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Herein we report the synthesis of a piezopolymer composed of chitosan (CS)/hydroxylated BaTiO3 (OH-BTO) nanoparticles with enhanced biocompatibility, non-toxicity, and piezoelectric behavior that can be advantageously used in biomedical applications. Our CS/OH-BTO nanocomposites exhibit piezoelectric coefficient (d33 = 11.29 pC/N) between those of dry skin (0.05-0.19 pC/N) and bone (4-11 pC/N), demonstrating biocompatibility in contact with human fibroblasts (HF) cells after 24 h. SEM, XRD, FTIR and Raman measurements were performed to assess the mechanism of interaction between CS matrix and OH-BTO NPs and their correlation with the biological responses. Cytotoxicity assays with HF cells reveal that hydroxylation of BTO NPs does not affect the cell viability of CS/OH-BTO films with NPs concentration from 1 to 30 wt.%. In contrast, non-hydroxylated BTO NPs showed significant cell damage, which could be traced to uncontrollable NPs agglomeration. This behavior suggests that CS/OH-BTO nanocomposites can act as active material that promotes cell growth and can be used for biomedical purposes.

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In this work, a high-resolution atomic force acoustic microscopy imaging technique is developed in order to obtain the local indentation modulus at the nanoscale level. The technique uses a model that gives a qualitative relationship between a set of contact resonance frequencies and the indentation modulus. It is based on white-noise excitation of the tip-sample interaction and uses system theory for the extraction of the resonance modes. During conventional scanning, for each pixel, the tip-sample interaction is excited with a white-noise signal. Then, a fast Fourier transform is applied to the deflection signal that comes from the photodiodes of the atomic force microscopy (AFM) equipment. This approach allows for the measurement of several vibrational modes in a single step with high frequency resolution, with less computational cost and at a faster speed than other similar techniques. This technique is referred to as stochastic atomic force acoustic microscopy (S-AFAM), and the frequency shifts of the free resonance frequencies of an AFM cantilever are used to determine the mechanical properties of a material. S-AFAM is implemented and compared with a conventional technique (resonance tracking-atomic force acoustic microscopy, RT-AFAM). A sample of a graphite film on a glass substrate is analyzed. S-AFAM can be implemented in any AFM system due to its reduced instrumentation requirements compared to conventional techniques.

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The effects of the simultaneous incorporation of Cu and O in CdSe films grown by sputtering are presented. The Cu and O contents varied between 1 and 5 at.% in films deposited at 150, 200, 250 and 300 °C. Concentrations of 2, 3, 4 and 5 at.% of CuO in the target promoted the formation of copper selenide clusters immersed within the CdSe:Cu:O host. Energy considerations (enthalpy of formation and bond dissociation energy) were used to discuss the absence of copper oxide and the formation of copper selenide aggregates, as well as the film thickness dependence on the concentration of CuO in the target. The band gap of the films ranged from 1.21 to 2.07 eV, depending upon growth conditions. Significant below-band-gap absorption was observed which was ascribed to the copper selenide micro and nano clusters. Good crystalline quality of the films, for high substrate temperatures, was evidenced through the appearance of overtones of the vibrational longitudinal optic modes detected by Raman micro spectroscopy. It was determined that the electronic properties, optical transmission and electrical conductivity depended on the chemical composition and crystalline structure. This characteristic is relevant because through copper and oxygen co-doping is possible to control these technologically important physical properties of CdSe in a simple and reliable manner.

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Differences on herringbone molecular arrangement in two forms of long-chain 1,ω-alkanediols (CnH2n+2O2 with n = 10, 11, 12, 13) are explained from the analysis of O-H···O hydrogen-bond sequences in infinite chains and the role of a C-H···O intramolecular hydrogen-bond in stabilization of a gauche defect, as well as the inter-grooving effectiveness on molecular packing. GIXD (Glancing Incidence X-ray Diffraction) experiments were conducted on polycrystalline monophasic samples. Diffracted intensities were treated with the multi-axial March-Dollase method to correlate energetic and geometrical features of molecular interactions with the crystalline morphology and textural pattern of samples. The monoclinic (P21/c, Z = 2) crystals of the even-numbered members (n = 10, 12; DEDOL and DODOL, respectively) are diametrical prisms with combined form {104}/{-104}/{001} and present a two-fold platelet-like preferred orientation, whereas orthorhombic (P212121, Z = 4) odd-numbered members (n = 11, 13; UNDOL and TRDOL, respectively) present a dominant needle-like orientation on direction [101] (fiber texture). We show that crystalline structures of medium complexity and their microstructures can be determined from rapid GIXD experiments from standard radiation, combined with molecular replacement procedure using crystal structures of compounds with higher chain lengths as reference data.

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Molecular relaxations of chitosan films have been investigated in the wide frequency range of 0.1 to 3 × 10(9) Hz from -10 °C to 110 °C using dielectric spectroscopy. For the first time, two high-frequency relaxation processes (in the range 10(8) to 3 × 10(9) Hz) are reported in addition to the low frequency relaxations α and ß. These two relaxation processes are related to the vibrations of OH and NH2/NH3(+), respectively. The high-frequency relaxations exhibit Arrhenius-type dependencies in the temperature range 10 °C to 54 °C with negative activation energy; this observation is traceable to hydrogen bonding reorientation. At temperatures above the glass transition temperature (54 °C), the activation energy changes from negative to positive values due to breaking of hydrogen bonding and water loss. Upon cooling in a sealed environment, the activation energies of two relaxation processes are nearly zero. FTIR and XRD analyses reveal associated structural changes upon heating and cooling. These two new high-frequency relaxation processes can be attributed to the interaction of bound water with OH and NH2/NH3(+), respectively. A plausible scenario for these high-frequency relaxations is discussed in light of impedance spectroscopy, TGA, FTIR and XRD measurements.

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