Fabrication of silver nanosheets on quartz glass substrates through electroless plating approach

Silver nanosheets (NSs) have been synthesized by an electroless plating approach using a complexation mechanism of triethanolamine (TEA) and Ag⁺ to reduce the oxidation–reduction potential difference and slow down the deposition speed of Ag on quartz glass substrates. The synthesized Ag NSs with 500 nm in edge length and 30 nm in thickness stand on the substrates and are dispersed uniformly. The formation mechanism of Ag NSs is proposed. The formation of Ag NSs is attributed to the molar ratio of AgNO₃ to TEA, the concentration of AgNO₃ and the influence of reaction temperature. This study is important in vertical immobilization Ag NSs on solid substrates, which could provide substrates for catalysis or surface-enhanced Raman scattering.     

Photocatalysis of novel reduced graphene oxide-CoSe nanocomposites with efficient interface-induced effect

In this work, reduced graphene oxide–CoSe (rGO–CoSe) nanocomposites were synthesized with chemical solution reaction and characterized by X-ray diffraction, scanning electron microscopy, Raman spectroscopy, Fourier transform infrared spectroscopy, UV–vis spectroscopy, and photodegradation of toxicity malachite green in the water. The effects of rGO/CoSe ratio, initial solution pH, and H₂O₂ concentration on the photodegradation effeciency were studied. The nanocomposites showed excellent sunlight-excited photocatalytic activity to toxicity malachite green in the water. The photodegradation rate increased with increasing rGO/CoSe ratio and initial solution pH. Significantly, remarkable Fenton-like photocatalytic activity enhanced with increasing rGO/CoSe ratio and H₂O₂ concentration was observed. The photodegradation rate constant, k obs, was determined under pseudo-first order conditions. The interface-induced mechanism on enhanced photocatalysis with rGO/CoSe was suggested.     

Conformational flexibility of xanthene‐based covalently linked dimers

The conformational flexibility of three covalently linked dimers consisting of two xanthene‐based moieties connected by a diphenyl ether linker was studied using NMR spectroscopy, X‐ray crystallography, and density functional theory (DFT) calculations. The three dimers interconvert as a function of pH: the doubly cationic dimer (Xan⁺)₂ exists in acidic solutions (pH < 0.5), the mono‐alcohol monocation Xan⁺–Xan‐OH at intermediate pH values (pH = 1–3), and the neutral diol at the highest pH‐values (pH > 3). Each dimer exhibits conformational degrees of freedom associated with rotations of either the xanthene moiety or of the diphenyl ether (DPE) linker. The barriers for rotation of the xanthylium moiety were evaluated using DFT calculations, yielding values of 23 kcal/mol for (Xan⁺)₂ and 11 kcal/mol for (Xan‐OH)₂, respectively. The rotational barrier for the diphenyl ether linker in Xan⁺–Xan‐OH (15 kcal/mol) was experimentally determined using variable temperature NMR measurements. The relative orientation of the two –OH groups in (Xan‐OH)₂ diol was investigated in solution and the solid state using NMR spectroscopy and X‐ray crystallography. The conformer observed in the solid state was found to be the In–Out conformer, while free rotation of the xanthenol units is thought to occur on the NMR timescale at room temperature. These studies are relevant for the design of linkers for efficient water oxidation catalysts. Copyright © 2016 John Wiley & Sons, Ltd.     

Interaction of transferrin with cefuroxime sodium

ABSTRACT

The interaction between cefuroxime sodium and transferrin in physiological buffer (pH 7.4) was investigated by spectroscopy at 298, 310, and 318?K. The analysis of data indicated that quenching mechanism of the transferrin–cefuroxime sodium system was probably static. The electrostatic force played an important role in the conjugation reaction between transferrin and cefuroxime sodium. The order of magnitude of binding constants (K_a) was 10⁴, and the number of binding site (n) in the binary system was approximately equal to 1. Besides, the values of Hill’s coefficients were lager than 1, which indicated very weakly positive cooperativity in the transferrin–cefuroxime sodium system. The synchronous fluorescence spectra and circular dichroism spectra revealed that the microenvironment and the conformation of transferrin were changed during the binding reaction.     

Engineering birnessite-type MnO2 nanosheets on fiberglass for pH-dependent degradation of methylene blue

We construct hierarchical MnO₂ nanosheets @ fiberglass nanostructures via one-pot hydrothermal method without any surfactants. The morphology and structure of MnO₂-modified fiberglass composites are examined by focus ion beam scanning electron microscopy (FIB/SEM), X-Ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR). The birnessite-type MnO₂ nanosheets are observed to grow vertically on the surface of fiberglass. Furthermore, the birnessite-type MnO₂-fiberglass composites exhibit good ability for degradation of methylene blue (MB) in different pH levels. In neutral solution (pH 6.5–7.0), it achieves a high removal rate of 96.1% (2 h, at 60 °C) in the presence of H₂O₂; and in acidic environment (pH 1.5), 96.8% of MB solution (20 mg/L, 100 mL) is decomposed by oxidation within only 5 min. In principles, the rational design of MnO₂ nanosheets-decorated fiberglass architectures demonstrated the suitability of the low-cost MnO₂-modified fiberglass nanostructure for water treatment.     

EPR Technology Spectroscopic Investigation of Generation of Reactive Oxygen Species Free Radicals in Laccase-Activated Jute Fiber

Lignins in jute fibers can be activated by laccase to generate reactive oxygen species (ROS) free radicals for subsequent use in radical graft polymerization. The effect of incubation conditions on the generation of ROS free radicals when jute powders were incubated with laccase was investigated through spin-trapping technique to detect the spin adduct of N-tert-butyl-α-phenylnitrone and ROS free radical using electron paramagnetic resonance spectroscopy. Results revealed that the highest concentrations of ROS free radicals were generated when jute was incubated with laccase (0.54 U/mL) and copper ions (10 mM) in solution at pH 3.5 and a temperature of 60 °C for 1 h.     

A197Au Mössbauer study of the adsorption of aurocyanide onto activated carbon

The chemical state of gold adsorbed on activated carbon from solutions of KAu(CN)₂ has been studied by¹⁹⁷Au Mössbauer spectroscopy as a function of the pH and concentration of the solution, the loading of the carbon, and the drying conditions of the samples. On freshly prepared specimens Au(CN) ₂ ^? is always the dominant species. Drying leads to the formation of other forms of gold, mainly in samples loaded from strongly acidic media. An oligomeric form of AuCN is, however, also formed when samples loaded at high pH values are dried at temperatures around 100°C.     

ESR Study in Reactive Oxygen Species Free Radical Production of Pinus kesiya var. langbianensis Heartwood Treated with Laccase

Enzymatic oxidation of lignin phenolic hydroxyl groups can enhance the level of autoadhesion between wood fibers or particles depending upon the bonding mechanism of wood-based materials without synthetic adhesives such as urea and phenol formaldehyde. The adhesive effect is caused by an increased number of reactive oxygen groups at the fiber surface. The parameters of laccase-treated wood fibers play vital roles in generating reactive oxygen species (ROS) free radicals. Laccase I (white-rot fungi) and laccase II (Aspergillus sp.) are used to catalyze the oxidation of heartwood powder of Pinus kesiya var. langbianensis in suspension under different pH values, temperatures, treatment times and different laccase concentrations. Electron spin resonance spectroscopy and spin trapping technique were used to detect the ROS free radicals generated in the laccase-treated heartwood powder and it was found that in it the concentration of ROS free radicals was higher than that in the control. Analysis of variance indicates that there was a significant difference between the ROS concentration values of laccase-treated heartwood powder under different pH values, treatment temperatures and times, and laccase dosages for both laccase I and II. Furthermore, the concentration of ROS free radicals generated by laccase I is higher than that generated by laccase II. It was found that the optimum conditions for generation of ROS in laccase-treated heartwood powder by the two kinds of laccase are pH 3.0; treatment temperature, 50 °C; treatment time, 2 h; enzyme concentration, 20 units/g of wood powder. Authors' address: Xinfang Duan, Research Institute of Wood Industry, Chinese Academy of Forestry, Wan Shou Shan, Beijing 100091, People's Republic of China     

Spectroscopic investigation on the sonodynamic activity of Safranine T to bovine serum albumin damage

In this paper, the Safranine T (ST) was used as sonosensitive compound to study the sonodynamic damage to bovine serum albumin (BSA) under ultrasonic irradiation using fluorescence and UV–vis spectroscopy. The experimental results revealed the obvious synergetic effect of Safranine T (ST) and ultrasonic irradiation during the damage of BSA molecules. In addition, some influencing factors such as ultrasonic irradiation time, Safranine T (ST) concentration, pH value and ionic strength on the sonodynamic damage of BSA molecules were also considered. Finally, the generation of reactive oxygen species (ROS) in sonodynamic process was estimated by the method of Oxidation-Extraction Photometry (OEP). Meanwhile, several radical scavengers were used to determine the kind of generated ROS. Experiments showed that under ultrasonic irradiation the Safranine T (ST) can generate several kinds of ROS at the same time, at least including singlet oxygen (¹O₂) and hydroxyl radicals (OH).     

Synthesis and hyperfine interactions of the amine intercalates of FeOCl

Some amine derivatives were intercalated into the van der Waals gap of layered compound FeOCl. These compounds were characterized by X-ray powder diffraction and Mössbauer spectroscopy. The isomer shift and the quadrupole splitting are characteristic of the high-spin ferric iron. The magnetic structure of FeOCl was affected by intercalation of amine molecules in the interlayer region of FeOCl. The magnetic hyperfine field in the low temperature is larger in the intercalates than it is in unintercalated FeOCl. The sign of the EFG tensor at the iron atom is dependent of the type of amine intercalated.     

Surface anchoring mode‐dependent hydrolysis reactions of hydrazone groups on gold examined by pH‐dependent Raman spectroscopy

We conducted a comparative study of the pH‐dependent anchoring behaviors of 3‐methyl‐2‐benzothiazolinone hydrazone (3M2BH) and benzophenone hydrazone (BPH) on gold nanoparticles (AuNPs) by means of interfacial Raman spectroscopy. We found that several bands of 3M2BH in the highly alkaline pH region disappeared as the colloidal conditions became more neutral and acidic. The vibrational band at 919, 1174, and 1222 cm⁻¹ at pH 10.0 disappeared below pH 9.2, which may be because of the hydrolysis reactions that cleave the labile N―NH₂ group of 3M2BH, indicating a rather perpendicular orientation via the sulfur atom at the surfaces. A fairly high transition pH value was assumed to be because of the interaction of the N―NH₂ group in the vicinity of the surfaces. Several characteristic bands, including 1584 and 1617 cm⁻¹, also exhibited different intensities, suggesting that the adsorbates on Au surfaces underwent structural transformations of the N―NH₂ group after the pH value became neutral or acidic. These changes were not observed for BPH, presumably because of the direct and robust binding of the hydrazone onto Au surfaces. Our results revealed that the pH‐dependent cleavage reactions may vary depending on the surface anchoring modes of the adsorbates. Copyright © 2015 John Wiley & Sons, Ltd.     

Adsorption study of 4‐MBA on TiO2 nanoparticles by surface‐enhanced Raman spectroscopy

In this paper, the adsorption of 4‐mercaptobenzoic acid (4‐MBA) on TiO₂ nanoparticles was studied mostly by surface‐enhanced Raman spectroscopy (SERS) and UV‐vis spectroscopy, at different pH values as well as under different temperatures and concentrations. The results show that the 4‐MBA molecules are bonded to the TiO₂ surface both through the sulfur atoms and COO⁻ groups at neutral or alkaline pH, but only through the sulfur atom at acidic pH. Furthermore, the 4‐MBA molecules possess high adsorptive stability on TiO₂ at a comparatively high temperature (150 °C). Concentration‐dependent SERS experiments show that the saturation concentration for 4‐MBA adsorbed on TiO₂ is about 10⁻³ M in natural case (pH = 6). Copyright © 2009 John Wiley & Sons, Ltd.     

Vertically aligned γ-AlOOH nanosheets on Al foils as flexible and reusable substrates for NH<Subscript>3</Subscript> adsorption

Vertically aligned γ-AlOOH nanosheets (NSs) have been successfully fabricated on flexible Al foils via a solvothermal route without morphology-directing agents. Three different reaction temperature (25, 80, and 120 ?C) and time (30 min, 45 min, and 24 h) are discussed for the growth period, which efficiently tune the density and size of the γ-AlOOH NSs. Meanwhile, the growth speed of the nanosheets confirms that dominant growth stage is seen in the initial 45 min. Furthermore, the interlayer of the γ-AlOOH NSs displays an average height of 140 nm and superhydrophilicity. By dynamic adsorption, the assynthesized γ-AlOOH NSs exhibit an outstanding NH₃ adsorption capacity of up to 146 mg/g and stably excellent regeneration for 5 cycles. The mechanism of NH₃ adsorption on the in-plane of the γ-AlOOH NSs is explained by the Lewis acid/base theory. The H-bond interactions among the NH₃ molecules and the edge groups (-OH) further improve the capture ability of the nanosheets.     

Degradation of magnetite nanoparticles in biomimetic media

Magnetic nanoparticles (NPs) of magnetite Fe₃O₄ obtained by coprecipitation (COP), thermal decomposition (DT), and commercial sample (CM) have been degraded in similar conditions to physiological medium at pH 4.7 and in simulated body fluid (SBF) at pH 7.4. The formation of the nanoparticles was confirmed by FTIR spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). In view of medical and environmental applications, the stability of the particles was measured with dynamic light scattering. The degradation processes were followed with atomic absorption spectroscopy (EAA) and TEM. Magnetic measurements were carried out using vibrating sample magnetometry (VSM). Our results revealed that the structural and magnetic properties of the remaining nanoparticles after the degradation process were significantly different to those of the initial suspension. The degradation kinetics is affected by the pH, the coating, and the average particle size of the nanoparticles.     

Spectroscopic investigation on the sonodynamic activity of amsacrine (AMSA) to bovine serum albumin (BSA) damage

The sonodynamic damage of bovine serum albumin (BSA) under ultrasonic irradiation in the presence of amsacrine (AMSA) was studied by hyperchromic effect of UV-vis spectra and quenching effect of intrinsic fluorescence. In addition, several influencing factors such as ultrasonic irradiation time, AMSA concentration, system acidity and ionic strength about the damage of BSA molecules were reviewed. The results showed that the damage degree was obviously enhanced with the increase of ultrasonic irradiation time and AMSA concentration, but it was only slightly increased with the increase of solution pH value and ionic strength. Furthermore, the binding and damaging sites to BSA molecules were estimated by synchronous fluorescence spectra. The different chances to damage tryptophan (Trp) and tyrosine (Tyr) residues were found through the ratios of synchronous fluorescence quenching (R_SFQ). At last, the generation of reactive oxygen species (ROS) in sonodynamic process was estimated by the method of oxidation-extraction Spectrometry (OES). And then, several radical scavengers were used to determine the kind of ROS, which includes singlet oxygen (¹O₂) and hydroxyl radicals (·OH). Perhaps, the result would bring a certain guiding significance to use sonosensitive drugs in the fields of tumor treatment.     

Mössbauer study of the kinetics of simulated corrosion process of iron in chlorinated aqueous solution around room temperature: The hyperfine structure of ferrous hydroxides and Green Rust I

The hyperfine structure of the two ferrous hydroxides, Fe(OH)₂, [2Fe(OH)₂, FeOCl] and Green Rust I obtained during the oxidation of iron in chlorinated aqueous medium is determined. The structure of GRI is proposed. The kinetics of oxidation and the role of the chlorine concentration is thoroughly discussed.     

pH-Responsive Biocompatible Fluorescent Core-Shell Nanogel for Intracellular Imaging and Control Drug Release

This study reports a fluorescence iron core-carbonized biocompatible hybrid poly(ethylene glycol) (PEG)-oriented nanogel (Fe₂O₃@C@PEG-COOH nanogel). The fluorescence Fe₂O₃@C@PEG-COOH nanogel is prepared using a facile one-pot polycondensation reaction without organic solvents or catalysts. The properties of the fluorescenceFe₂O₃@C@PEG-COOH nanogel are investigated by fluorescence spectroscopy, transmission electron microscopy, X-ray diffraction, and thermogravimetric analysis. A change in pH as a stimulus can trigger the release of loaded doxorubicin (DOX). Under acidic conditions, the nanogel releases the highly loaded drug slowly compared to the neutral and basic conditions, which is important for cancer treatment. The synthesized fluorescenceFe₂O₃@C@PEG-COOH nanogel is well dispersed in water and shows fluorescence with high photostability, good biocompatibility with a paramagnetic nature. Furthermore, the nanogel can act as a potential fluorescent probe for cell imaging.     

Mechanism of formation of magnetite from ferrous hydroxide in aqueous corrosion processes

The stoichiometric conditions for the formation of ferrous hydroxide Fe(OH)₂, by mixing Fe²⁺ ions with caustic soda NaOH, leads by oxidation to magnetite, irrelevant of the foreign anions, e.g. Cl^? or SO₄ ^2?, as demonstrated from Mössbauer spectroscopy. The electrochemical potential E_h and pH value of the initial conditions correspond to the drastic change from basic to acidic medium, observed when varying the initial Fe²⁺/OH^? ratio. Mössbauer analysis of the end products of oxidation at various temperatures shows that magnetite is only obtained at stoichiometry at very low temperature, but extends off stoichiometry at higher temperatures. The mechanism of formation of magnetite through an intermediate compound is discussed.     

Characterization of the adsorption and decomposition of methanol on Ni(110)

The chemisorption, condensation, desorption, and decomposition of methanol, both CH₃OH and CH₃OD, on a clean Ni(110) surface have been characterized using high resolution electron energy loss spectroscopy, temperature programmed reaction spectroscopy, and low energy electron diffraction. The vibrational spectrum of the saturated chemisorbed layer, 7.4 × 10¹⁴ molecules cm^?2, is almost identical to the infrared spectrum of liquid or solid methanol. Condensation of multilayers of methanol is facile at 80 K. The only quasi-stable intermediate isolated during the decomposition is a methoxy species, CH₃O, which decomposes thermally to CO and H. The evolution of both CO and H₂ occurs in desorption limited processes.     

Quantitative analysis of dilute mixtures of SO<Subscript>2</Subscript> in N<Subscript>2</Subscript> at 7.4 μm by difference frequency spectroscopy

We describe a 7.4-μm source based on difference frequency generation with 6.5 mW of 1278-nm radiation from an extended cavity laser and 66 mW of 1544-nm radiation from another extended cavity laser, amplified in an erbium-doped fibre amplifier. Optimum focusing of the input beams in the 5×5×10-mm³ AgGaSe₂ crystal, and the spatial and temporal characteristics of the output beam, are determined. The source is used for accurate determination of line parameters for selected lines of the ν₃ band of SO₂, centred at 1361 cm^-1. Subsequently, these lines are used for performing quantitative analysis of gas mixtures containing SO₂ at concentration levels down to 4 ppm without relying on any calibration with certified gas mixtures. This demonstrates the potential of infrared spectroscopy as a primary method for low-concentration gas analysis. Received: 16 January 2003 / Revised version: 19 February 2003 / Published online: 9 April 2003 RID="*" ID="*"Corresponding author. Fax: +45-4593/1137, E-mail: jh@dfm.dtu.dk