Bacterial Nanocellulose/MoS2 Hybrid Aerogels as Bifunctional Adsorbent/Photocatalyst Membranes for in-Flow Water Decontamination.

To address the problems associated with the use of unsupported nanomaterials, in general, and molybdenum disulfide (MoS2), in particular, we report the preparation of self-supported hybrid aerogel membranes that combine the mechanical stability and excellent textural properties of bacterial nanocellulose (BC)-based organic macro/mesoporous scaffolds with the excellent adsorption-cum-photocatalytic properties and high contaminant removal performance of MoS2 nanostructures. A controlled hydrothermal growth and precise tuning of the synthetic parameters allowed us to obtain BC/MoS2-based porous, self-supported, and stable hybrid aerogels with a unique morphology resulting from a molecular precision in the coating of quantum-confined photocatalytic MoS2 nanostructures (2-4 nm crystallite size) on BC nanofibrils. These BC/MoS2 samples exhibit high surface area (97-137 m2·g-1) and pore volume (0.28-0.36 cm3·g-1) and controlled interlayer distances (0.62-1.05 nm) in the MoS2 nanostructures. Modification of BC with nanostructured MoS2 led to an enhanced pollutants removal efficiency of the hybrid aerogels both by adsorptive and photocatalytic mechanisms, as indicated by a detailed study using a specifically designed membrane photoreactor containing the developed photoactive/adsorptive BC/MoS2 hybrid membranes. Most importantly, the prepared BC/MoS2 aerogel membranes showed high performance in the photoassisted in-flow removal of both organic dye (methylene blue (MB)) molecules (96% removal within 120 min, Kobs = 0.0267 min-1) and heavy metal ions (88% Cr(VI) removal within 120 min, Kobs = 0.0012 min-1), separately and/or simultaneously, under UV-visible light illumination as well as excellent recyclability and photostability. Samples with interlayer expanded MoS2 nanostructures were particularly more efficient in the removal of smaller species (CrO42-) as compared to larger (MB) dye molecules. The prepared hybrid aerogel membranes show promising behavior for application in in-flow water purification, representing a significant advancement in the use of self-supported aerogel membranes for photocatalytic applications in liquid media.

Qualitative and Semiquantitative Determination of the Atomic and Molecular Tungsten Distributions in Hybrid Hydroxyurethanes-Poly(dimethylsiloxane) Films Containing Phosphotungstates ([PW12O40]3-).

In this study, hybrid poly(dimethylsiloxane)-derived hydroxyurethanes films (PDMSUr-PWA) containing phosphotungstic acid (H3PW12O40/PWA) were characterized using field emission gun scanning electron microscopy (FEG-SEM), in attenuated total reflectance Fourier transform mid-infrared mode (ATR FT-MIR), and analyzed using synchrotron radiation micro-X-ray fluorescence (SR-µXRF), synchrotron radiation grazing incidence X-ray fluorescence (SR-GIXRF), laser-induced breakdown spectroscopy (LIBS), and instrumental neutron activation analysis (NAA) in order to correlate the distribution patterns of tungsten and properties of PDMSUr-PWA films. PDMS constitute elastomers with good mechanical, thermal, and chemical (hydrophobicity/non-hygroscopy) resistance. Currently, products based on urethanes (e.g., polyurethanes) are widely used in many applications as plastics, fiber-reinforced polymers, high-performance adhesives, corrosion-resistant coatings, photochromic films, among others. The possibility to combine inorganic and organic components can produce a hybrid material with unique properties. PWA has an important role as agent against the corrosion of steel surfaces in different media, besides exhibiting amazing catalytic and photochromic properties in these films. PWA kept its structure inside of these hybrid films through interactions between the organic matrix of PDMSUr and silanol from the inorganic part (organically modified silica), as was shown using ATR FT-MIR spectra. The FEG-SEM/SR-µXRF/wide-angle X-ray scattering (WAXS)/X-ray diffraction (XRD)/energy dispersive X-ray results proved the presence of PWA in the composition of domains of PDMSUr-PWA films. At PWA concentrations higher than 50 wt%/wt, tungsten segregation across the thickness is predominant, while that at PWA concentrations lower than 35 wt%/wt, tungsten segregation at surface is predominant. Inhomogeneities in the tungsten distribution patterns (at micrometric and millimetric level) may play an important role in the mechanical properties of these films (elastic modulus and hardness).

Effect of Heavy Metals Contamination from Cigarette Smoke on Sound and Caries-Like Enamel.

In this study, we sought to evaluate the influence of cigarette smoke and pH cycling on the chemical composition and surface/cross-sectional enamel microhardness. A total of 40 dental blocks obtained from bovine incisors were divided into four groups (n=10): no treatment (control); exposure to cigarette smoke (CS); exposure to pH cycling (PC); and exposure to cigarette smoke and pH cycling (CS-PC). The samples were analyzed by synchrotron radiation micro X-ray fluorescence, bench mode X-ray fluorescence, as well as surface microhardness (SMH) and cross-sectional microhardness (CSMH) testing. The SMH results were submitted to analysis of variance (ANOVA) and Tukey's test. The CSMH results were evaluated using split-plot ANOVA and Tukey's test. A high amount of Cd and Pb and traces of Ni and As were observed in enamel and dentin after exposure to cigarette smoke (CS and CS-PC). The SMH and CSMH of CS were statistically higher when compared with the control. The PC and CS-PC showed lower SMH and CSMH. We conclude that exposure to cigarette smoke promoted heavy metal deposition in enamel/dentin. In addition, it increased the enamel microhardness but did not promote a protective effect on the in vitro development of caries. The clinical significance of this work is that there is significant bioaccumulation of heavy metals from cigarette smoke on the surface and in the enamel and dentin.

Acidic Dressing Based on Agarose/Cs2.5H0.5PW12O40 Nanocomposite for Infection Control in Wound Care.

Regulation of wound pH from alkaline to acidic is a simple and powerful approach to reduce wound microbial colonization and infection. Here, we present a nanocomposite material possessing intrinsic acidic surface pH as an innovative antimicrobial wound dressing. This material comprises an agarose matrix nanocomposite containing nanoparticles (NPs) of the cesium salt of phosphotungstic heteropolyacid (Cs2.5H0.5PW12O40). Self-supporting films were prepared by a casting method incorporating 5-20 wt % Cs2.5H0.5PW12O40 NPs into the matrix. Films are flexible with tensile strengths between 28.55 and 32.15 MPa and exhibit broad biocidal activity against neutralophilic pathogens, including Gram-positive bacteria, Gram-negative bacteria, yeast, and filamentous fungi. The nano-antimicrobial Cs2.5H0.5PW12O40 functions as an efficient and self-controlled proton delivery agent that lowers the surface pH of the nanocomposites to the range 7.0 > pH ≥ 3.0. Nanocomposite films containing 20 wt % Cs2.5H0.5PW12O40 NPs presented a surface pH of 3.0 and highest antimicrobial activity. Using quantitative reverse transcription polymerase chain reaction, we demonstrated that the antimicrobial mechanism of the nanocomposites is acid-induced because of the transcriptional induction of glutamate-dependent acid resistance genes in Escherichia coli. Additionally, nanocomposite films do not damage skin according to an in vivo rabbit skin model with no derived edema or erythema. The wound care safety of this material is due to low release of heavy metal heteropolyanions ([PW12O40]3-), no nanoparticle leaching, and proton controlled release resulting in nonirritating acid levels for human skin models.

New Hybrid Nanomaterial Based on Self-Assembly of Cyclodextrins and Cobalt Prussian Blue Analogue Nanocubes.

Supramolecular self-assembly has been demonstrated to be a useful approach to developing new functional nanomaterials. In this work, we used a cobalt Prussian blue analogue (PBA, Co3[Co(CN)6]2) compound and a ß-cyclodextrin (CD) macrocycle to develop a novel host-guest PBA-CD nanomaterial. The preparation of the functional magnetic material involved the self-assembly of CD molecules onto a PBA surface by a co-precipitation method. According to transmission electronic microscopy results, PBA-CD exhibited a polydisperse structure composed of 3D nanocubes with a mean edge length of 85 nm, which became shorter after CD incorporation. The supramolecular arrangement and structural, crystalline and thermal properties of the hybrid material were studied in detail by vibrational and electronic spectroscopies and X-ray diffraction. The cyclic voltammogram of the hybrid material in a 0.1 mol · L(-1) NaCl supporting electrolyte exhibited a quasi-reversible redox process, attributed to Co2+/Co3+ conversion, with an E1/2 value of 0.46 V (vs. SCE), with higher reversibility observed for the system in the presence of CD. The standard rate constants for PBA and PBA-CD were determined to be 0.07 and 0.13 s(-1), respectively, which suggests that the interaction between the nanocubes and CD at the supramolecular level improves electron transfer. We expect that the properties observed for the hybrid material make it a potential candidate for (bio)sensing designs with a desirable capability for drug delivery.

Effects of the long-term administration of alendronate on the mechanical properties of the basal bone and on osseointegration.

OBJECTIVE: To evaluate the effect of the long-term administration of alendronate on the mechanical properties of the basal bone and on osseointegration. MATERIAL AND METHODS: One hundred and sixty female rats were randomly allocated into two equally sized groups: the control (CTL) group, which received the subcutaneous administration of saline solution, and the alendronate (ALD) group, which received the subcutaneous administration of alendronate (1 mg/kg/week). After 120 days of these therapies, one implant was placed in each rat tibia. Ten animals in each group were euthanized at 5, 10, 15, 20, 25, 30, 45, or 60 days after surgery. The tibias with implants evaluated regarding the removal torque, bone-implant contact (BIC), the bone area fraction occupancy (BAFO), and Ca/P ratio. The femurs were evaluated regarding bone mineral density (BMD) and using mechanical tests to evaluate the maximal force of fracture, stiffness, and tenacity. RESULTS: The ALD group presented statistically significant higher BMD (all periods except 15 days), maximal force of fracture (at 20, 30, and 45 days), tenacity (at 10, 20, 30, and 45 days), stiffness (45 days), removal torque (at 20, 25 and 30 days), BIC (at 20 and 60 days), and BAFO (at 20, 30, and 45 days) than the CTL group. No differences were found between the groups regarding the Ca/P ratio. CONCLUSION: Previous long-term therapy with alendronate caused an increase in the BMD, maximal force of fracture of the bone without changing the inorganic composition and elastic deformability of this tissue. Furthermore, the ALD therapy enhanced osseointegration.

Contactless conductivity biosensor in microchip containing folic acid as bioreceptor.

We report a glass/PDMS-based microfluidic biosensor that integrates contactless conductivity transduction and folic acid, a target for tumor biomarker, as a bioreceptor. The device presents relevant advantages such as direct determination--dismiss the use of redox mediators as in faradaic electrochemical techniques--and the absence of the known drawbacks related to the electrode-solution interface. Characterizations of the functionalization processes and chemical sensor are described in this communication.

The ethanol electrooxidation at Pt layers deposited on polycrystalline Au.

The ethanol electro-oxidation reaction was evaluated using a polycrystalline Au substrate modified with two different amounts of Pt using the galvanic exchange methodology. FTIR results suggest that Pt deposits have a greater ability to break the C-C bond present in the ethanol molecule. However, under potentiostatic conditions both modified Au surfaces undergo faster deactivation in comparison with polycrystalline platinum as indicated by the chronoamperometric results. XPS results indicate the presence of two phases depending on the Pt content. These are: (i) Pt-Au alloy and (ii) segregated Pt. The structural and electronic properties of these phases were related to the differences observed in the catalytic activity.

Poly(imide)/Organically-Modified Montmorillonite Nanocomposite as a Potential Membrane for Alkaline Fuel Cells.

In this work we evaluated the potentiality of a poly(imide) (PI)/organically-modified montmorillonite (O-MMT) nanocomposite membrane for the use in alkaline fuel cells. Both X-ray diffraction and scanning electron microscopy revealed a good dispersion of O-MMT into the PI matrix and preservation of the O-MMT layered structure. When compared to the pure PI, the addition of O-MMT improved thermal stability and markedly increased the capability of absorbing electrolyte and ionic conductivity of the composite. The results show that the PI/O-MMT nanocomposite is a promising candidate for alkaline fuel cell applications.

Strategies to optimize biosensors based on impedance spectroscopy to detect phytic acid using layer-by-layer films.

Impedance spectroscopy has been proven a powerful tool for reaching high sensitivity in sensor arrays made with nanostructured films in the so-called electronic tongue systems, whose distinguishing ability may be enhanced with sensing units capable of molecular recognition. In this study we show that for optimized sensors and biosensors the dielectric relaxation processes involved in impedance measurements should also be considered, in addition to an adequate choice of sensing materials. We used sensing units made from layer-by-layer (LbL) films with alternating layers of the polyeletrolytes, poly(allylamine) hydrochloride (PAH) and poly(vinyl sulfonate) (PVS), or LbL films of PAH alternated with layers of the enzyme phytase, all adsorbed on gold interdigitate electrodes. Surprisingly, the detection of phytic acid was as effective in the PVS/PAH sensing system as with the PAH/phytase system, in spite of the specific interactions of the latter. This was attributed to the dependence of the relaxation processes on nonspecific interactions such as electrostatic cross-linking and possibly on the distinct film architecture as the phytase layers were found to grow as columns on the LbL film, in contrast to the molecularly thin PAH/PVS films. Using projection techniques, we were able to detect phytic acid at the micromolar level with either of the sensing units in a data analysis procedure that allows for further optimization.

A regenerable ruthenium tetraammine nitrosyl complex immobilized on a modified silica gel surface: preparation and studies of nitric oxide release and nitrite-to-NO conversion.

Silica gel bearing isonicotinamide groups was prepared by further modification of 3-aminopropyl-functionalized silica by a reaction with isonicotinic acid and 1,3-dicyclohexylcarbodiimide to yield 3-isonicotinamidepropyl-functionalized silica gel (ISNPS). This support was characterized by means of infrared spectroscopy, elemental analysis, and specific surface area. The ISNPS was used to immobilize the [Ru(NH(3))(4)SO(3)] moiety by reaction with trans-[Ru(NH(3))(4)(SO(2))Cl]Cl, yielding [Si(CH(2))(3)(isn)Ru(NH(3))(4)(SO(3))]. The related immobilized [Si(CH(2))(3)(isn)Ru(NH(3))(4)(L)](3+/2+) (L=SO(2), SO(2-)(4), OH(2), and NO) complexes were prepared and characterized by means of UV-vis and IR spectroscopy, as well as by cyclic voltammetry. Syntheses of the nitrosyl complex were performed by reaction of the immobilized ruthenium ammine [Si(CH(2))(3)(isn)Ru(NH(3))(4)(OH(2))](2+) with nitrite in acid or neutral (pH 7.4) solution. The similar results obtained in both ways indicate that the aqua complex was able to convert nitrite into coordinated nitrosyl. The reactivity of [Si(CH(2))(3)(isn)Ru(NH(3))(4)(NO)](3+) was investigated in order to evaluate the nitric oxide (NO) release. It was found that, upon light irradiation or chemical reduction, the immobilized nitrosyl complex was able to release NO, generating the corresponding Ru(III) or Ru(II) aqua complexes, respectively. The NO material could be regenerated from these NO-depleted materials obtained photochemically or by reduction. Regeneration was done by reaction with nitrite in aqueous solution (pH 7.4). Reduction-regeneration cycles were performed up to three times with no significant leaching of the ruthenium complex.

Fabrication of phytic acid sensor based on mixed phytase-lipid Langmuir-Blodgett films.

This paper reports the surface activity of phytase at the air-water interface, its interaction with lipid monolayers, and the construction of a new phytic acid biosensor on the basis of the Langmuir-Blodgett (LB) technique. Phytase was inserted in the subphase solution of dipalmitoylphosphatidylglycerol (DPPG) Langmuir monolayers, and its incorporation to the air-water interface was monitored with surface pressure measurements. Phytase was able to incorporate into DPPG monolayers even at high surface pressures, ca. 30 mN/m, under controlled ionic strength, pH, and temperature. Mixed Langmuir monolayers of phytase and DPPG were characterized by surface pressure-area and surface potential-area isotherms, and the presence of the enzyme provided an expansion in the monolayers (when compared to the pure lipid at the interface). The enzyme incorporation also led to significant changes in the equilibrium surface compressibility (in-plane elasticity), especially in liquid-expanded and liquid-condensed regions. The dynamic surface elasticity for phytase-containing interfaces was investigated using harmonic oscillation and axisymmetric drop shape analysis. The insertion of the enzyme at DPPG monolayers caused an increase in the dynamic surface elasticity at 30 mN m(-)(1), indicating a strong interaction between the enzyme and lipid molecules at a high-surface packing. Langmuir-Blodgett (LB) films containing 35 layers of mixed phytase-DPPG were characterized by ultraviolet-visible and fluorescence spectroscopy and crystal quartz microbalance nanogravimetry. The ability in detecting phytic acid was studied with voltammetric measurements.

Heterometallic manganese/zinc-phytate complex as a model compound for metal storage in wheat grains.

Myo-inositol-1,2,3,4,5,6-hexakisphosphate, also known as phytate, is a natural metal chelate present in cereals, an important feedstock worldwide. This article reports the characterization of three metal storage model complexes: the homometallic Mn(II) myo-inositol-1,2,3,4,5,6-hexakisphosphate (IP6), the heterometallic Zn(II), Mn(II) analogue Na4MnZn4(C6H6O24P6) x (NO3)2 x 8H2O (MnZn4IP6) and the homometallic Zn(II) metal complex Na3Zn5(C6H6O24P6)OH x 9H2O (Zn5IP6). The techniques of high-resolution 23Na, 13C and 31P NMR, electron paramagnetic resonance (EPR) and X-ray photoelectron spectroscopy (XPS) were applied in this study. The complexation of Zn(II) and Mn(II) by phosphate groups of IP6 is demonstrated by NMR and XPS results. 13C NMR results show a conformation for IP6 consisting of five equatorial phosphate groups to one axial group showing only one chemical environment for Zn and two for Mn, when characterized by XPS and EPR, in both Mn complexes. These results support, for the first time, a probable supramacromolecular structure for phytate complexes of transition metals. Based on the similarity between the EPR spectra of wheat seeds and that of the MnZn4IP6 compound, the manganese storage centers in wheat grains can be assigned to similar heterometallic phytate complexes.

Adsorption of silanes bearing nitrogenated Lewis bases on SiO2/Si (100) model surfaces.

The present paper describes the one-pot procedure for the formation of self-assembled thin films of two silanes on the model oxidized silicon wafer, SiO2/Si. SiO2/Si is a model system for other surfaces, such as glass, quartz, aerosol, and silica gel. MALDI-TOF MS with and without a matrix, XPS, and AFM have confirmed the formation of self-assembled thin films of both 3-imidazolylpropyltrimethoxysilane (3-IPTS) and 4-(N-propyltriethoxysilane-imino)pyridine (4-PTSIP) on the SiO2/Si surface after 30 min. Longer adsorption times lead to the deposition of nonreacted 3-IPTS precursors and the formation of agglomerates on the 3-IPTS monolayer. The formation of 4-PTSIP self-assembled layers on SiO2/Si is also demonstrated. The present results for the flat SiO2/Si surface can lead to a better understanding of the formation of a stationary phase for affinity chromatography as well as transition-metal-supported catalysts on silica and their relationship with surface roughness and ordering. The 3-IPTS and 4-PTSIP modified SiO2/Si wafers can also be envisaged as possible built-on-silicon thin-layer chromatography (TLC) extraction devices for metal determination or N-heterocycle analytes, such as histidine and histamine, with "on-spot" MALDI-TOF MS detection.

Activation of carbon dioxide by bicyclic amidines.

Activation of the carbon dioxide molecule was achieved using bicyclic amidines (DBU, PMDBD, and DBN). The solution reaction of CO(2) with amidines yielded the corresponding zwitterionic complexes through the formation of a N-CO(2) bond. (13)C NMR data confirmed the carbamic nature of the carbamic zwitterions, DBU-CO(2) and PMDBD-CO(2). However, when these adducts were crystallized, the X-ray analyses of the single crystals were in agreement with bisamidinium bicarbonate salt structures, indicating that structural changes occurred in the crystallization process. The elemental and thermogravimetric analysis data for the carbamic zwitterions, DBU-CO(2) and PMDBD-CO(2), initially obtained by the direct reaction of amidines with CO(2), suggest that these molecules are probably associated with one molecule of water by hydrogen-bond formation (amidinium(+)-COO(-)...H(2)O). A correlation was observed between the thermal stability and the transcarboxylating activity for the amidine-CO(2) complexes. Theoretical calculations of hardness were performed at the B3LYP/cc-pVTZ level of theory and showed concordance with the experimental reactivity of DBU and PMDBD toward CO(2).