Development of a simple process to obtain luminescent YVO4:Eu3+ nanoparticles for Fiber Optic Dosimetry

YVO4:Eu3+ is a red emitter phosphor commercially available as micrometric powder due to its high luminescence efficiency under electron-beam excitation. Although some published results have demonstrated the potential of using this micrometer material in Fiber Optic Dosimetry systems, there is no information regarding its use on a nanometric scale. In order to obtain a nanometric material with high luminescent efficiency, a simple synthetic combustion method was developed and the results were compared with both, those of a commercial material and those obtained by a typical coprecipitation synthesis. A single crystalline phase was obtained when the combustion route was employed for the preparation meanwhile two crystalline phases were obtained via coprecipitation synthesis. The particle size of YVO4:Eu3+ obtained by combustion route ranges from 55 up to 200 nm. Fourier Transform Infrared Spectroscopy and Thermogravimetric Analysis indicated that annealing at 600 °C promote the degradation of the impurities that remained adsorbed onto nanoparticles surface after the synthesis. However, to improve the Radioluminescence intensity, an annealing process at 1000 °C was required. The method allows obtaining a nanometric material with a scintillation intensity almost twice higher than that of the commercial powder.Fil: Mentasti, Luciana. Universidad Nacional del Centro de la Provincia de Buenos Aires. Centro de Investigaciones en Física e Ingeniería del Centro de la Provincia de Buenos Aires. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tandil. Centro de Investigaciones en Física e Ingeniería del Centro de la Provincia de Buenos Aires. - Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas. Centro de Investigaciones en Física e Ingeniería del Centro de la Provincia de Buenos Aires; ArgentinaFil: Martínez Clemente, Nahuel Facundo. Universidad Nacional del Centro de la Provincia de Buenos Aires. Centro de Investigaciones en Física e Ingeniería del Centro de la Provincia de Buenos Aires. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tandil. Centro de Investigaciones en Física e Ingeniería del Centro de la Provincia de Buenos Aires. - Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas. Centro de Investigaciones en Física e Ingeniería del Centro de la Provincia de Buenos Aires; ArgentinaFil: Zucchi, Ileana Alicia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; ArgentinaFil: Santiago, Martin Alejo. Universidad Nacional del Centro de la Provincia de Buenos Aires. Centro de Investigaciones en Física e Ingeniería del Centro de la Provincia de Buenos Aires. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tandil. Centro de Investigaciones en Física e Ingeniería del Centro de la Provincia de Buenos Aires. - Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas. Centro de Investigaciones en Física e Ingeniería del Centro de la Provincia de Buenos Aires; ArgentinaFil: Barreto, Gastón Pablo. Universidad Nacional del Centro de la Provincia de Buenos Aires. Centro de Investigaciones en Física e Ingeniería del Centro de la Provincia de Buenos Aires. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tandil. Centro de Investigaciones en Física e Ingeniería del Centro de la Provincia de Buenos Aires. - Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas. Centro de Investigaciones en Física e Ingeniería del Centro de la Provincia de Buenos Aires; Argentin

Supramolecular Networks Obtained by Block Copolymer Self-Assembly in a Polymer Matrix: Crystallization Behavior and Its Effect on the Mechanical Response

In recent years, there has been growing interest in the study of supramolecular networks obtained by self-assembly of amphiphilic molecules due to their responsive behavior to different external stimuli. The possibility of embedding supramolecular networks into polymer matrices opens access to a new generation of functional polymers with great potential for various applications. However, very little is known about how the dynamics of the supramolecular network is affected by diffusional and topological limitations imposed by the polymer matrix. In this work, we investigate the behavior of supramolecular networks embedded into a rubbery polymer. Crystallization-driven self-assembly of a poly(ethylene-block-ethylene oxide) (PE-b-PEO) diblock copolymer was used to generate supramolecular networks in dimethacrylate monomers, which were then photopolymerized at room temperature. PE-b-PEO self-assembles into nanoribbons with a semicrystalline PE core bordered by coronal chains of PEO, and the nanoribbons, in turn, bundle into lamellar aggregates with an average stacking period of around 45 nm. The nanoribbons are interconnected through crystalline nodes in a 3D network structure. Small-angle X-ray scattering experiments show that the polymer matrix preserves the structure of the supramolecular network and avoids its disintegration when the material is heated above the melting temperature of PE cores. Successive self-nucleation and annealing studies reveal that the polymer matrix does not influence the crystallization–melting processes of PE, which take place through the interconnected cores of the supramolecular network. In contrast, the matrix imposes strong effects of topological confinement on the crystallization of PEO, limiting the dimensions of the crystalline lamellae that can be formed. Mechanical tests show that the deformation capacity of these materials can be precisely tuned by programming the temperature within the melting range of the supramolecular network. This behavior was also characterized by shape memory cyclic tests.The financial support of the following institutions is gratefully acknowledged: National Research Council (CONICET, Argentina), National Agency for the Promotion of Research, Technological Development and Innovation (AgenciaI + D + i, Argentina), and University of Mar del Plata. This work has received funding from the Basque Government through grant IT1503-22. R.N.S. thanks Iberoamerican Association of Postgraduate Universities (AUIP) for a mobility fellowship

Block copolymer micelles generated by crystallization-driven self-assembly in polymer matrices

In this review we show how Crystallization-Driven Self-Assembly (CDSA), a method originally employed for the self-assembly of block copolymers in solution, was extended to the synthesis of elongated micellar nanostructures in polymer matrices. By highlighting some of the works published by our group in this area, the conditions to synthesize nanostructured polymers by CDSA are discussed. The knowledge of these conditions will allow developing a new generation of nanomaterials with tailored architecture according to a required application.Fil: Gutiérrez González, Jessica. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; ArgentinaFil: Schmarsow, Ruth Noemí. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; ArgentinaFil: Montoya Rojo, Ursula Maria. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Instituto de Tecnología en Polímeros y Nanotecnología. Universidad de Buenos Aires. Facultad de Ingeniería. Instituto de Tecnología en Polímeros y Nanotecnología; ArgentinaFil: Puig, Julieta. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; ArgentinaFil: Schroeder, Walter Fabian. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; ArgentinaFil: Zucchi, Ileana Alicia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; Argentin

Controlling the generation of bilayer and Q1 multilayer vesicles in block copolymer/epoxy blends by a slow photopolymerization process

Vesicles are a highly attractive morphology to achieve in micellar dispersions of block copolymers (BCP) in epoxy thermosets due to the fact that small amounts can affect a large volume fraction of the matrix, a fact that is important for toughening purposes. However, generating vesicles in epoxy matrices requires operating in a narrow range of formulations and processing conditions. In this report, we show that block-copolymer vesicles dispersed in an epoxy matrix could be obtained through a sphere-tocylinder-to-vesicle micellar transition induced by visible-light photopolymerization at room temperature. A 10 wt% colloidal solution of poly(ethylene-co-butene)-block-poly(ethylene oxide) (PEB-b-PEO) block copolymer (BCP) in an epoxy monomer (DGEBA) self-assembled into spherical micelles as shown by small-angle X-ray scattering (SAXS). During a slow photopolymerization of the epoxy monomer carried out at room temperature, a sphere-to-cylinder-to-vesicle transition took place as revealed by in situ SAXS and TEM images. This was driven by the tendency of the system to reduce the local interfacial curvature as a response to a decrease in the miscibility of PEO blocks in the polymerizing epoxy matrix. When the BCP concentration was increased from 10 to 20 and 40 wt%, the final structure evolved from bilayer vesicles to multilayer vesicles and to lamellae, respectively. In particular, for 20 wt% PEB-b-PEO, transient structures such as partially fused multilayered vesicles were observed by TEM, giving insight into the growth mechanism of multilayer vesicles. On the contrary, when a relatively fast thermal polymerization was performed at 80 1C, the final morphology consisted of kinetically trapped spherical micelles. Hopefully, this study will lead to new protocols for the preparation of vesicles dispersed in epoxy matrices in a controlled way.Facultad de Ciencias ExactasInstituto de Investigaciones Fisicoquímicas Teóricas y Aplicada

Remote activation by green-light irradiation of shape memory epoxies containing gold nanoparticles

Shape memory epoxies (SMEs) that can be remotely activated by the use of green light, are described. An epoxy matrix based on on diglycidylether of bisphenol A (DGEBA cured with a mixture of n-dodecylamine (DA) and m-xylylenediamine (MXDA), exhibits excellent shape memory properties as described in a previous paper (Leonardi et al., 2011). Au NPs with an average diameter close to 5 nm could be uniformly dispersed in this matrix using poly(ethylene oxide) (PEO) chains as stabilizer. These NPs showed a significant photothermal effect even at very low concentrations (0.01 wt% as metallic gold), when irradiated with a 532 nm laser at a power close to 2 W/cm2. Under these conditions, a bended bar (1.4-mm thickness) recovered its initial shape in a few seconds. This formulation may be used to build up devices with the necessary mechanical strength and with the possibility to produce shape recovery by remote activation using green light. A second example was analyzed employing an amphiphilic epoxy matrix to produce a uniform dispersion of Au NPs stabilized with dodecyl chains (average diameter close to 3 nm). A bar (1.4-mm thickness) of the SME with 0.04 wt% Au NPs (as metallic gold) showed a fast recovery of its initial shape by irradiation with a 532 nm laser at a power close to 2 W/cm2. This example shows the feasibility of adapting the epoxy chemistry to disperse Au NPs stabilized with different ligands and obtained through robust synthetic methods.Fil: Leonardi, Agustina Belen. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; ArgentinaFil: Puig, Julieta. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; ArgentinaFil: Antonacci, Julian. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Departamento de Física; ArgentinaFil: Arenas, Gustavo Francisco. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Departamento de Física; ArgentinaFil: Zucchi, Ileana Alicia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; ArgentinaFil: Hoppe, Cristina Elena. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; ArgentinaFil: Reven, Linda. McGill University; CanadáFil: Zhu, Liu. Peking University Shenzhen Graduate School; ChinaFil: Toader, Violeta. McGill University; CanadáFil: Williams, Roberto Juan Jose. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; Argentin

The heparan sulfate proteoglycan syndecan-1 regulates colon cancer stem cell function via a focal adhesion kinase—Wnt signaling axis

In colon cancer, downregulation of the transmembrane heparan sulfate proteoglycan syndecan‐1 (Sdc‐1) is associated with increased invasiveness, metastasis, and dedifferentiation. As Sdc‐1 modulates signaling pathways relevant to stem cell function, we tested the hypothesis that it may regulate a tumor‐initiating cell phenotype. Sdc‐1 small‐interfering RNA knockdown in the human colon cancer cell lines Caco2 and HT‐29 resulted in an increased side population (SP), enhanced aldehyde dehydrogenase 1 activity, and higher expression of CD133, LGR5, EPCAM, NANOG, SRY (sex‐determining region Y)‐box 2, KLF2, and TCF4/TCF7L2. Sdc‐1 knockdown enhanced sphere formation, cell viability, Matrigel invasiveness, and epithelial‐to‐mesenchymal transition‐related gene expression. Sdc‐1‐depleted HT‐29 xenograft growth was increased compared to controls. Decreased Sdc‐1 expression was associated with an increased activation of β1‐integrins, focal adhesion kinase (FAK), and wingless‐type (Wnt) signaling. Pharmacological FAK and Wnt inhibition blocked the enhanced stem cell phenotype and invasive growth. Sequential flow cytometric SP enrichment substantially enhanced the stem cell phenotype of Sdc‐1‐depleted cells, which showed increased resistance to doxorubicin chemotherapy and irradiation. In conclusion, Sdc‐1 depletion cooperatively enhances activation of integrins and FAK, which then generates signals for increased invasiveness and cancer stem cell properties. Our findings may provide a novel concept to target a stemness‐associated signaling axis as a therapeutic strategy to reduce metastatic spread and cancer recurrence.DatabasesThe GEO accession number of the Affymetrix transcriptomic screening is GSE58751

Environmental and Occupational Risk Factors of Amyotrophic Lateral Sclerosis: A Population-Based Case-Control Study

Objectives: Amyotrophic lateral sclerosis (ALS) is a progressive and fatal neurodegenerative disease with still unknown etiology. We aimed at investigating the association between environmental and occupational factors with ALS risk. Methods: We performed a population-based case-control study in four Italian provinces (Catania, Modena, Novara, and Reggio Emilia) by administration of tailored questionnaires to ALS cases (n = 95) and randomly selected population referents (n = 135). We estimated ALS risk by calculating the odds ratio (OR) with its 95% confidence interval (CI) using an unconditional logistic regression model. Results: We found a positive association with disease risk for history of occupation in the agricultural sector (OR = 2.09, 95% CI 0.79-7.54), especially for longer than 10 years (OR = 2.72, 95% 1.02-7.20). Overall occupational exposure to solvents also suggested a positive association, especially for thinners (OR = 2.27, 95% CI 1.14-4.54) and paint removers (OR = 2.01, 95% CI 0.90-4.48). Both occupational and environmental exposure to electromagnetic fields show a slightly increased risk with OR = 1.69 (95% CI 0.70-4.09) and 2.41 (95% CI 1.13-5.12), respectively. Occupational but not environmental exposure to pesticides (OR = 1.22, 95% CI 0.63-2.37), particularly fungicides, and exposure to metals (OR = 4.20, 95% CI 1.88-9.38), particularly lead, mercury, and selenium, showed an imprecise but positive association. Finally, there was an indication of increased risk for living in proximity to water bodies. Conclusions: Despite the caution that needs to be used due to some study limitations, such as the low number of exposed subjects and the possibility of recall bias, these results suggest the potential role of some environmental and occupational factors in ALS etiology

Clinical and Lifestyle Factors and Risk of Amyotrophic Lateral Sclerosis: A Population-Based Case-Control Study

Background: Amyotrophic lateral sclerosis (ALS) is a progressive, fatal neurodegenerative disease of the motor neurons. The etiology of ALS remains largely unknown, particularly with reference to the potential environmental determinants. Methods: We performed a population-based case-control study in four provinces from both Northern and Southern Italy in order to assess non-genetic ALS risk factors by collecting through tailored questionnaires information about clinical and lifestyle factors. We estimated ALS risk by calculating odds ratio (OR) with its 95% confidence interval (CI) using unconditional logistic regression models adjusted for sex, age and educational attainment. Results: We recruited 230 participants (95 cases and 135 controls). We found a possible positive association of ALS risk with trauma, particularly head trauma (OR = 2.61, 95% CI 1.19-5.72), electric shock (OR = 2.09, 95% CI 0.62-7.06), and some sports, although at a competitive level only. In addition, our results suggest an increased risk for subjects reporting use of private wells for drinking water (OR = 1.38, 95% CI 0.73-2.27) and for use of herbicides during gardening (OR = 1.95, 95% CI 0.88-2.27). Conversely, there was a suggestion of an inverse association with overall fish consumption (OR = 0.27, 95% CI 0.12-0.60), but with no dose-response relation. Consumption of some dietary supplements, namely those containing amino acids and, in the Southern Italy population, vitamins and minerals such as selenium, seemed associated with a statistically imprecise increased risk. Conclusions: Our results suggest a potential etiologic role a number of clinical and lifestyle factors with ALS risk. However, caution is needed due to some study limitations. These include the small sample size and the low number of exposed subjects, which affect statistical precision of risk estimates, the potential for exposure misclassification, and the uncertainties about mechanisms underpinning the possible association between these factors and disease risk

A transcriptional sketch of a primary human breast cancer by 454 deep sequencing

Background: The cancer transcriptome is difficult to explore due to the heterogeneity of quantitative and qualitative changes in gene expression linked to the disease status. An increasing number of "unconventional" transcripts, such as novel isoforms, non-coding RNAs, somatic gene fusions and deletions have been associated with the tumoral state. Massively parallel sequencing techniques provide a framework for exploring the transcriptional complexity inherent to cancer with a limited laboratory and financial effort. We developed a deep sequencing and bioinformatics analysis protocol to investigate the molecular composition of a breast cancer poly(A)+ transcriptome. This method utilizes a cDNA library normalization step to diminish the representation of highly expressed transcripts and biology-oriented bioinformatic analyses to facilitate detection of rare and novel transcripts. Results: We analyzed over 132,000 Roche 454 high-confidence deep sequencing reads from a primary human lobular breast cancer tissue specimen, and detected a range of unusual transcriptional events that were subsequently validated by RT-PCR in additional eight primary human breast cancer samples. We identified and validated one deletion, two novel ncRNAs (one intergenic and one intragenic), ten previously unknown or rare transcript isoforms and a novel gene fusion specific to a single primary tissue sample. We also explored the non-protein-coding portion of the breast cancer transcriptome, identifying thousands of novel non-coding transcripts and more than three hundred reads corresponding to the non-coding RNA MALAT1, which is highly expressed in many human carcinomas. Conclusion: Our results demonstrate that combining 454 deep sequencing with a normalization step and careful bioinformatic analysis facilitates the discovery and quantification of rare transcripts or ncRNAs, and can be used as a qualitative tool to characterize transcriptome complexity, revealing many hitherto unknown transcripts, splice isoforms, gene fusion events and ncRNAs, even at a relatively low sequence sampling