Ultrasound assisted biobleaching of cotton

In this study, the effect of ultrasound on the activity of the glucose oxidase (GOx) enzyme for bleaching of the cotton fabrics was investigated. Hydrogen peroxide generation with the GOx enzyme from glucose was carried out under ultrasonic homogenizer (UH) and ultrasonic bath support. The aim of using ultrasonic support was to increase the yield of the enzyme reactions. The enzymatically generated hydrogen peroxide was used for bleaching of cotton fabrics. The bleaching process was performed at 90 °C and pH 11 (with NaOH) for 60 min, followed by rinsing at 70 and 50 °C then cold washing. The whiteness degrees of the cotton samples that were bleached by the generated peroxide were compared to the whiteness degrees of the conventionally bleached cotton fabrics. Sufficient whiteness degrees in cotton fabrics could be obtained by enzymatically generated hydrogen peroxide by UH support. The initial whiteness degree of the cotton fabric was 59.9 Stensby degrees; the whiteness was increased to 75.6 Stensby degrees by the GOx enzyme under UH support where the conventional bleaching process yielded a whiteness value of 76.7 Stensby degrees. For efficient cotton bleaching by the GOx enzyme, UH support contributed to the concentration of enzymatically generated hydrogen peroxide by the GOx enzyme. Bleaching of cotton by the GOx enzyme was approved as a more environmentally friendly process compared to the conventional bleaching method in respect of the results of chemical oxygen demand tests.     

Heat of reaction and curing of epoxy resin

The heat of reaction and kinetics of curing of diglycidyl ether of bisphenol-A (DGEBA) type of epoxy resin with catalytic amounts of ethylmethylimidazole (EMI) have been studied by differential power-compensated calorimetry as a part of the program for the study of process monitoring for composite materials. The results were compared with those from 1∶1 and 1∶2 molar mixtures of DGEBA and EMI. A method of determination of heat of reaction from dynamic thermoanalytical instruments was given according to basic thermodynamic principles. The complicated mechanism, possibly involving initial ionic formation, has also been observed in other measurements, such as by time-domain dielectric spectroscopy. The behavior of commercially available DGEBA resin versus purified monomeric DGEBA were compared. The melting point of purified monomeric DGEBA crystals is 41.4 °C with a heat of fusion of 81 J/g. The melt of DGEBA is difficult to crystallize upon cooling. The glass transition of purified DGEBA monomer occurs around ?22 °C with aΔC _p of 0.60 J/K/g.     

Thermal decomposition study of HAuCl4·3H2O and AgNO3 as precursors for plasmonic metal nanoparticles

Thermal decomposition of HAuCl₄·3H₂O and AgNO₃, as precursors for Au and Ag nanoparticles, respectively, was monitored by coupled TG–DTA with TG/EGA–FTIR and EGA–MS techniques in a flowing 80 %Ar + 20 %O₂ and Ar atmospheres in the temperature range of 30–600 °C. The intermediate and final products of thermal decomposition were analysed by ex situ XRD and FTIR techniques. The thermal degradation of HAuCl₄·3H₂O starts immediately after melting at 75 °C and takes place in three steps in the temperature range of 75–320 °C with total mass loss of 49.4 and 49.7 % in artificial air and Ar atmospheres, respectively. EGA by MS and FTIR revealed a simultaneous release of H₂O and HCl in the temperature range of 75–235 °C. EGA by MS revealed a release of Cl₂ at around 225 °C and in the interval of 250–320 °C. According to the XRD analysis, the main solid product in the end of the first decomposition step at 190 °C is AuCl₃; in the end of the second decomposition step at 240 °C is AuCl and the final product at 320 °C is Au. The thermal decomposition of AgNO₃ takes place in a single step in the temperature range of 360–515 °C with a total mass loss of 39.0 and 37.8 % in flowing artificial air and Ar atmospheres, respectively. According to EGA–MS and EGA–FTIR the main evolved gases are NO₂, NO and O₂. The final product of the thermal decomposition at 600 °C is Ag irrespective of the atmosphere.     

Fluorescent protein-based FRET sensor for intracellular monitoring of redox status in bacteria at single cell level

Monitoring of intracellular redox status in a bacterial cell provides vital information about the physiological status of the cell, which can be exploited in several applications such as metabolic engineering and computational modeling. Fluorescent protein-based genetically encoded sensors can be used to monitor intracellular oxidation/reduction status. This study reports the development of a redox sensor for intracellular measurements using fluorescent protein pairs and the phenomenon of Förster resonance energy transfer (FRET). For the development of the sensor, fluorescent proteins Citrine and Cerulean were genetically modified to carry reactive cysteine residues on the protein surface close to the chromophore and a constructed FRET pair was fused using a biotinylation domain as a linker. In oxidized state, the FRET pairs are in close proximity by labile disulfide bond formation resulting in higher FRET efficiency. In reducing environment, the FRET is diminished due to the increased distance between FRET pairs providing large dynamic measurement range to the sensor. Intracellular studies in Escherichia coli mutants revealed the capability of the sensor in detecting real-time redox variations at single cell level. The results were validated by intensity based and time resolved measurements. The functional immobilization of the fluorescent protein-based FRET sensor at solid surfaces for in vitro applications was also demonstrated. Graphical Abstract

Schematic representation of FRET-based redox sensor     

Structural and thermal properties of HDPE/n-AlN polymer nanocomposites

High-density polyethylene (HDPE) containing various volume fractions (0–20 vol%) of aluminum nitride nanoparticles (n-AlN) is prepared by melt mixing. Structural and morphological characterizations of the prepared composites are carried out by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HR-TEM), and atomic force microscopy (AFM). Thermal stability and degradation kinetics of HDPE/AlN (nano) composites are investigated by Thermogravimetric analysis (TG). HR-TEM micrographs confirm fairly uniform dispersion of AlN nanoparticles, as well as the existence of long interconnected chain-like aggregates. AFM images also confirm homogeneous dispersion of n-AlN in the polymer matrix. Roughness analysis from the AFM data indicates the presence of substantial undulation from the mean surface level. Thermogravimetric data indicate small improvement in the thermal stability of the composites. Kinetic parameters, viz., the activation energy (E _a), frequency factor (A), and reaction order (n) are estimated using the isoconversional methods of Kissinger, Flynn–Wall–Ozawa (FWO), KAS, and Friedman. Activation energies (E _a) calculated by the above four models display nearly similar features and are enhanced by the presence of AlN nanoparticles. Kinetics of degradation of HDPE-AlN (nano) composites follows a first-order reaction.     

Structure and spacing of cellulose microfibrils in woody cell walls of dicots

The structure of cellulose microfibrils in situ in wood from the dicotyledonous (hardwood) species cherry and birch, and the vascular tissue from sunflower stems, was examined by wide-angle X-ray and neutron scattering (WAXS and WANS) and small-angle neutron scattering (SANS). Deuteration of accessible cellulose chains followed by WANS showed that these chains were packed at similar spacings to crystalline cellulose, consistent with their inclusion in the microfibril dimensions and with a location at the surface of the microfibrils. Using the Scherrer equation and correcting for considerable lateral disorder, the microfibril dimensions of cherry, birch and sunflower microfibrils perpendicular to the [200] crystal plane were estimated as 3.0, 3.4 and 3.3 nm respectively. The lateral dimensions in other directions were more difficult to correct for disorder but appeared to be 3 nm or less. However for cherry and sunflower, the microfibril spacing estimated by SANS was about 4 nm and was insensitive to the presence of moisture. If the microfibril width was 3 nm as estimated by WAXS, the SANS spacing suggests that a non-cellulosic polymer segment might in places separate the aggregated cellulose microfibrils.     

Preparation of Cu (II)/PEI–QPEI/SiO2 nanopowder as antibacterial material

The silica nanoparticles were prepared by the sol–gel process, and then twice modified and grafted by polyethylenimine (PEI) on their surface. After quaternary ammonium reaction and chelated copper reaction, the PEI/SiO₂, QPEI/SiO₂, PEI–QPEI/SiO₂ and Cu (II)/PEI–QPEI/SiO₂ nanopowders were obtained in turn. The morphology and structure of the products were characterized through SEM, EDX, HRTEM, FTIR and element analysis. At the same time, the antibacterial activity of the products to E. coli and Candida were evaluated through quantification and qualitative ways, e.g. microcalorimetric method and culture dish method. The results suggested that the Cu (II)/PEI–QPEI/SiO₂, a novel three-component functional nanopowder, presented the best antibacterial activity to both E. coli and Candida duo to the synergistic sterilization capability of the ammonium salt and copper ions, compared with other products. It indicated that the Cu (II)/PEI–QPEI/SiO₂ nanopowder could be a novel antibacterial nanomaterial to widely application in preventing and minimizing bacteria of the organism and environment in future.     

Application of polymeric nanoparticles prepared by an antisolvent diffusion with preferential solvation for iontophoretic transdermal drug delivery

Indomethacin-loaded poly(lactide-co-glycolide) (PLGA) nanoparticles with an average diameter of 100 nm were prepared by using a combination of an antisolvent diffusion method with preferential solvation (bare nanoparticles). Polyvinyl alcohol (PVA)-coated indomethacin-loaded PLGA nanoparticles with an average diameter of 100 nm were also prepared by emulsification and the solvent evaporation method (PVA-coated nanoparticles). Bare nanoparticles do not have a hydrophilic stabilizer on the surface; therefore, they have high hydrophobicity and negative charges. Electrophoretic mobility of bare nanoparticles at 5 mM NaCl solution was about 68 times higher than that of PVA-coated nanoparticles. Permeability of bare nanoparticles through rat skin was significantly higher than that of PVA-coated nanoparticles when iontophoresis was applied ex vivo. Indomethacin amount inside the skin after the permeation study by using bare nanoparticles was much higher than that by using PVA-coated nanoparticles. Indomethacin transition to circulation and accumulation in muscle by the transdermal delivery of indomethacin-loaded PLGA nanoparticles were significantly enhanced by using the combination of bare nanoparticles and iontophoresis in vivo. As for transdermal route of nanoparticles, both bare and PVA-coated nanoparticles were revealed to penetrate through the transfollicular pathway, and the migration of nanoparticles to follicles was enhanced by the application of iontophoresis. PLGA nanoparticles prepared by the antisolvent diffusion with preferential solvation are beneficial for iontophoretic transdermal delivery of therapeutic agents.     

Relating surface-enhanced Raman scattering signals of cells to gold nanoparticle aggregation as determined by LA-ICP-MS micromapping

The cellular response to nanoparticle exposure is essential in various contexts, especially in nanotoxicity and nanomedicine. Here, 14-nm gold nanoparticles in 3T3 fibroblast cells are investigated in a series of pulse-chase experiments with a 30-min incubation pulse and chase times ranging from 15 min to 48 h. The gold nanoparticles and their aggregates are quantified inside the cellular ultrastructure by laser ablation inductively coupled plasma mass spectrometry micromapping and evaluated regarding the surface-enhanced Raman scattering (SERS) signals. In this way, both information about their localization at the micrometre scale and their molecular nanoenvironment, respectively, is obtained and can be related. Thus, the nanoparticle pathway from endocytotic uptake, intracellular processing, to cell division can be followed. It is shown that the ability of the intracellular nanoparticles and their accumulations and aggregates to support high SERS signals is neither directly related to nanoparticle amount nor to high local nanoparticle densities. The SERS data indicate that aggregate geometry and interparticle distances in the cell must change in the course of endosomal maturation and play a critical role for a specific gold nanoparticle type in order to act as efficient SERS nanoprobe. This finding is supported by TEM images, showing only a minor portion of aggregates that present small interparticle spacing. The SERS spectra obtained after different chase times show a changing composition and/or structure of the biomolecule corona of the gold nanoparticles as a consequence of endosomal processing.     

Thermal decomposition of polymethylmethacrylate synthesized with anionic catalysts

TG and DTA data are used to show that the thermal decomposition of polymethylmethacrylate (PMMA) synthesized with anionic catalysts depends on the nature of the catalyst. It is found that the thermal stability of PMMA obtained by using anionic amide catalysts is higher than that of radical PMMA and of PMMA obtained with other anionic catalysts, and depends on the temperature of polymerization and on the molecular weight of the polymer.     

SDS 800 — The new data system for quantitative depth profiling of inhomogeneous samples by SIMS

More than 13 years of SIMS application field experience of numerous users of the ATOMIKA Ionmicroprobes have been the basis for the new SIMS Data System SDS 800. The hardware and software concept of the SDS 800, therefore, pays special attention to the following requirements:

1. Convenient set-up, modification and re-use of the measuring parameter sets for easy, time-saving operation.
2. Individual parameter selection from the very broad range of SIMS measuring parameters for optimum SIMS data quality.
3. Multitasking operation for simultaneous handling of SIMS measurement, data processing, data output and of auxiliary techniques.
4. Simultaneous depth profile/ion image acquisition and processing to enhance data quality and to validate data interpretation.
5. User-friendly data processing and output.

     

Characterization of Volatile Organic Metabolites in Lung Cancer Pleural Effusions by SPME–GC/MS Combined with an Untargeted Metabolomic Method

Headspace solid-phase microextraction and gas chromatography/mass spectrometry (HS-SPME–GC/MS) method combined with XCMS Online was tentatively applied to characterize the dysregulated volatile organic metabolites (VOMs) in benign and malignant pleural effusions. A total of 9 dysregulated feature groups were isolated from metabolic features in 35 pleural effusion samples (20 benign effusions and 15 malignant ones from lung cancer patients). Principle component analysis, partial least squares discriminant analysis (PLS-DA) and orthogonal PLS-DA were built to separate benign from malignant pleural effusion groups and to find dysregulated metabolites in significantly different amounts between the two groups. Four dysregulated VOMs such as 2-ethyl-1-hexanol, cyclohexanone, 1,2,4,5-tetramethylbenzene and naphthalene were selected according to the variable influence on the projection value. The concentration of the four dysregulated VOMs in benign and malignant effusions were further determined by external standard method. The median concentrations of 4 VOMs in malignant effusion samples were from 4.7 to 91,121.9 nM, whereas their median levels were only 1.9–318.3 nM in benign ones. The results show that the proposed SPME–GC/MS-based metabolomic approach combined with XCMS Online data processing is a simple, rapid and available method for the characterization of dysregulated VOMs in malignant and benign pleural effusions.     

The role of octanol in the extraction of hydrochloric acid by trilaurylamine dissolved in benzene

The extraction of hydrochloric acid by trilaurylamine (TLA) dissolved in benzene was studied in the presence and in absence of n-octanol. The extraction of HCl was found to be enhanced by the addition of octanoi to the organic phase. In order to explain this effect by means of the law of mass action, the systems TLA-HCL-benzene and n-octanol-HCl-benzene as well as TLA-octanol-benzene were also studied. It was found that TLA reacts with octanol to form a complex, TLAROH, while the octanol itself associates in benzene to form dimers and tetramers, although it does not extract HCl alone from the dilute solutions used in the present study. The enhancement of the extraction of HCl by TLA upon the addition of n-octanol could be described by the formation of the species TLA·ROH·HCl and its stability constant was determined.     

On synthesis of Fe2SiO4/SiO2 and Fe2O3/SiO2 composites through sol–gel and solid-state reactions

Major processing factors in forming Fe₂SiO₄/SiO₂ and Fe₂O₃/SiO₂ powders via sol–gel synthesis followed by solid-state reactions are investigated. The results clearly indicate that the chemical compositions of the precursors, the ratio of the precursors, the nature of the catalyst used, and the gas atmosphere during solid-state reactions can all affect the outcome of the reaction product(s). The formation of Fe₂SiO₄/SiO₂ is enhanced by using the precursor iron(III) acetylacetonate as the Fe source with the precursor ratio of iron(III) acetylacetonate to tetraethyl orthosilicate being 1:1 and the addition of formic acid. Otherwise, crystalline Fe and Fe₃C are formed in place of Fe₂SiO₄. By altering the gas atmosphere during solid-state reactions from argon to oxygen, the reaction products change from Fe₂SiO₄/SiO₂ to Fe₂O₃/SiO₂. All of the observed phenomena can be rationalized via the degree of mixing of the Fe–O and Si–O domains at the molecular level in the gel network during sol–gel reactions and the presence of a reducing or oxidizing atmosphere during the solid-state reaction.     

Non-isothermal reduction of silica-supported nickel catalyst precursors in hydrogen atmosphere: a kinetic study and statistical interpretation

A series of silica-supported nickel catalyst precursors was synthesized with different SiO₂/Ni mole ratios (0.20, 0.80 and 1.15). Non-isothermal reduction of Ni catalyst precursors was investigated by temperature-programmed reduction at four different heating rates (2, 5, 10 and 20 °C min^?1), in a hydrogen atmosphere. Kinetic parameters (E _a, A) were determined using Friedman isoconversional method. It was found that for all mole ratios, apparent activation energy is practically constant in conversion range of α = 30–70 %. In considered conversion range, the following values of apparent activation energy were found: E _a = 129.5 kJ mol^?1 (SiO₂/Ni = 0.20), E _a = 133.8 kJ mol^?1 (SiO₂/Ni = 0.80) and E _a = 125.0 kJ mol^?1 (SiO₂/Ni = 1.15). Using two special functions (y(α) and z(α)), the kinetic model was determined. It was established that reduction of Ni catalyst precursors with different SiO₂/Ni mole ratios is a complex process and can be described by two-parameter ?esták–Berggren (SB) autocatalytic model. Based on established values of SB parameters for each mole ratio, the possible mechanism was discussed. It was found that for all investigated ratios, the Weibull distribution function fits very well the experimental data, in the wide range of conversions (α = 5–95 %). Based on obtained values of Weibull shape parameter (θ), it was found that experimentally evaluated density distribution functions of the apparent activation energies can be approximated by the unbalanced peaked normal distribution.     

Characterisation and comparison of biomass ashes with different thermal histories using TG-DSC

The present research is focused on the characterisation and comparison of biomass ashes from wood pellet with different thermal histories. One of the ashes is obtained in a muffle furnace until its mass stabilization reaching a temperature of 550 °C, low temperature ash (LTA); the other one came from an experimental fixed bed combustor after 4 h of stable combustion in which the temperature reached is above 1,000 °C, high temperature ash (HTA). The samples were studied using Thermogravimetry and Differential Scanning Calorimetry (TG-DSC) techniques, and they were subjected to a heating up to 900 °C under an inert atmosphere with the objective of perceiving the differences in their thermal behaviour. At these temperatures, complex phase transformations occur, related to decomposition of carbonates and formation of silicates. TG and DSC curves are compared and some differences in mass loss, temperature peaks and enthalpy associated to endothermic effects are detected and they are explained based on the different compositions of both samples obtained at different temperatures. Other techniques were applied for the determination of the chemical composition of the ashes; X-ray fluorescence and Scanning electron microscopy with energy dispersive X-ray spectroscopy showed the elements present in the ashes, and X-ray diffraction revealed the crystalline phases and confirms that LTA is mainly composed of carbonates, while HTA mostly consists of silicates.     

Analysis of citrate-capped gold and silver nanoparticles by thiol ligand exchange capillary electrophoresis

We report on the capillary electrophoretic behavior of citrate-capped gold and silver nanoparticles in aqueous medium when applying a ligand-exchange surface reaction with thiols. Gold nanoparticles (AuNPs) and silver nanoparticles (AgNPs) of similar size (39?±?6 and 41?±?7 nm, respectively) and shape were synthesized, covered with a citrate shell, and characterized by microscopic and spectroscopic techniques. The analysis of these NPs by CE was accomplished by using a buffer solution (pH 9.7; 40 mM SDS, 10 mM CAPS; 0.1 % methanol) containing the anions of thioctic acid or thiomalic acid. These are capable of differently interacting with the surface of the AuNPs and AgNPs and thus introducing additional negative charges. This results in different migration times due to the formation of differently charged nanoparticles. Figure

Capillary electrophoretic behavior of citrate-capped gold and silver nanoparticles (NPs) in aqueous medium when applying a ligand-exchange surface reaction with thiols (thioctic and thiomalic acids), which introduces additional negative charges, has been studied     

Thermal behaviour of a modified encapsulation agent

Thermal behaviour of heptakis-6-iodo-6-deoxy-beta-cyclodextrin (HIDBCD) under inert and oxidative conditions was investigated by TG/DTG/DTA, FTIR, and using the hyphenate technique TG–FTIR. Due to the fact that thermal behaviour of HIDBCD was not studied before, we set our goal in the investigation of thermal degradation process in a dynamic air atmosphere vs. nitrogen atmosphere at a heating rate of 10 °C min^?1, up to 500 °C, respectively, 600 °C. It was found that the degradation process in air occurs in a single step, with a total mass loss of 99.9 %. The results of TG/DTG/DTA–FTIR indicated that the thermal behaviour of this cyclodextrin can be divided into three stages and more information was provided about the reaction sequences and the relevant products of reaction.     

Stereoselective separation and pharmacokinetic dissipation of the chiral neonicotinoid sulfoxaflor in soil by ultraperformance convergence chromatography/tandem mass spectrometry

Ultraperformance convergence chromatography/tandem triple quadrupole mass spectrometry (UPC²-MS/MS) is a novel tool in separation science that combines the advantages of supercritical fluid chromatography with ultraperformance liquid chromatography/MS/MS technology. The use of nontoxic CO₂ fluid and a postcolumn additive to complement MS/MS allows better control of analyte retention for chiral separation and high-sensitivity determination with different chiral stationary phases. This paper reports the stereoselective separation and determination of the chiral neonicotinoid sulfoxaflor in vegetables and soil by UPC²-MS/MS. Baseline resolution (Rs?≥?1.56) of and high selectivity (LOQ?≤?1.83 μg/kg) for the four stereoisomers were achieved by postcolumn addition of 1 % formic acid–methanol to a Chiralpak IA-3 using CO₂/isopropanol/acetonitrile as the mobile phase at 40 °C, 2,500 psi, and for 6.5 min in electrospray ionization positive mode. Rearranged Van’t Hoff equations afforded the thermodynamic parameters ΔH ^ο and ΔS ^ο, which were analyzed to promote understanding of the enthalpy-driven separation of sulfoxaflor stereoisomers. The interday mean recovery, intraday repeatability, and interday reproducibility varied from 72.9 to 103.7 %, from 1.8 to 9.2 %, and from 3.1 to 9.4 %, respectively. The proposed method was used to study the pharmacokinetic dissipation of sulfoxaflor stereoisomers in soil under greenhouse conditions. The estimated half-life ranged from 5.59 to 6.03 d, and statistically nonsignificant enantioselective degradation was observed. This study not only demonstrates that the UPC²-MS/MS system is an efficient and sensitive method for sulfoxaflor stereoseparation, but also provides the first experimental evidence of the pharmacokinetic dissipation of sulfoxaflor stereoisomers in the environment. Graphical Abstract

Chemical structure and UPC²-MS/MS separation chromatogram of sulfoxaflor. (* stereogenic center)