Laboratory Studies about Microplastic Aging and Its Effects on the Adsorption of Chlorpyrifos.

The constant change in microplastics (MP) due to exposure to environmental conditions leads to physical and chemical changes that enhance their ability to transport other pollutants, increasing the concern about their widespread presence in the environment. This work aimed to simulate the aging process of six MP (polyamide 6, unplasticized polyvinyl chloride, low-density polyethylene, polystyrene, polyethylene-co-vinyl acetate, polypropylene) in freshwater and seawater ecosystems at laboratory scale and evaluate its effects through optical microscope observation, Fourier transform infrared spectroscopy-Attenuated Total Reflectance (FTIR-ATR), Raman spectroscopy, and thermal gravimetric analysis (TGA). Through a combined experimental study of aged MP, the degradation by UV interaction was evidenced by the appearance of new infrared bands in the FTIR spectra assigned to ketones and hydroxyl groups. While Raman analysis and microscope images reveal the appearance of pores, wrinkles, and roughness in the MP surfaces. Variations in the temperature of the maximum weight loss of the MP were observed in the TGA analysis. The adsorption of chlorpyrifos (CPF), a common pesticide widely used in agriculture, by the pristine and aged MP was also studied. The highest affinity for CPF was observed for pristine LDPE and the lowest for PP. The batch adsorption studies revealed an increase in adsorption capacity as a consequence of the aging process for both MP. These results proved that the weathering effects caused changes in the behavior of MP, namely in the interaction with other pollutants.

Magnetostructural coupling in RFeO3 (R = Nd, Tb, Eu and Gd).

We investigate the interplay of magnetization and lattice vibrations in rare-earth orthoferrites RFeO3, with a specific focus on non-symmetry-breaking anomalies. To do so, we study the magnetization, magnon excitations and lattice dynamics as a function of temperature in NdFeO3, TbFeO3, EuFeO3 and GdFeO3. The magnetization shows distinct temperature anomalous behavior for all investigated rare-earth orthoferrites, even in the compounds with no phase transitions occurring at those temperatures. Through spin-phonon coupling, these magnetic changes are mirrored by the FeO6 rotation mode for all the studied RFeO3, revealing a common magnetostructural effect associated with the octahedra rotations. The R3+ oscillation modes evidence a Fe3+/R3+ spins cross-talk for the NdFeO3 and TbFeO3 cases. Our work sheds light into the common magnetostructural coupling in rare-earth orthoferrites, and the important role of magnetic anisotropy and spin-orbit coupling strength of the R-Fe interactions on the spin-reorientation transition at high temperatures.

Nanomaterials in cancer: Reviewing the combination of hyperthermia and triggered chemotherapy.

Nanoparticle mediated hyperthermia has been explored as a method to increase cancer treatment efficacy by heating tumours inside-out. With that purpose, nanoparticles have been designed and their properties tailored to respond to external stimuli and convert the supplied energy into heat, therefore inducing damage to tumour cells. Moreover, the combination of hyperthermia with chemotherapy has been described as a more effective strategy due to the synergy between the high temperature and the drug's effects, also associated with a remote controlled and on-demand drug release. In this review, the methods behind nanoparticle mediated hyperthermia, namely material design, external stimuli response and energy conversion will be discussed and critically analysed. We will address the most relevant studies on hyperthermia and temperature triggered drug release for cancer treatment. Finally, the advantages, difficulties and challenges of this therapeutic strategy will be discussed, while giving insight for future developments.

Environmental diagnosis with Raman Spectroscopy applied to diatoms.

Freshwater quality has been changing due to the ever greater use of water resources and the contamination load resulting from human activities. Management of these systems, thus, requires constant diagnose of water quality with fast and efficient methodologies. The conventional methods adopted are, however, time-consuming, often very expensive, and require specialised expertise. Raman spectroscopy (RS) is a simple, fast and label-free technique that can be applied to environmental diagnosis using diatoms. Here, we developed a diagnostic method based on Raman spectroscopy applied to freshwater diatoms. For this, Raman spectra were recorded from diatoms of three lakes of a natural city park. The data acquired was analysed by chemometrics methods to describe the data (Partial Least Squares Regression), infer relationships in the dataset (Cluster Analysis) and produce classification models (Artificial Neural Network). The classification models developed diagnosed the lakes with excellent accuracy (89%) without requiring taxonomic information about the diatom species recorded. This study provides a proof-of-concept for the application of diatom Raman spectroscopy to diagnosing water quality, laying an important foundation for future environmental studies aiming at assessing freshwater systems, to be replicated at larger scales and to varied geographic settings.

Dielectric spectroscopy of melt-extruded polypropylene and as-grown carbon nanofiber composites.

In this work, different weight contents of as-grown carbon nanofibers (CNFs), produced by chemical vapor deposition, were melt-extruded with polypropylene (PP) and their morphologic, structure and dielectric properties examined. The morphologic analysis reveals that the CNFs are randomly distributed in the form of agglomerates within the PP matrix, whereas the structural results depicted by Raman analysis suggest that the degree of disorder of the as-received CNFs was not affected in the PP/CNF composites. The AC conductivity of PP/CNF composites at room temperature evidenced an insulator-conductor transition in the vicinity of 2 wt.%, corresponding to a remarkable rise of the dielectric permittivity up to [Formula: see text] 12 at 400 Hz, with respect to the neat PP ([Formula: see text] 2.5). Accordingly, the AC conductivity and dielectric permittivity of PP/CNF 2 wt.% composites were evaluated by using power laws and discussed in the framework of the intercluster polarization model. Finally, the complex impedance and Nyquist plots of the PP/CNF composites are analyzed by using equivalent circuit models, consisting of a constant phase element (CPE). The analysis gathered in here aims at contributing to the better understanding of the enhanced dielectric properties of low-conducting polymer composites filled with carbon nanofibers.

Raman spectroscopy applied to diatoms (microalgae, Bacillariophyta): Prospective use in the environmental diagnosis of freshwater ecosystems.

Diatom species are good pollution bioindicators due to their large distribution, fast response to changes in environmental parameters and different tolerance ranges. These organisms are used in ecological water assessment all over the world using autoecological indices. Such assessments commonly rely on the taxonomic identification of diatom species-specific shape and frustule ornaments, from which cell counts, species richness and diversity indices can be estimated. Taxonomic identification is, however, time-consuming and requires years of expertise. Additionally, though the diatom autoecological indices are region-specific, they are often applied indiscriminately across regions. Raman spectroscopy is a simpler, fast and label-free technique that can be applied to environmental diagnosis with diatoms. However, this approach has been poorly explored. This work reviews Raman spectroscopy studies involving the structure, location and conformation of diatom cell components and their variation under different conditions. A critical appreciation of the pros and cons of its application to environmental diagnosis is also given. This knowledge provides a strong foundation for the development of environmental protocols using Raman spectroscopy in diatoms. Our work aims at stimulating further research on the application of Raman spectroscopy as a tool to assess physiological changes and water quality under a changing climate.

Strain relaxation dynamics of multiferroic orthorhombic manganites.

Resonant ultrasound spectroscopy has been used to characterise strain coupling and relaxation behavior associated with magnetic/magnetoelectric phase transitions in GdMnO3, TbMnO3and TbMn0.98Fe0.02O3through their influence on elastic/anelastic properties. Acoustic attenuation ahead of the paramagnetic to colinear-sinusoidal incommensurate antiferromagnetic transition at ∼41 K correlates with anomalies in dielectric properties and is interpreted in terms of Debye-like freezing processes. A loss peak at ∼150 K is related to a steep increase in electrical conductivity with a polaron mechanism. The activation energy,Ea, of ≳0.04 eV from a loss peak at ∼80 K is consistent with the existence of a well-defined temperature interval in which the paramagnetic structure is stabilised by local, dynamic correlations of electric and magnetic polarisation that couple with strain and have relaxation times in the vicinity of ∼10-6s. Comparison with previously published data for Sm0.6Y0.4MnO3confirms that this pattern may be typical for multiferroic orthorhombicRMnO3perovskites (R= Gd, Tb, Dy). A frequency-dependent loss peak near 10 K observed for TbMnO3and TbMn0.98Fe0.02O3, but not for GdMnO3, yieldedEa⩾ ∼0.002 eV and is interpreted as freezing of some magnetoelastic component of the cycloid structure. Small anomalies in elastic properties associated with the incommensurate and cycloidal magnetic transitions confirm results from thermal expansion data that the magnetic order parameters have weak but significant coupling with strain. Even at strain magnitudes of ∼0.1-1‰, polaron-like strain effects are clearly important in defining the development and evolution of magnetoelectric properties in these materials. Strains associated with the cubic-orthorhombic transition due to the combined Jahn-Teller/octahedral tilting transition in the vicinity of 1500 K are 2-3 orders of magnitude greater. It is inevitable that ferroelastic twin walls due to this transition would have significantly different magnetoelectric properties from homogeneous domains due to magnetoelastic coupling with steep strain gradients.

Discrimination of Benign and Malignant Lesions in Canine Mammary Tissue Samples Using Raman Spectroscopy: A Pilot Study.

Breast cancer is a health problem that affects individual life quality and the family system. It is the most frequent type of cancer in women, but men are also affected. As an integrative approach, comparative oncology offers an opportunity to learn more about natural cancers in different species. Methods based on Raman spectroscopy have shown significant potential in the study of the human breast through the fingerprinting of biological tissue, which provides valuable information that can be used to identify, characterize and discriminate structures in breast tissue, in both healthy and carcinogenic environments. One of the most important applications of Raman spectroscopy in medical diagnosis is the characterization of microcalcifications, which are highly important diagnostic indicators of breast tissue diseases. Raman spectroscopy has been used to analyze the chemical composition of microcalcifications. These occur in benign and malignant lesions in the human breast, and Raman helps to discriminate microcalcifications as type I and type II according to their composition. This paper demonstrates the recent progress in understanding how this vibrational technique can discriminate through the fingerprint regions of lesions in unstained histology sections from canine mammary glands.

Strain-Engineered Tetragonal Phase and Ferroelectricity in GdMnO3 Thin Films Grown on SrTiO3 (001).

A previously unreported tetragonal phase has been discovered in a epitaxially strained GdMnO3 thin films deposited on (001)-oriented SrTiO3 substrates by radio frequency (RF) magnetron sputtering. The tetragonal axis of the films grown up to a 35 nm thickness is perpendicular to the film surface and the basal lattice parameters are imposed by the cubic structure of the substrate. Furthermore, the emergence of a spontaneous electric polarization below ~32 K points to the stabilization of an improper ferroelectric phase at low temperatures, which is not observed in bulk GdMnO3. This work shows how strain engineering can be used to tailor the structure and properties of strongly correlated oxides.

Hysteretic Characteristics of Pulsed Laser Deposited 0.5Ba(Zr0.2Ti0.8)O3-0.5(Ba0.7Ca0.3)TiO3/ZnO Bilayers.

In the present work, we study the hysteretic behavior in the electric-field-dependent capacitance and the current characteristics of 0.5Ba(Zr0.2Ti0.8)O3-0.5(Ba0.7Ca0.3)TiO3 (BCZT)/ZnO bilayers deposited on 0.7 wt % Nb-doped (001)-SrTiO3 (Nb:STO) substrates in a metal-ferroelectric-semiconductor (MFS) configuration. The X-ray diffraction measurements show that the BCZT and ZnO layers are highly oriented along the c-axis and have a single perovskite and wurtzite phases, respectively, whereas high-resolution transmission electron microscopy revealed very sharp Nb:STO/BCZT/ZnO interfaces. The capacitance-electric field ( C- E) characteristics of the bilayers exhibit a memory window of 47 kV/cm and a capacitance decrease of 22%, at a negative bias. The later result is explained by the formation of a depletion region in the ZnO layer. Moreover, an unusual resistive switching (RS) behavior is observed in the BCZT films, where the RS ratio can be 500 times enhanced in the BCZT/ZnO bilayers. The RS enhancement can be understood by the barrier potential profile modulation at the depletion region, in the BCZT/ZnO junction, via ferroelectric polarization switching of the BCZT layer. This work builds a bridge between the hysteretic behavior observed either in the C- E and current-electric field characteristics on a MFS structure.

Enhanced resistive switching characteristics in Pt/BaTiO3/ITO structures through insertion of HfO2:Al2O3 (HAO) dielectric thin layer.

An enhanced resistive switching (RS) effect is observed in Pt/BaTiO3(BTO)/ITO ferroelectric structures when a thin HfO2:Al2O3 (HAO) dielectric layer is inserted between Pt and BTO. The P-E hysteresis loops reveal the ferroelectric nature of both Pt/BTO/ITO and Pt/HAO/BTO/ITO structures. The relation between the RS and the polarization reversal is investigated at various temperatures in the Pt/HAO/BTO/ITO structure. It is found that the polarization reversal induces a barrier variation in the Pt/HAO/BTO interface and causes enhanced RS, which is suppressed at Curie temperature (Tc = 140 °C). Furthermore, the Pt/HAO/BTO/ITO structures show promising endurance characteristics, with a RS ratio >103 after 109 switching cycles, that make them potential candidates for resistive switching memory devices. By combining ferroelectric and dielectric layers this work provides an efficient way for developing highly efficient ferroelectric-based RS memory devices.

Tuning the Stoichiometry of Ag2S Thin Films for Resistive Switching Applications.

In this work silver-rich and sulfur-rich silver sulfide (Ag2S) thin films were fabricated using a diversified set of experimental methods, namely ion beam deposition and atmosphere- and solution-based sulfurizations. The composition of the Ag2S thin films was studied using X-ray diffraction, Raman spectroscopy, scanning electron microscopy and energy dispersive X-ray spectroscopy. We found that it strongly depends on the fabrication conditions, such as sulfurization time and temperature. These conditions, in turn, affect the electrical characteristics of the thin films, namely the resistivity and resistive switching. We were able to control the Ag2S stoichiometry and infer its dependence on the fabrication parameters for all the followed methods.

Polymer surface adsorption as a strategy to improve the biocompatibility of graphene nanoplatelets.

The biointeractions of graphene-based materials depend on their physico-chemical properties. These properties can be manipulated by polymer adsorption. Graphene nanoplatelets (GNP-C) were modified with PVA, HEC, PEG, PVP, chondroitin, glucosamine, and hyaluronic acid. These materials were characterized by SEM, DLS, XPS, Raman spectroscopy, and TGA. Surface adsorption was confirmed for all polymers. Biocompatibility evaluation showed that all of these materials induced low haemolysis (<1.7%) at concentrations up to 500µgmL(-1). GNP-C-PVA and GNP-C-HEC presented the lowest haemolysis percentages and were therefore more thoroughly studied. The morphology of HFF-1 cells was investigated by microscopy (optical, fluorescence, TEM) in order to evaluate interactions with GNP materials. Small GNP-C nanoplatelets were observed to enter cells independently of the surface treatment. For pristine GNP-C at a concentration of 50µgmL(-1), ROS production increased 4.4-fold. This effect is lower for GNP-C-PVA (3.3-fold) and higher for GNP-C-HEC (5.1-fold). Resazurin assays showed that GNP-C caused toxicity in HFF-1 cells at concentrations above 20µgmL(-1) at 24h, which decreased at 48 and 72h. PVA surface adsorption rendered GNP-C non-toxic at concentrations up to 50µgmL(-1). LIVE/DEAD assays showed that at 20 and 50µgmL(-1) cell death is significantly lower for GNP-C-PVA compared to pristine GNP-C. Modification of nanoplatelets with HEC resulted in no benefit in terms of biocompatibility, whereas PVA considerably improved the biocompatibility.

Breaking the geometric magnetic frustration in controlled off-stoichiometric LuMn1+zO3+δ compounds.

This study explores controlled off-stoichiometric LuMn1+zO3+δ (|z| < 0.1) compounds, intended to retain the utter LuMnO3 intrinsic hexagonal symmetry and ferroelectric properties. X-ray powder diffraction measurements evidenced a single phase P63cm structure. Thermo-gravimetric experiments show a narrow impact of oxygen vacancies while a distinguishable gas exchange at ∼700 K, a surprisingly lower temperature when compared to perovskite systems. A comparison of different nominal ceramics revealed pertinent structural and magnetic property variations owing to subtle self-doping effects. Deviations from the archetypal antiferromagnetic state were detected below ∼90 K suggesting local rearrangements of the nominal Mn(3+) ions matrix, breaking the ideal geometrical spin frustration, leading to a non-compensated magnetic structure.

Competing exchanges and spin-phonon coupling in Eu(1-x)R(x)MnO3 (R=Y, Lu).

This work is focused on the phase diagrams and physical properties of Y-doped and Lu-doped EuMnO3. The differences in the corresponding phase boundaries in the (x,T) phase diagram could be overcome by considering a scaling of the Y(3+) and Lu(3+) concentrations to the tolerance factor. This outcome evidences that the tolerance factor is in fact a more reliable representative of the lattice deformation induced by doping. The normalization of the phase boundaries using the tolerance factor corroborates previous theoretical outcomes regarding the key role of competitive FM and AFM exchanges in determining the phase diagrams of manganite perovskites. However, significant differences in the nature and number of phases at low temperatures and concentrations could not be explained by just considering the normalization to the tolerance factor. The vertical phase boundary observed just for Lu-doped EuMnO3, close to 10% Lu, is understood by considering a low temperature Peierls-type spin-phonon coupling, which stabilizes the AFM-4 phase in Lu-doped EuMnO3.

Magnetically-induced lattice distortions and ferroelectricity in magnetoelectric GdMnO3.

In this work we investigate the magnetic field dependence of A(g) octahedra rotation (tilt) and B(2g) symmetric stretching modes frequencies at different temperatures. Our field-dependent Raman investigation at 10 K is interpreted by an ionic displacive nature of the magnetically-induced ferroelectric phase transition. The increasing frequency of the A(g) tilt mode with magnetic field gives evidence for the increase of the MnO(6) tilt angle, which in turn leads to a weakening of the ferromagnetic exchange interaction, yielding the necessary conditions for the onset of ferroelectricity on the basis of the inverse Dzyaloshinskii-Moriya interaction. The frequency change of the B(2g) symmetric stretching mode at the ferroelectric phase transition enables one to estimate the shift of oxygen ion positions and the corresponding spontaneous polarization of 480 µC m(-2) in magnitude, which is of the same order as earlier reported values in single crystals.

Polar behaviour induced by lithium in potassium tantalate ceramics.

Polar behaviour in K(1-x)Li(x)TaO(3) ceramics with x = 0:02, 0.05 and 0.10, processed by the conventional solid state method, is studied by Raman spectroscopy and thermally stimulated depolarization current (TSDC) techniques between 10 and 290 K. The TO1 mode of KTaO(3) is revealed to harden in the whole temperature range and to split in the low-temperature range by Li doping. One splitting is observed for x = 0:02 and two consequent splittings are detected for x = 0:05 and 0.10. The temperatures, where TO1 mode splitting occurs, are found to correspond to those of the peaks of TSDC, and hence to the onset of the electric polarization. Such behaviour provides evidence for the order-disorder ferroelectric phase transition induced in KTaO(3) by lithium doping, which emerges from deformations of the cubic phase developed on cooling either in one (for x = 0:02) or two steps (for x = 0:05 and 0.10).

Synthesis and characterization of HAp nanorods from a cationic surfactant template method.

Hydroxyapatite (HAp) [Ca(10)(PO(4))(6)(OH)(2)] nanorods were synthesized using a surfactant templating method, with cetyltrimethylammonium bromide (CTAB) micelles acting as template for HAp growth. The effects of the sintering temperature on the morphological and crystallographic characteristics and on chemical composition of the "as-prepared" structures are discussed. The experimental results show that low heat-treatment temperatures are preferred in order to obtain high quality nanorods, with diameters ranging between 20 and 50 nm. High heat-treatment temperatures enhance the thermal decomposition of HAp into other calcium phosphate compounds, and the sintering of particles into micrometer ball-like structures. The stability of aqueous suspensions of HAp nanorods is also discussed.