Direct Determination of Ca, K, and Mg in Soy Leaf Samples Using Laser-Induced Breakdown Spectroscopy.

This study was dedicated to developing analytical methods for determining macronutrients (Ca, K, and Mg) in soy leaf samples with and without petioles. The study's primary purpose was to present Laser-induced breakdown spectroscopy (LIBS) as a viable alternative for directly analyzing leaf samples using chemometric tools to interpret the data obtained. The instrumental condition chosen for LIBS was 70 mJ of laser pulse energy, 1.0 µs of delay time, and 100 µm of spot size, which was applied to 896 samples: 305 of soy without petioles and 591 of soy with petioles. The reference values of the analytes for the proposition of calibration models were obtained using inductively coupled plasma optical emission spectroscopy (ICP-OES) technique. Twelve normalization modes and two calibration strategies were tested to minimize signal variations and sample matrix microheterogeneity. The following were studied: multivariate calibration using partial least squares and univariate calibration using the area and height of several selected emission lines. The notable normalization mode for most models was the Euclidean norm. No analyte showed promising results for univariate calibrations. Micronutrients, P and S, were also tested, and no multivariate models presented satisfactory results. The models obtained for Ca, K, and Mg showed good results. The standard error of calibration ranged from 2.3 g/kg for Ca in soy leaves without petioles with two latent variables to 5.0 g/kg for K in soy leaves with petioles with two latent variables.

Impact of electrostatic potential on microcapsule-formation and physicochemical analysis of surface structure: Implications for therapeutic cell-microencapsulation.

Cell-encapsulation is used for preventing therapeutic cells from being rejected by the host. The technology to encapsulate cells in immunoprotective biomaterials, such as alginate, commonly involves application of an electrostatic droplet generator for reproducible manufacturing droplets of similar size and with similar surface properties. As many factors influencing droplet formation are still unknown, we investigated the impact of several parameters and fitted them to equations to make procedures more reproducible and allow optimal control of capsule size and properties. We demonstrate that droplet size is dependent on an interplay between the critical electric potential (Uc,), the needle size, and the distance between the needle and the gelation bath, and that it can be predicted with the equations proposed. The droplet formation was meticulously studied and followed by a high-speed camera. The X-ray photoelectron analysis demonstrated optimal gelation and substitution of sodium with calcium on alginate surfaces while the atomic force microscopy analysis demonstrated a low but considerable variation in surface roughness and low surface stiffness. Our study shows the importance of documenting critical parameters to guarantee reproducible manufacturing of beads with constant and adequate size and preventing batch-to-batch variations.

In vitro antimicrobial and anticancer properties of TiO2 blow-spun nanofibers containing silver nanoparticles.

Nanosilver immobilized on TiO2 nanometric fibers (Ag/TiO2) was produced by solution blow spinning and characterized using scanning electron microscopy, transmission electron microscopy, N2 adsorption/desorption, X-ray diffraction, X-ray photoelectron spectroscopy, water contact angle, and inductively coupled plasma emission spectroscopy analyses. The in vitro antimicrobial and anticancer activities of the produced nanofibers was also investigated. Ag/TiO2 nanofibers revealed a crystalline structure compatible with the rutile crystalline phase, as well as a mesoporous and superhydrophilic nature. XPS profiles showed Ti4+ and Ag0, indicating a strong interaction between the Ag nanoparticles and TiO2. The Ag/TiO2 nanofibers presented antimicrobial activity against Staphylococcus aureus, Enterococcus faecalis, and Escherichia coli. The release of silver ions from 5 mg∙mL-1 and 50 mg∙mL-1 of Ag/TiO2 nanofibers was approximately 0.08 µg∙mL-1 and 0.18 µg∙mL-1, respectively. The nanofiber cytotoxicity in both macrophages (ATCC RAW 264.7) and cancer cells (murine AT-84 oral squamous carcinoma cells) was dose-dependent. A concentration of 5 mg∙mL-1 induced partial suppression growth and migration of cancer cells, while a concentration of 50 mg∙mL-1 resulted in complete inhibition of proliferation and migration of murine AT-84 cells. The overall results indicate that Ag/TiO2 nanofibers can selectively inhibit the cellular mechanism of AT-84 by apoptosis with DNA damage and cell death. The antimicrobial and anticancer performance of Ag/TiO2 nanofibers is probably the result of its nanometric dimension, high surface reactivity, and the interaction between TiO2 and Ag. Electron transfer at the metal-semiconductor interface and reactive oxygen species production, in addition to the biological activity of released silver ions, confirm the potential for use as an agent in antimicrobial and anticancer therapy.

Geometry-dependent DNA-TiO2 immobilization mechanism: A spectroscopic approach.

DNA nucleotides are used as a molecular recognition system on electrodes modified to be applied in the detection of various diseases, but immobilization mechanisms, as well as, charge transfers are not satisfactorily described in the literature. An electrochemical and spectroscopic study was carried out to characterize the molecular groups involved in the direct immobilization of DNA structures on the surface of nanostructured TiO2 with the aim of evaluating the influence of the geometrical aspects. X-ray photoelectron spectroscopy at O1s and P2p core levels indicate that immobilization of DNA samples occurs through covalent (POTi) bonds. X-ray absorption spectra at the Ti2p edge reinforce this conclusion. A new species at 138.5eV was reported from P2p XPS spectra analysis which plays an important role in DNA-TiO2 immobilization. The POTi/OTi ratio showed that quantitatively the DNA immobilization mechanism is dependent on their geometry, becoming more efficient for plasmid ds-DNA structures than for PCR ds-DNA structures. The analysis of photoabsorption spectra at C1s edge revealed that the molecular groups that participate in the C1s→LUMO electronic transitions have different pathways in the charge transfer processes at the DNA-TiO2 interface. Our results may contribute to additional studies of immobilization mechanisms understanding the influence of the geometry of different DNA molecules on nanostructured semiconductor and possible impact to the charge transfer processes with application in biosensors or aptamers.

Surface-Altered Protonation Studied by Photoelectron Spectroscopy and Reactive Dynamics Simulations.

The extent to which functional groups are protonated at aqueous interfaces as compared to bulk is deemed essential to several areas in chemistry and biology. The origin of such changes has been the source of intense debate. We use X-ray photoelectron spectroscopy and all-atom reactive molecular dynamics simulations as two independent methods to probe, at the molecular scale, both bulk and surface distributions of protonated species of cysteine in an aqueous solution. We show that the distribution of the cysteine species at the surface is quite different from that in the bulk. We argue that this finding, however, cannot be simply related to a change in the extent of proton sharing between the two conjugate acid/base pairs that may occur between these two regions. The present theoretical simulations identify species at the surface that are not present in the bulk.

VUV photodissociation of thiazole molecule investigated by TOF-MS and photoelectron photoion coincidence spectroscopy.

Photoelectron photoion coincidence measurements have been performed for the thiazole (C3H3NS) molecule in gas phase, using time-of-flight mass spectrometry in the electron-ion coincidence mode and vacuum ultraviolet synchrotron radiation. photoelectron photoion coincidence spectra have been recorded as a function of the photon energy covering the valence range from 10 to 21 eV. The resulting photoionization products as well as the dissociation pathways leading to the ionic species were proposed and discussed. We have also performed density functional theory and ab initio calculations for the neutral molecule, its cation and the ion fragments produced in order to determine their electronic and structural parameters.

XPS analysis of enzyme and mediator at the surface of a layer-by-layer self-assembled wired enzyme electrode.

High potential purified Trametes trogii laccase has been deposited in mono- and multilayer thin films on gold surfaces by layer-by-layer electrostatic adsorption self-assembly. The osmium bipyridil redox relay sites on polycation poly(allylamine) backbone efficiently work as a molecular "wire" in oxygen cathodes for biofuel cells. X-ray photoelectron spectroscopy of Cu 2p3/2 and Os 4f signals provided chemical information on the enzyme and redox mediator surface concentrations after different adsorption steps. The electrical charge involved in oxidation-reduction cycles of the osmium sites, the ellipsometric enzyme film thickness, and the mass uptake from quartz crystal microbalance experiments, correlate with the XPS surface concentration, which provides unique evidence on the chemical identity of the composition in the topmost layers. XPS is shown to be an important analytical tool to investigate stratified copper and osmium distribution in LbL thin films relevant to biosensors and biofuel cells.

Tuning protein GlnB-Hs surface interaction with silicon: FTIR-ATR, AFM and XPS study.

Herbaspirillum seropedicae GlnB (GlnB-Hs) is a signal transduction protein involved in the control of nitrogen, carbon and energetic metabolism. The adsorption of GlnB-Hs deposited by spin coating on hydrophilic and hydrophobic silicon forms a thin layer that was characterized using atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared attenuated total reflectance spectroscopy (FTIR-ATR). AFM allowed the identification of globular, face-up donut like array of protein on hydrophilic silicon substrate, favoring deprotonated residues to contact the silicon oxide surface. Over hydrophobic silicon, GlnB-Hs adopts a side-on conformation forming a filament network, avoiding the contact of protonated residues with silicon surface. XPS allowed us to determine the protonated and non-protonated states of nitrogen 1s (N 1s). The FTIR-ATR measurements provided information about protein secondary structure and its conservation, after surface adsorption.

ZnO-coated glass fibers for the analysis of trihalomethanes by headspace-solid phase microextraction-gas chromatography.

Li(2)O-ZrO(2)-BaO-SiO(2) glass fibers were produced and their surfaces were coated with zinc oxide. The fibers' surface morphology was examined by scanning electron microscopy and the zinc oxide layer was characterized by mapping the K(α) and L(α) lines of zinc by energy dispersive X-ray spectroscopy. The results indicated that a homogeneous and porous layer of ZnO was formed on the fibers' surface. This layer was subjected to a simultaneous determination of trihalomethanes using headspace-solid phase microextraction-gas chromatography. The study was conducted after evaluating the ideal time of incubation (15 min), extraction (15 min) and desorption (10 min), as well as the effect of the addition of salt (15%, m/v) on the analytical response. A good linear dynamic range was observed individually for trihalomethanes aqueous solutions containing 20 µg L(-1) and 500 µg L(-1) of trichloromethane, 15 µg L(-1) and 250 µg L(-1) of dichlorobromomethane and dibromochloromethane and 10 µg L(-1) and 100 µg L(-1) of tribromomethane, with all the compounds showing correlation coefficients higher than 0.9900.