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Although the physics and chemistry of materials are driven by exposed surfaces in the morphology, they are fleeting, making them inherently challenging to study experimentally. The rational design of their morphology and delivery in a synthesis process remains complex because of the numerous kinetic parameters that involve the effective shocks of atoms or clusters, which end up leading to the formation of different morphologies. Herein, we combined functional density theory calculations of the surface energies of ZnO and the Wulff construction to develop a simple computational model capable of predicting its available morphologies in an attempt to guide the search for images obtained by field-emission scanning electron microscopy (FE-SEM). The figures in this morphology map agree with the experimental FE-SEM images. The mechanism of this computational model is as follows: when the model is used, a reaction pathway is designed to find a given morphology and the ideal step height in the whole morphology map in the practical experiment. This concept article provides a practical tool to understand, at the atomic level, the routes for the morphological evolution observed in experiments as well as their correlation with changes in the properties of materials based solely on theoretical calculations. The findings presented herein not only explain the occurrence of changes during the synthesis (with targeted reaction characteristics that underpin an essential structure-function relationship) but also offer deep insights into how to enhance the efficiency of other metal-oxide-based materials via matching.

The chemical pressure approach offers a new paradigm for property control in functional materials. In this work, we disclose a correlation between the β → α pressure-induced phase transition in SnMoO 4 and the substitution process of Mo 6+ by W 6+ in SnMo 1- x W x O 4 solid solutions ( x = 0-1). Special attention is paid to discriminating the role of the lone pair Sn 2+ cation from the structural distortive effect along the Mo/W substitution process, which is crucial to disentangle the driven force of the transition phase. Furthermore, the reverse α → β transition observed at high temperature in SnWO 4 is rationalized on the same basis as a negative pressure effect associated with a decreasing of W 6+ percentage in the solid solution. This work opens a versatile chemical approach in which the types of interactions along the formation of solid solutions are clearly differentiated and can also be used to tune their properties, providing opportunities for the development of new materials.

Size and morphology control during the synthesis of materials requires a molecular-level understanding of how the addition of surface ligands regulates nucleation and growth. In this work, this control is achieved by using three carboxylic acids (tartaric, benzoic, and citric) during sonochemical syntheses. The presence of carboxylic acids affects the kinetics of the nucleation process, alters the growth rate, and governs the size and morphology. Samples synthesized with citric acid revealed excellent photocatalytic activity for the degradation process of Rhodamine B, and recyclability experiments demonstrate that it retains 91% of its photocatalytic activity after four recycles. Scavenger experiments indicate that both the hydroxyl radical and the hole are key species for the success of the transformation. A reaction pathway is proposed that involves a series of dissolution-hydration-dehydration and precipitation processes, mediated by the complexation of Ag + . We believe these studies contribute to a fundamental understanding of the crystallization process and provide guidance as to how carboxylic acids can influence the synthesis of materials with controlled size and morphology, which is promising for multiple other scientific fields, such as sensor and catalysis fields.

In this work, α-Ag 2-2 x Cu x WO 4 (0 ≤ x ≤ 0.16) solid solutions with enhanced antibacterial (against methicillin-resistant Staphylococcus aureus ) and antifungal (against Candida albicans ) activities are reported. A plethora of techniques (X-ray diffraction with Rietveld refinements, inductively coupled plasma atomic emission spectrometry, micro-Raman spectroscopy, attenuated total reflectance-Fourier transform infrared spectroscopy, field emission scanning electron microscopy, ultraviolet-visible spectroscopy, photoluminescence emissions, and X-ray photoelectron spectroscopy) were employed to characterize the as-synthetized samples and determine the local coordination geometry of Cu 2+ cations at the orthorhombic lattice. To find a correlation between morphology and biocide activity, the experimental results were sustained by first-principles calculations at the density functional theory level to decipher the cluster coordinations and electronic properties of the exposed surfaces. Based on the analysis of the under-coordinated Ag and Cu clusters at the (010) and (101) exposed surfaces, we propose a mechanism to explain the biocide activity of these solid solutions.

Silver tungstate (Ag 2 WO 4 ) shows structural polymorphism with different crystalline phases, namely, orthorhombic, hexagonal, and cubic structures that are commonly known as α, β, and γ, respectively. In this work, these Ag 2 WO 4 polymorphs were selectively and successfully synthesized through a simple precipitation route at ambient temperature. The polymorph-controlled synthesis was conducted by means of the volumetric ratios of the silver nitrate/tungstate sodium dehydrate precursors in solution. The structural and electronic properties of the as-synthesized Ag 2 WO 4 polymorphs were investigated by using a combination of X-ray diffraction and Rietveld refinements, X-ray absorption spectroscopy, X-ray absorption near-edge structure spectroscopy, field-emission scanning electron microscopy images, and photoluminescence. To complement and rationalize the experimental results, first-principles calculations, at the density functional theory level, were carried out, leading to an unprecedented glimpse into the atomic-level properties of the morphology and the exposed surfaces of Ag 2 WO 4 polymorphs. Following the analysis of the local coordination of Ag and W cations (clusters) at each exposed surface of the three polymorphs, the structure-property relationship between the morphology and the photocatalytic and antibacterial activities against amiloride degradation under ultraviolet light irradiation and methicillin-resistant Staphylococcus aureus , respectively, was investigated. A possible mechanism of the photocatalytic and antibacterial activity as well the formation process and growth of the polymorphs is also explored and proposed.

Bacterial and organic pollutants are major problems with potential adverse impacts on human health and the environment. A promising strategy to alleviate these impacts consists in designing innovative photocatalysts with a wider spectrum of application. In this paper, we report the improved photocatalytic and antibacterial activities of chemically precipitated Ag 3 PO 4 microcrystals by the incorporation of W at doping levels 0.5, 1, and 2 mol %. The presence of W directly influences the crystallization of Ag 3 PO 4 , affecting the morphology, particle size, and surface area of the microcrystals. Also, the characterization via experimental and theoretical approaches evidenced a high density of disordered [AgO 4 ], [PO 4 ], and [WO 4 ] structural clusters due to the substitution of P 5+ by W 6+ into the Ag 3 PO 4 lattice. This leads to new defect-related energy states, which decreases the band gap energy of the materials (from 2.27 to 2.04 eV) and delays the recombination of e'-h • pairs, leading to an enhanced degradation process. As a result of such behaviors, W-doped Ag 3 PO 4 (Ag 3 PO 4 :W) is a better visible-light photocatalyst than Ag 3 PO 4 , demonstrated here by the photodegradation of potential environmental pollutants. The degradation of rhodamine B dye was 100% in 4 min for Ag 3 PO 4 :W 1%, and for Ag 3 PO 4 , the obtained result was 90% of degradation in 15 min of reaction. Ag 3 PO 4 :W 1% allowed the total degradation of cephalexin antibiotic in only 4 min, whereas pure Ag 3 PO 4 took 20 min to achieve the same result. For the degradation of imidacloprid insecticide, Ag 3 PO 4 :W 1% allowed 90% of degradation, whereas Ag 3 PO 4 allowed 40%, both in 20 min of reaction. Moreover, the presence of W-dopant results in a 16-fold improvement of bactericidal performance against methicillin-resistant Staphylococcus aureus . The outstanding results using the Ag 3 PO 4 :W material demonstrated its potential multifunctionality for the control of organic pollutants and bacteria in environmental applications., Competing Interests: The authors declare no competing financial interest., (Copyright © 2020 American Chemical Society.)

Present theoretical and experimental work provides an in-depth understanding of the morphological, structural, electronic, and optical properties of hexagonal and monoclinic polymorphs of bismuth phosphate (BiPO 4 ). Herein, we demonstrate how microwave irradiation induces the transformation of a hexagonal phase to a monoclinic phase in a short period of time and, thus, the photocatalytic performance of BiPO 4 . To complement and rationalize the experimental results, first-principles calculations have been performed within the framework of density functional theory. This was aimed at obtaining the geometric, energetic, and structural parameters as well as vibrational frequencies; further, the electronic properties (band structure diagram and density of states) of the bulk and corresponding surfaces of both the hexagonal and monoclinic phases of BiPO 4 were also acquired. A detailed characterization of the low vibrational modes of both the hexagonal and monoclinic polymorphs is key to explaining the irreversible phase transformation from hexagonal to monoclinic. On the basis of the calculated values of the surface energies, a map of the available morphologies of both phases was obtained by using Wulff construction and compared to the observed scanning electron microscopy images. The BiPO 4 crystals obtained after 16-32 min of microwave irradiation provided excellent photodegradation of Rhodamine B under visible-light irradiation. This enhancement was found to be related to the surface energy and the types of clusters formed on the exposed surfaces of the morphology. These findings provide details of the hexagonal-to-monoclinic phase transition in BiPO 4 during microwave irradiation; further, the results will assist in the design of electronic devices with higher efficiency and reliability.

Controlling the structural organization and crystallinity of functional oxides is key to enhancing their performance in technological applications. In this work, we report a strong enhancement of the structural organization and crystallinity of Bi 2 WO 6 samples synthetized by a microwave-assisted hydrothermal method after exposing them to femtosecond laser irradiation. X-ray diffraction, UV-vis and Raman spectroscopies, photoluminescence emissions, energy dispersive spectroscopy, field emission scanning electron microscopy, and transmission electron microscopy were employed to characterize the as-synthetized samples. To complement and rationalize the experimental results, first-principles calculations were employed to study the effects of femtosecond laser irradiation. Structural and electronic effects induced by femtosecond laser irradiation enhance the long-range crystallinity while decreasing the free carrier density, as it takes place in the amorphous and liquid states. These effects can be considered a clear cut case of surface-enhanced Raman scattering.

In the current communication, the synthesis of metallic Bi nanoparticles with coexisting crystallographic structures (rhombohedral, monoclinic, and cubic) obtained via direct femtosecond laser irradiation of NaBiO3 is demonstrated for the first time. By exploring the use of high laser power values, it is revealed that the promoted laser-mediated reactions lead to the synthesis of coexisting phases in metal nanoparticles, which may be a widely occurring phenomenon in other materials under femtosecond laser irradiation, and a fundamental concern for laser-based nanofabrication.

The present joint experimental and theoretical work provides in-depth understanding on the morphology and structural, electronic, and optical properties of ZnWO 4 nanocrystals. Monoclinic ZnWO 4 nanocrystals were prepared at three different temperatures (140, 150, and 160 °C) by a microwave hydrothermal method. Then, the samples were investigated by X-ray diffraction with Rietveld refinement analysis, field-emission scanning electron microscopy, transmission electronic microscopy, micro-Raman and Fourier transform infrared spectroscopy, ultraviolet-visible spectroscopy, and photoluminescence measurements. First-principles theoretical calculations within the framework of density functional theory were employed to provide information at the atomic level. The band structure diagram, density of states, Raman and infrared spectra were calculated to understand the effect of structural order-disorder on the properties of ZnWO 4 . The effects of the synthesis temperature on the above properties were rationalized. The band structure revealed direct allowed transitions between the VB and CB and the experimental results in the ultraviolet-visible region were consistent with the theoretical results. Moreover, the surface calculations allowed the association of the surface energy stabilization with the temperature used in the synthesis of the ZnWO 4 nanocrystals. The photoluminescence properties of the ZnWO 4 nanocrystals prepared at 140, 150, and 160 °C were attributed to oxygen vacancies in the [WO 6 ] and [ZnO 6 ] clusters, causing a red shift of the spectra. The ZnWO 4 nanocrystals obtained at 160 °C exhibited excellent photodegradation of Rhodamine under ultraviolet light irradiation, which was found to be related to the surface energy and the types of clusters formed on the surface of the catalyst.

A theoretical study was elaborated to support the experimental results of the Zn-doped α-Ag 2 WO 4 . Theses α-Ag 2-2x Zn x WO 4 (0 ≤ x ≤ 0.25) solid solutions were obtained by coprecipitation method. X-ray diffraction data indicated that all α-Ag 2-2x Zn x WO 4 (0 ≤ x ≤ 0.25) microcrystals presented an orthorhombic structure. The experimental values of the micro-Raman frequencies were in reasonable agreement with both previously reported and calculated results. Microscopy images showed that the replacement of Ag + by Zn 2+ promoted a reduction in the average crystal size and modifications in the morphology, from rod-like with hexagonal shape to roll-like with a curved surface. A theoretical methodology based on the surfaces calculations and Wulff constructions was applied to study the particle shapes transformations and the surface energy variations in α-Ag 2-2x Zn x WO 4 (0 ≤ x ≤ 0.25) system. The decrease in the band gap value (from 3.18 to 3.08 eV) and the red shift in photoluminescence with the Zn 2+ addition were associated with intermediary energy levels between the valence and conduction bands. First-principles calculations with density functional theory associated with B3LYP hybrid functional were conducted. The calculated band structures revealed an indirect band gap for the α-Ag 2-2x Zn x WO 4 models. The electronic properties of α-Ag 2 WO 4 and α-Ag 2-2x Zn x WO 4 microcrystals were linked to distortion effects and oxygen vacancies (V O x ) present in the clusters, respectively. Finally, photoluminescence properties of α-Ag 2 WO 4 and α-Ag 2-2x Zn x WO 4 microcrystals were explained by means of distortional effects and oxygen vacancies (V O x ) in [AgO y ] (y = 2, 4, 6, and 7) and [WO 6 ] clusters, respectively, causing a red shift. Calculations revealed that the substitution for Ag + with Zn 2+ occurred randomly in the α-Ag 2 WO 4 lattice, and it was more favorable on the Ag4 site, where the local coordination of Ag + cations was four.

Efficacious patient safety monitoring should focus on the implementation of evidence-based practices that avoid unnecessary harm related to healthcare. The ISEP-Brazil project aimed to develop and validate indicators for best patient safety practices in Brazil. The basis was the translation and adaptation of the indicators validated in the ISEP-Spain project and the document Safe Practices for Better Healthcare (U.S. National Quality Forum), recommending 34 best practices. A 25-member expert panel validated the indicators. Reliability and feasibility were based on a pilot study in three hospitals with different management formats (state, federal, and private). Seventy-five best practice indicators were approved (39 structure; 36 process) for 31 of the 34 recommendations. The indicators were considered valid, reliable, and useful for monitoring patient safety in Brazilian hospitals.

In the present work, a combined theoretical and experimental study was performed on the structure, optical properties, and growth of Ag nanoparticles in metastable β-Ag2WO4 microcrystals. This material was synthesized using the precipitation method without the presence of surfactants. The structural behavior was analyzed using X-ray diffraction and Raman and infrared spectroscopy. Field-emission scanning electron microscopy revealed the presence of irregular spherical-like Ag nanoparticles on the β-Ag2WO4 microcrystals, which were induced by electron beam irradiation under high vacuum conditions. A detailed analysis of the optimized β-Ag2WO4 geometry and theoretical results enabled interpretation of both the Raman and infrared spectra and provided deeper insight into rationalizing the observed morphology. In addition, first-principles calculations, within the quantum theory of atoms in molecules framework, provided an in-depth understanding of the nucleation and early evolution of Ag nanoparticles. The Ag nucleation and formation is the result of structural and electronic changes of the [AgO6] and [AgO5] clusters as a constituent building block of β-Ag2WO4, which is consistent with Ag metallic formation.

Objective: To describe the tear ferning test (TFT) in healthy horses and its correlation with other parameters for evaluating the ocular surface., Animals Studied: Thirty male and female adult healthy horses (60 eyes), of no defined breed., Procedures: Tear sample was collected with a microcapillary tube, placed on the surface of a glass slide, and allowed to dry at room temperature. The crystallization pattern was classified according to Rolando (Chibret International Journal Ophthamology, 1984; 2, 32). The program STEPanizer(©) stereology tool, version 1.0, was utilized for counting points on the digitally captured crystallization image. A conjunctival biopsy was performed., Results: Tear ferning test was classified as Type I in 18 eyes (30%), Type II in 31 eyes (51.7%), and Type III in 11 eyes (18.3%), at a mean temperature of 27.3 ± 1.5 °C and relative humidity of 61.5 ± 5.7%. In the Type I crystallization, the count varied between 27 and 36 points (mean: 33.27 ± 2.40), in Type II between 22 and 31 points (25.42 ± 1.95), and in Type III between 13 and 25 points (16.82 ± 3.76). There was no statistical difference or correlation between the right and left eyes, nor was there a statistically significant influence (P < 0.05) on TFT by the factors evaluated. The mean goblet cells values were 50 ± 11.4 cells/field. All samples showed the presence of lymphocytes, plasmocytes, and eosinophils., Conclusion: Tear ferning test is easy to perform, without risks to the patient. Once standardized for horses, associated or not with the program STEPanizer(©) stereology tool, it is an additional method for evaluating the ocular surface., (© 2015 American College of Veterinary Ophthalmologists.)

Metastable silver tungstate (β-Ag2WO4) has attracted much attention lately because of its many potential applications. However, the synthesis of metastable phases of inorganic compounds is challenging because of the ease of transformation to the stable phase. We have overcome this challenge and have successfully synthesized β-Ag2WO4 microcrystals using a dropwise precipitation (DP) method in aqueous media at low temperature. The microcrystals were characterized by X-ray diffraction (XRD), including powder X-ray diffraction structural determination, field-emission scanning electron microscopy (FE-SEM), and micro-Raman/ultraviolet-visible (UV-vis) diffuse reflectance spectroscopy. To complement the experimental data, we present first-principles quantum-mechanical density functional theory (DFT) calculations. Using XRD data, Raman/UV-vis data, and the determined optical band gap, together with geometric optimization calculations, we confirmed the structure of this compound. β-Ag2WO4 has a hexagonal structure with a P63/m space group. The building blocks of the lattice comprise two types of W-O clusters, [WO4] and [WO5], coordinated to four and five O atoms, respectively, and two types of Ag-O clusters, [AgO6], and [AgO5], linked to six and five O atoms, respectively. This type of fundamental study, combining multiple experimental methods and first-principles calculations, helps to obtain a basic understanding of the local structure and bonding in the material.

Morphology is a key property of materials. Owing to their precise structure and morphology, crystals and nanocrystals provide excellent model systems for joint experimental and theoretical investigations into surface-related properties. Faceted polyhedral crystals and nanocrystals expose well-defined crystallographic planes depending on the synthesis method, which allow for thoughtful investigations into structure-reactivity relationships under practical conditions. This feature article introduces recent work, based on the combined use of experimental findings and first-principles calculations, to provide deeper knowledge of the electronic, structural, and energetic properties controlling the morphology and the transformation mechanisms of different metals and metal oxides: Ag, anatase TiO2, BaZrO3, and α-Ag2WO4. According to the Wulff theorem, the equilibrium shapes of these systems are obtained from the values of their respective surface energies. These investigations are useful to gain further understanding of how to achieve morphological control of complex three-dimensional crystals by tuning the ratio of the surface energy values of the different facets. This strategy allows the prediction of possible morphologies for a crystal and/or nanocrystal by controlling the relative values of surface energies.

This study is a framework proposal for understanding the antimicrobacterial effect of both α-Ag2WO4 microcrystals (AWO) synthesized using a microwave hydrothermal (MH) method and α-Ag2WO4 microcrystals with Ag metallic nanofilaments (AWO:Ag) obtained by irradiation employing an electron beam to combat against planktonic cells of methicillin-resistant Staphylococcus aureus (MRSA). These samples were characterized by X-ray diffraction (XRD), FT-Raman spectroscopy, ultraviolet visible (UV-vis) measurements, field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), and high resolution transmission electron microscopy (HRTEM). The results reveal that both AWO and AWO:Ag solutions have bacteriostatic and bactericidal effects, but the irradiated sample is more efficient; i.e., a 4-fold of the MRSA planktonic cells as compared to the nonirradiated sample was observed. In addition, first principles calculations were performed to obtain structural and electronic properties of AWO and metallic Ag, which provides strong quantitative support for an antimicrobacterial mechanism based on the enhancement of electron transfer processes between α-Ag2WO4 and Ag nanoparticles.

This paper presents the correlation among electronic and optical property effects induced by the addition of different concentrations of europium (Eu3+) in zinc sulfide (ZnS) by microwave-assisted solvothermal (MAS) method. A shift of the photoluminescence (PL) emission was observed with the increase of Eu3+. The periodic DFT calculations with the B3LYP hybrid functional were performed using the CRYSTAL computer code. The UV-vis spectra and theoretical results indicate a decrease in behavior of the energy gap as a function of dopant concentration. Therefore, new localized states are generated in the forbidden band gap region, the new states increase the probability of less energy transitions which may be responsible for a red shift in the PL bands spectrum.

In this paper, we investigate a correlation between theoretical calculations and experimental data to explain the electronic structure and optical properties of silver molybdate (β-Ag2MoO4) microcrystals synthesized by the microwave-assisted hydrothermal method. X-ray diffraction, Rietveld refinement, and micro-Raman spectroscopy confirmed that these microcrystals crystallize in a spinel-type cubic structure. Field-emission scanning electron microscopy images revealed that the processing temperatures influence in the final shape of microcrystals. Optical properties were analyzed by ultraviolet-visible diffuse reflectance spectroscopy; the increase in the optical band gap energy (Egap) (from 3.24 to 3.31 eV) with processing temperature is associated with the reduction of intermediary energy levels. First-principles quantum mechanical calculations based on the density functional theory at the B3LYP level were conducted. The calculated band structure revealed an indirect Egap of approximately 4.00 and 3.34 eV for the β-Ag2MoO4 without and with the formation of defects, respectively. Theoretical calculations based on density of states and electron density maps were employed to understand the polarization phenomenon induced by structural defects in the β-Ag2MoO4 crystals. Finally, photoluminescence properties at room temperature of β-Ag2MoO4 microcrystals were explained by the charge-transfer mechanism involving tetrahedral [MoO4] clusters.

In this letter, we report, for the first time, the real-time in situ nucleation and growth of Ag filaments on α-Ag2WO4 crystals driven by an accelerated electron beam from an electronic microscope under high vacuum. We employed several techniques to characterise the material in depth. By using these techniques combined with first-principles modelling based on density functional theory, a mechanism for the Ag filament formation followed by a subsequent growth process from the nano- to micro-scale was proposed. In general, we have shown that an accelerated electron beam from an electronic microscope under high vacuum enables in situ visualisation of Ag filaments with subnanometer resolution and offers great potential for addressing many fundamental issues in materials science, chemistry, physics and other fields of science.

The syringyl/guaiacyl ratio was determined for six different Eucalyptus spp. wood clones cultivated in four regions in Brazil. The determinants were made by pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) and the results were compared with those obtained by alkaline nitrobenzene oxidation method. The S/G ratios were obtained considering all the identified lignin derivatives in the pyrograms and also using two groups of markers. The first group of markers consisted of guaiacol, 4-methylguaiacol, 4-vinylguaiacol, trans-isoeugenol, syringol, 4-methylsyringol, 4-vinylsyringol and trans-4-propenylsyringol compounds as markers. The second group included guaiacol, 4-methylguaiacol, 4-vinylguaiacol, vanillin, 4-ethylsyringol, 4-vinylsyringol, syringaldehyde, syringylacetone and trans-4-propenylsyringol. It was observed from the statistical analysis that the values of S/G obtained by Py-GC-MS using the two groups of markers did not differ significantly from those obtained by nitrobenzene oxidation method., (Copyright 2010 Elsevier Ltd. All rights reserved.)