Absence of ferromagnetism in ferroelectric Mn-doped BaTiO3 nanofibers

Pure and Mn-doped barium titanate nanofibers were synthesized by the electrospinning method. The morphology, microstructure and crystal structure of as-spun and annealed composite nanofibers were characterized by scanning electron microscopy and transmission electron microscopy. After annealing at 850°C, we obtain nanofibers a few μm long, formed by nanoparticles of irregular shape with sizes around 100 nm. X-ray diffraction and Raman spectroscopy show that a partial phase transition from tetragonal to hexagonal takes place for BaTi_0.90Mn_0.10O₃. Vibrational phonon modes were calculated for BaTiO₃ within the density functional theory (DFT) framework. Ferroelectricity has been probed on pure and Mn-doped BaTiO₃ nanofibers, by means of piezoresponse force microscopy in an atomic force microscope, confirming the polar domain switching behavior of the fibers. The measured piezoelectric coefficient d₃₃ were 31 and 22 pm/V for BaTiO₃ and BaTi_0.90Mn_0.10O₃. Magnetic properties of the samples were probed in a superconducting quantum interference device. Diamagnetic and paramagnetic behaviors were found in pure and Mn-doped samples, respectively.     

Mechanical and microstructural analysis of geopolymer composites based on metakaolin and recycled silica

This paper evaluated mechanical and thermal stability of alkali-activated materials obtained from metakaolin and alternative silica sources, such as rice husk ash (RHA) and silica fume (SF), and were reinforced with recycled ceramic particles (RP) obtained by grinding bricks. Specimens were produced, and after 7 days of curing, they were exposed to temperatures between 300 and 1200°C to determine the influence that different percentages of RP had on the mechanical behavior and microstructure of the produced composites. The results showed a reduction in the linear contraction by 10.22% with 20 wt% RP and that the reinforcing materials improved the mechanical performance of the geopolymers after exposure to high temperatures; the compressive strengths reached 137.7 (±11.4)  MPa after being exposed to 1200°C for the matrix based on RHA and 180.6 (±19.15) MPa after being reinforced with 20 wt% RP. The improvement was mainly due to densification and the formation of crystalline products such as leucite, kalsilite, and mullite.     

Unmasking Sensory Defects of Olive Oils Flavored with Basil and Oregano Using an Electronic Tongue-Chemometric Tool

Olive oil price and consumers’ preference depend on the commercial grade classification that can decrease if any sensory defect is perceived leading to an economic loss. Enriched oils, obtained by incorporating dried aromatic herbs, spices, or essential oils, which is a common practice in the Mediterranean region, are commercially available. This practice may conceal the fraudulent purpose of masking the perception of sensory defects. The detection of this type of fraud is a difficult task, requiring sensory analysis. Thus, in this study, extra-virgin and lampante olive oils, the latter classification being due to the perception of an intense winey-vinegary defect, were deliberately enriched with different amounts of basil-dried herbs and oregano-dried herbs. Sensory analysis showed that, depending on the aromatic herb and on the added amount (0.011–0.110 g herb per kg oil), the defect intensity could be masked leading to an erroneous classification of flavored lampante oils as flavored virgin oils. In contrast, the electronic tongue-chemometric approach could unmask the defect in flavored oils (predictive sensitivities: 70–78%) and semiquantitatively discriminate flavored oils according to the added levels of basil or oregano (predictive sensitivities: 93–100%). The electronic tongue approach showed satisfactory unmasking performance when compared with the sensory panel, and so, its future application as a quality control taste-sensor device for disclosing olive oil sensory defects masked by the incorporation of flavoring agents may be forseen.     

Development of novel soy-protein-based superabsorbent matrixes through the addition of salts

The addition of salts, like sodium bicarbonate (SB) or carbonate (SC), into the formulation of bioplastic materials may alter their hydrophilic character to a significant extent. Soy protein isolate (SPI) is a byproduct of the soybean oil industry, which, when properly blended with glycerol (GL), can be further processed through a lab-scale injection molding device. A maximum in the water uptake around 2250 or 2500% is obtained for bioplastics obtained when either SB or SC content is around 1 wt %, respectively. Thus, they exceed the limit to be considered superabsorbent materials (SAMs). Regarding their mechanical properties, a higher presence of SB within the SPI/GL matrix provides materials with a higher extensibility and lower Young's modulus. A higher water uptake is observed after replacing SB for SC in the formulation, probably related to a higher alkalinization of the material as well as to the high hydrophilicity of the carbonate. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47012.     

Colloidal synthesis of Au nanoparticles using polyelectrolytes with 1,3,4-thiadiazole as reducing agents

Heterocyclic compounds are well known for their biological activity and coordination properties. Some heterocyclic compounds have been employed in the stabilization against coalescence of metallic nanoparticles in colloidal solutions, for example, tetrazole, triazole, and pyrazole. The aim of this work is to design new polyelectrolytes with heterocyclic pendant groups useful as reducing agents of Au³⁺ and as stabilizing agents for the synthesis of colloidal Au nanoparticles. Thus, polyelectrolytes with thiosemicarbazone and 1,3,4-thiadiazole pendant groups were used as reducing agents of Au³⁺ ions and stabilizing agents of Au nanoparticles. The voltammetry study of the polyelectrolytes showed that one with thiosemicarbazone pendant groups is the better reducing agent than polyelectrolytes with heterocyclic pendant groups. The polyelectrolytes can control the growth of the nanoparticles, obtaining structures with an average size of 9 nm. In this study, it was concluded that the nature of the heterocyclic group does not have an effect on the shape of nanoparticles and quasi-spherical nanoparticles were obtained with all polyelectrolytes. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47790.     

Temperature stimuli-responsive nanoparticles from chitosan-graft-poly(N-vinylcaprolactam) as a drug delivery system

This work describes the preparation of thermosensitive chitosan-graft-poly(N-vinylcaprolactam) nanoparticles by ionic gelation and their potential use as a controlled drug delivery system, using doxorubicin as a model drug. A systematic study of the effect of the main processing parameters on both the size and thermoresponsive behavior of nanoparticles was investigated. The size of the particles is strongly dependent on the length of the poly(N-vinylcaprolactam) grafted chains and the concentration of the copolymer and crosslinking agent solutions. The molecular structure of the copolymer plays an essential role in the phase transition temperature of the particles, which decreases with the length of PVCL grafted chain. The system displayed proper drug-association parameters, and the drug-loaded nanoparticles exhibited dose-dependent cytotoxicity. A significant increase in the doxorubicin delivery rate was observed above the phase transition temperature (40 °C). These features indicate that these nanoparticles are suitable for the development of a new thermally controlled anti-cancer drug delivery system. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47831.     

Wide range humidity sensors printed on biocomposite films of cellulose nanofibril and poly(ethylene glycol)

Cellulose nanofibril (CNF) films were prepared from side streams generated by the sugarcane industry, that is, bagasse. Two fractionation processes were utilized for comparison purposes: (1) soda and (2) hot water and soda pretreatments. 2,2,6,6-Tetramethylpiperidinyl-1-oxyl-mediated oxidation was applied to facilitate the nanofibrillation of the bagasse fibers. Poly(ethylene glycol) (PEG) was chosen as plasticizer to improve the ductility of CNF films. The neat CNF and biocomposite films (CNF and 40% PEG) were used for fabrication of self-standing humidity sensors. CNF-based humidity sensors exhibited high change of impedance, within four orders of magnitude, in response to relative humidity (RH) from 20 to 90%. The use of plasticizer had an impact on sensor kinetics. While the biocomposite film sensors showed slightly longer response time, the recovery time of these plasticized sensors was two times shorter in comparison to sensors without PEG. This study demonstrated that agroindustrial side streams can form the basis for high-end applications such as humidity sensors, with potential for, for example, packaging and wound dressing applications. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47920.     

Enhancements in sugar immobilization in polymeric macroporous matrices for affinity capture

The use of macroporous monolithic matrices in the purification of biocompounds is constantly growing and developing. In this work, the objective was to optimize the quantity of N-acetyl-D-glucosamine (D-GlcNAc) immobilized on the surface of macroporous polymeric cryogels for capture of lectins from less clarified solutions. Surface response methodology was applied and it was observed that the immobilization temperature of the glutaraldehyde (GLU) and the D-GlcNAc concentration influenced the amount of sugar immobilized. The matrices produced with 1.1% of allyl glycidyl ether were functionalized by GLU. Optimal maximum condition was obtained with mean value of 160.39 ± 26.38 mg of D-GlcNAc immobilized per gram of dry cryogel. Characterization analyses of the matrices showed that the activation process was effective, maintaining the macroporous structure and physical characteristics. The adsorbents produced were tested for capture of lectins from a crude protein solution of barley. At tested conditions, adsorbent capture around 11% of protein in solution but reduce the hemaglutinating capacity in 40%, demonstrating its selectivity. The cryogels functionalized with D-GlcNAc present potential for use in capture compounds by affinity with carbohydrates, such as lectins. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47956.     

Flexible oligomeric silicon-containing poly(ether-azomethine)s obtained from epoxide derivatives. Synthesis and characterization

Three new diamines derived from epoxide compounds were synthesized. The preparation of diamine monomers implied the reaction between a phenoxyalkyloxirane (alkyl: H, methyl, isopropyl) and bisphenol A, obtaining the respective aliphatic diols, which produced the corresponding dinitro derivatives. Finally, these derivatives were reduced by using palladium/carbon activated as catalyst and hydrazine as a hydrogen source. Then, six oligomeric poly(ether-azomethine)s (PEAzMs) were obtained from a polycondensation reaction between the new diamines and bis(4-formylbiphenyl-4-yl)dialkylsilane (alkyl: methyl, phenyl) with 84–93% yields. The structural characterization of the diamines and PEAzMs was performed by elemental analysis, infrared spectroscopy, and nuclear magnetic resonance spectroscopy (¹H, ¹³C, and ²⁹Si). Furthermore, polymers were analyzed by solubility tests, gel permeation chromatography, ultraviolet–visible (UV–vis) spectroscopy, thermogravimetry, and differential scanning calorimetry analysis. The results showed PEAzMs with 2–11 repetitive units, where the design of the monomers allowed to obtain improved solution processability in comparison with previously reported silylated poly(azomethine)s and good thermal stability. Additionally, all samples showed high transparency in the UV–vis region. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48055.     

Enthalpy- versus Entropy-Driven Molecular Recognition in the Era of Biologics

Our laboratory has recently identified two nanobodies (small antibodies produced by camelids)—Nb1 and Nb6—that bind efficiently to epithelial growth factor (EGF) and inhibit its ability to activate its receptor (EGFR). Because of the relevance of the EGF/EGFR axis as a target in oncology, these new nanobodies have promising therapeutic potential. This article, however, is focused on another feature of these nanobodies: their distinct thermodynamic signatures. Nb1 binds to EGF through an entropy-driven mechanism whereas Nb6 binds to this factor under enthalpic control. We discuss the advantages and disadvantages of each mechanism in the contexts of traditional medical chemistry (small-molecule drugs) and also of biological drugs. In this latter case, the implications in terms of selectivity are far from being clearly established and further experimental data are required. Their monomeric natures, high stability, and ease of recombinant production make nanobodies ideally suited for thermodynamic studies. Moreover, nanobodies, thanks to their simpler structures in comparison with conventional antibodies, might provide better understanding of the structural basis of the thermodynamic parameters of antigen recognition.