser excitation at 322 nm; i.e., the charge transfer band, provides emission in the same regions, as well as infrared emission. This system is a promising candidate for applications in solar cells, optical amplifiers, and biomarkers because it can be excited at different wavelengths. Graphical Abstract Schematic diagram of the energy level of lanthanides and vanadate ions, and energy transfer.

Effect of gadolinium incorporation on the structure and luminescence properties of niobium-based materials.

In this work, we have investigated how the concentration of Gd3+ ions affects the structural and luminescent properties of niobium oxide-based matrices doped with Eu3+ ions obtained by the adapted non-hydrolytic sol-gel route. X-ray diffractograms revealed that increasing the concentration of Gd3+ ions favored the onset of the Gd2O3 structure decreasing the GdNbO4 phase. The excitation spectra (λ em = 613 nm) presented bands corresponding to the 7F0 â†’ 5LJ transitions (L = D, G, and L, where J = 0-7), attributed to the Eu3+ ions, and a broad band at 270 nm, assigned to the charge transfer of the [Formula: see text] group. The emission spectra contained bands refer to the 5D0 â†’ 7FJ internal configuration transitions (J = 0, 1, 2, 3, and 4). Finally, the CIE chromaticity coordinates met the standard for the color red established by the National Television Standard Committee (NTSC).

Europium(III)-doped yttrium vanadate nanoparticles reduce the toxicity of cisplatin.

The aim of this study was to evaluate the antitumor efficiency of chemotherapy with cisplatin alone and incorporated into europium(III)-doped yttrium vanadate nanoparticles functionalized with 3­chloropropyltrimethoxysilane with folic acid and without folic acid in a syngeneic mouse melanoma model. Histopathological, biochemical and genotoxic analyses of treated animals were performed to assess the toxicity of treatments. The treatment of the animals with cisplatin alone and the nanoparticles functionalized with cisplatin at a dose of 5 mg/kg b.w. for 5 days reduced tumor weight about 86% and 65%, respectively. Histopathological analysis showed lower mean frequency of mitoses in tumor tissue of the groups receiving cisplatin alone (90% reduction) and the nanoparticles functionalized with cisplatin (70% reduction) compared to the tumor control group. A reduction in body and liver weight and an increase in serum creatinine and urea levels were observed in animals treated with CDDP, but not in those receiving the nanoparticles functionalized with cisplatin. Genotoxicity assessment by the comet assay revealed lower frequencies of DNA damage in animals treated with the nanoparticles functionalized with cisplatin (mean score = 140.80) compared to those treated with cisplatin alone (mean score = 231.80). Marked toxic effects were observed in animals treated with cisplatin alone, while treatment with the nanoparticles functionalized with cisplatin showed no toxicity. Moreover, folic acid in the inorganic nanoparticles reduced the genotoxicity of cisplatin in the bone marrow micronucleus test (10 ±â€¯1.4 and 40 ±â€¯0.0 micronucleus, respectively). These results demonstrate the antitumor efficiency and significantly reduced systemic toxicity of the nanoparticles compared to CDDP.

Poly(L-lactic acid) membranes: absence of genotoxic hazard and potential for drug delivery.

The use of poly(L-lactic acid) (PLA) has been considered an important alternative for medical devices once this polyester presents biomechanical, optical and biodegradable properties. Moreover, the use of PLA results in less inflammatory reactions and more recently it has been proposed its application in drug delivery systems. Genotoxicological evaluations are considered part of the battery assays in toxicological analysis. Considering the wide applications of PLA, the present work evaluated the potential cytotoxic and genotoxic effects of PLA in CHO-K1 cells, as well as its physicochemical properties. No cytotoxic effects of PLA were detected by colorimetric tetrazolium assay (XTT) analysis, and the clonogenic survival assay showed that PLA did not disrupt the replicative cell homeostasis, neither exhibited genotoxic effects as evidenced by comet and micronucleus assays. Thermogravimetric properties of PLA were not altered after contact with cells and this film exhibited ability in absorb and release Europium(III) complex. All these data suggest genotoxicological safety of PLA for further applications in drug delivery systems.

Synthesis and biocompatibility of an experimental glass ionomer cement prepared by a non-hydrolytic sol-gel method.

The aims of this study were to demonstrate the synthesis of an experimental glass ionomer cement (GIC) by the non-hydrolytic sol-gel method and to evaluate its biocompatibility in comparison to a conventional glass ionomer cement (Vidrion R). Four polyethylene tubes containing the tested cements were implanted in the dorsal region of 15 rats, as follows: GI - experimental GIC and GII - conventional GIC. The external tube walls was considered the control group (CG). The rats were sacrificed 7, 21 and 42 days after implant placement for histopathological analysis. A four-point (I-IV) scoring system was used to graduate the inflammatory reaction. Regarding the experimental GIC sintherization, thermogravimetric and x-ray diffraction analysis demonstrated vitreous material formation at 110oC by the sol-gel method. For biocompatibility test, results showed a moderate chronic inflammatory reaction for GI (III), severe for GII (IV) and mild for CG (II) at 7 days. After 21 days, GI presented a mild reaction (II); GII, moderate (III) and CG, mild (II). At 42 days, GI showed a mild/absent inflammatory reaction (II to I), similar to GII (II to I). CG presented absence of chronic inflammatory reaction (I). It was concluded that the experimental GIC presented mild/absent tissue reaction after 42 days, being biocompatible when tested in the connective tissue of rats.

Synthesis and biocompatibility of an experimental glass ionomer cement prepared by a non-hydrolytic sol-gel method

The aims of this study were to demonstrate the synthesis of an experimental glass ionomer cement (GIC) by the non-hydrolytic sol-gel method and to evaluate its biocompatibility in comparison to a conventional glass ionomer cement (Vidrion R). Four polyethylene tubes containing the tested cements were implanted in the dorsal region of 15 rats, as follows: GI - experimental GIC and GII - conventional GIC. The external tube walls was considered the control group (CG). The rats were sacrificed 7, 21 and 42 days after implant placement for histopathological analysis. A four-point (I-IV) scoring system was used to graduate the inflammatory reaction. Regarding the experimental GIC sintherization, thermogravimetric and x-ray diffraction analysis demonstrated vitreous material formation at 110oC by the sol-gel method. For biocompatibility test, results showed a moderate chronic inflammatory reaction for GI (III), severe for GII (IV) and mild for CG (II) at 7 days. After 21 days, GI presented a mild reaction (II); GII, moderate (III) and CG, mild (II). At 42 days, GI showed a mild/absent inflammatory reaction (II to I), similar to GII (II to I). CG presented absence of chronic inflammatory reaction (I). It was concluded that the experimental GIC presented mild/absent tissue reaction after 42 days, being biocompatible when tested in the connective tissue of rats.

O objetivo deste estudo foi demonstrar a sinterização pelo método sol-gel não-hidrolítico de um cimento de ionômero de vidro experimental (CIV) e avaliar sua biocompatibilidade em relação a um cimento de ionômero de vidro convencional (Vidrion R). Quatro tubos de polietileno contendo os cimentos testados foram implantados no dorso de 15 ratos, da seguinte maneira: GI - CIV Experimental e GII - CIV Convencional. A lateral do tubo foi considerada Grupo Controle. Os ratos foram sacrificados em 7, 21 e 42 dias pós-implantação para análise histopatológica. Uma escala de I a IV foi utilizada como sistema de score para graduar a reação inflamatória. Em relação à sinterização do CIV experimental, as análises termogravométrica e por difração de raio-x demonstraram a formação de material vítreo aos 110oC pelo método sol-gel. Para o teste de biocompatibilidade, os resultados mostraram uma reação inflamatória moderada para o GI (III), severa para o GII (IV) e branda para o Grupo Controle (II) aos 7 dias. Após 21 dias, GI apresentou uma reação branda (II); GII, moderada (III) e Grupo Controle, branda (II). Aos 42 dias, GI apresentou uma reação inflamatória branda/ausente (II a I), similar ao GII (II a I). O Grupo Controle demonstrou ausência de reação inflamatória (I). Concluiu-se que o CIV Experimental apresentou reação tecidual branda/ausente após 42 dias, sendo biocompatível quando testado em tecido conjuntivo de ratos.