Melt miscibility of HDPE/UHMWPE,LDPE/UHMWPE,and LLDPE/UHMWPE blends detected by dynamic rheometer

The dynamic rheological behavior of high density polyethylene (HDPE)/ultrahigh molecular weight polyethylene (UHMWPE) blends, low density polyethylene (LDPE)/UHMWPE blends and linear low density polyethylene (LLDPE)/ UHMWPE blends was measured in parallel plate rheometer at 200°C. The analysis of log-additivity rule, Cole-Cole plots and Han curves of the three series blends indicated that the LDPE/UHMWPE blends were miscible in the melt, while the HDPE/UHMWPE blends and LLDPE/UHMWPE blends showed phase separation. The DSC results of LLDPE/UHMWPE blends and HDPE/UHMWPE blends were consistent with the rheological properties, while for the thermal properties of LDPE/UHMWPE blends, results revealed three endothermic peaks, which indicated a liquid-solid phase separation in LDPE/UHMWPE blends.     

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.

     

Solid-phase microextraction/gas chromatography–mass spectrometry method optimization for characterization of surface adsorption forces of nanoparticles

A complete characterization of the different physico-chemical properties of nanoparticles (NPs) is necessary for the evaluation of their impact on health and environment. Among these properties, the surface characterization of the nanomaterial is the least developed and in many cases limited to the measurement of surface composition and zetapotential. The biological surface adsorption index approach (BSAI) for characterization of surface adsorption properties of NPs has recently been introduced (Xia et al. Nat Nanotechnol 5:671–675, 2010; Xia et al. ACS Nano 5(11):9074–9081, 2011). The BSAI approach offers in principle the possibility to characterize the different interaction forces exerted between a NP's surface and an organic—and by extension biological—entity. The present work further develops the BSAI approach and optimizes a solid-phase microextraction gas chromatography–mass spectrometry (SPME/GC-MS) method which, as an outcome, gives a better-defined quantification of the adsorption properties on NPs. We investigated the various aspects of the SPME/GC-MS method, including kinetics of adsorption of probe compounds on SPME fiber, kinetic of adsorption of probe compounds on NP's surface, and optimization of NP's concentration. The optimized conditions were then tested on 33 probe compounds and on Au NPs (15 nm) and SiO₂ NPs (50 nm). The procedure allowed the identification of three compounds adsorbed by silica NPs and nine compounds by Au NPs, with equilibrium times which varied between 30 min and 12 h. Adsorption coefficients of 4.66?±?0.23 and 4.44?±?0.26 were calculated for 1-methylnaphtalene and biphenyl, compared to literature values of 4.89 and 5.18, respectively. The results demonstrated that the detailed optimization of the SPME/GC-MS method under various conditions is a critical factor and a prerequisite to the application of the BSAI approach as a tool to characterize surface adsorption properties of NPs and therefore to draw any further conclusions on their potential impact on health. Graphical Abstract

The basic principle of SPME/GC-MS method for characterization of nanoparticles surface adsorption forces     

Angular dependent post-collision interaction in auger processes

We have reformulated the theory of post-collision interaction (PCI) for Auger-decay following inner-shell photoionisation in order to take the time into account with the Auger-electron need to overtake the slow electron. The energy-shift of the Auger-electron due to PCI is calculated by solving in a reasonable approximation the classical equation of motion for the Auger electron. In contrast to the theory of Russek and Mehlhorn we derive analytical expressions for the transition amplitude, the line shape and the line shift of the Auger-electrons. If in our model the Auger electron and the slow electron are treated uncorrelated in direction our analytical expressions agree well with the numerical results of Russek and Mehlhorn. However if we account for directional electron-electron correlations, we show that deviations from the theory of Russek and Mehlhorn are to be expected. The possibility of detecting these deviations is discussed.     

Development of novel sol–gel coatings by chemically bonded ionic liquids for stir bar sorptive extraction—application for the determination of NSAIDS in real samples

In this work, a novel ionic liquid (IL) chemically bonded sol–gel coating was prepared for stir bar sorptive extraction (SBSE) of nonsteroidal anti-inflammatory drugs (NSAIDs) followed by high-performance liquid chromatography-ultraviolet detection (HPLC-UV). By using γ-(methacryloxypropyl)trimethoxysilane (KH-570) as a bridging agent, 1-allylimidazolium tetrafluoroborate ([AIM][BF₄]) was chemically bonded onto the bare stir bar, and the prepared IL-bonded sol–gel stir bar coating showed higher extraction efficiency and better adsorption/desorption kinetics for target NSAIDs over other polydimethylsiloxane (PDMS)-based or monolithic stir bar coatings. The mechanical strength and durability (chemical/thermal stability) of the prepared IL-bonded sol–gel coating were excellent. The influencing factors of SBSE, such as sample pH, salt effect, stirring rate, extraction time, desorption solvent, and desorption time, were optimized, and the analytical performance of the developed SBSE-HPLC-UV method was evaluated under the optimized conditions. The limits of detection (LODs) of the proposed method for three NSAIDs were in the range of 0.23–0.31 μg L^?1, and the enrichment factors (EFs) were in the range of 51.6–56.3 (theoretical enrichment factor was 100). The reproducibility was also investigated at concentrations of 5, 20, and 100 μg L^?1, and the relative standard deviations (RSDs) were found to be less than 9.5, 7.5, and 7.6 %, respectively. The proposed method was successfully applied for the determination of NSAIDs in environmental water, urine, and milk samples. Graphical Abstract

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Kinetics and possible mechanism of hydrogen chloride oxidation over supported copper-containing salt catalysts: I. Kinetics of HCl oxidation in the deacon and methane oxychlorination reactions over a copper-potassium salt catalyst

The kinetics of HCl oxidation at 350–425°C over a (CuCl₂-KCl)/support catalyst in two complementary processes—Deacon and methane oxychlorination reactions—has been investigated using a gradientless technique. This has allowed the range of \(P_{Cl_2 }\) in the reaction mixture to be markedly extended. New kinetic features of HCl oxidation under conditions such that this process does and does not depend on P _HCl have been discovered. The kinetic equations obtained in this study fit experimental data in a wider range of conditions than the equations proposed earlier. The results of this study suggest the existence of two HCl oxidation pathways in the Deacon reaction.     

Development of a fast and selective UHPLC-DAD-QTOF-MS/MS method for the qualitative and quantitative assessment of destruxin profiles

A fast and selective ultrahigh-performance liquid chromatography diode array detector (UHPLC-DAD) method combined with an off-line solid phase extraction (SPE) protocol was established to monitor destruxins (dtxs), a secondary metabolite class of highly bioactive cyclic depsipeptides. Sample purification via SPE was tailored to remove both more polar and apolar matrix constituents by applying analyte class-selective washing and elution conditions. To separate and detect destruxin congeners an UHPLC-DAD system hyphenated to a quadrupole–time-of-flight (Q-TOF) hybrid mass spectrometer was utilized. Analyses were performed on a sub-2-μm-particle-size RP-18 column with an acidified (0.02 % acetic acid) 12 min water/acetonitrile solvent gradient. In the dtx congener elution zone 22 chromatographic peaks were separated. Four of these were identified by comparison with reference materials as dtx A, dtx B, dtx E, and dtx E-diol; 16 were tentatively assigned as known or novel dtx congeners by the analysis of high resolution UHPLC-DAD-QTOF-MS/MS data recorded in the positive electrospray ionization (ESI) mode. The applicability of the UHPLC-DAD assay to investigate biological materials in a qualitative and quantitative manner was proven by the application of the platform to monitor the dtx production profile of three Metarhizium brunneum strain fungal culture broths.     

Biomolecular Imaging with a C60-SIMS/MALDI Dual Ion Source Hybrid Mass Spectrometer: Instrumentation,Matrix Enhancement,and Single Cell Analysis

We describe a hybrid MALDI/C₆₀-SIMS Q-TOF mass spectrometer and corresponding sample preparation protocols to image intact biomolecules and their fragments in mammalian spinal cord, individual invertebrate neurons, and cultured neuronal networks. A lateral spatial resolution of 10 μm was demonstrated, with further improvement feasible to 1 μm, sufficient to resolve cell outgrowth and interconnections in neuronal networks. The high mass resolution (>13,000 FWHM) and tandem mass spectrometry capability of this hybrid instrument enabled the confident identification of cellular metabolites. Sublimation of a suitable matrix, 2,5-dihydroxybenzoic acid, significantly enhanced the ion signal intensity for intact glycerophospholipid ions from mammalian nervous tissue, facilitating the acquisition of high-quality ion images for low-abundance biomolecules. These results illustrate that the combination of C₆₀-SIMS and MALDI mass spectrometry offers particular benefits for studies that require the imaging of intact biomolecules with high spatial and mass resolution, such as investigations of single cells, subcellular organelles, and communities of cells. Graphical Abstract

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Carbon nanotubes induced poly(vinylidene fluoride) crystallization from a miscible poly(vinylidene fluoride)/poly(methyl methacrylate) blend

Different contents of carbon nanotubes (CNTs) were introduced into a miscible poly(vinylidene fluoride) (PVDF)/poly(methyl methacrylate) (PMMA) blend. The interfacial affinity between CNTs and components of the blend was evaluated by calculating the interfacial tension. The dispersion and microstructure of CNTs in the nanocomposites were investigated through scanning electron microscope and rheological measurement. The effect of CNTs on the crystallization of PVDF was comparatively investigated through nonisothermal and isothermal crystallization processes. The results showed that CNTs exhibited stronger interfacial affinity to PMMA. Homogeneous dispersion of CNTs in the nanocomposites was achieved. Largely enhanced crystallization temperature and increased crystallinity of PVDF were obtained by adding CNTs during the nonisothermal crystallization process. The results obtained from the isothermal crystallization process proved that CNTs induced the concentration fluctuation in the sample, which resulted in the formation of spherulites with different types, i.e., the banded spherulites and compact spherulites. Furthermore, both the crystallization temperature and the content of CNTs exhibited great influence on the crystalline morphology of PVDF.     

Facile formation of stimuli-responsive,fluorescent and magnetic nanoparticles based on cellulose stearoyl ester via nanoprecipitation

In comparison to stimuli-responsive, multi-functional nanoparticles (NPs) from synthetic polymers, such NPs based on sustainable, naturally occurring polysaccharides are still scarce. In the present study, stable stimuli-responsive, fluorescent and magnetic NPs were fabricated using cellulose stearoyl esters (CSEs) consisting of cellulose and stearoyl groups. The multifunctional NPs with the average diameters between 80 and 250 nm were obtained after facile nanoprecipitation using CSE solutions containing Fe₃O₄-NPs. Using the aqueous solution of fluorescent rhodamine B as precipitant, NPs with rhodamine B on NP surface were obtained. Rhodamine B could be released depending on the temperature. In comparison, stearoylaminoethyl rhodamine B can be encapsulated in CSE-NPs, which renders obtained NPs reversible fluorescence in response to UV illumination and heat treatment.     

Polyoxotungstate nanoclusters supported on silica as an efficient solid-phase microextraction fiber of polycyclic aromatic hydrocarbons

A highly porous silica-supported tungstophosphoric acid (PW) nanocluster was prepared for use in solid-phase microextraction (SPME) of polycyclic aromatic hydrocarbons (PAHs). The PWs represent a class of discrete transition metal-oxide nanoclusters and their structures resemble discrete fragments of metal-oxide structures of definite size and shape. Transition metal-oxide nanoclusters display large structural diversity, and their monodisperse sizes can be tuned from several Ångstroms up to 10 nm. The highly porous silica-supported tungstophosphoric acid nanocluster material is found to be capable of efficiently extracting PAHs from aqueous sample solutions. The nanomaterial was immobilized on a stainless steel wire for fabrication of the SPME fiber. Following thermal desorption, the PAHs were quantified by GC-MS. Analytical merits include limits of detection that range from 0.02 to 0.1 pg mL^?1 and a dynamic range as wide as from 0.001 to 100 ng mL^?1. Under optimum conditions, the repeatability for one fiber (n?=?3), expressed as the relative standard deviation, is between 4.3 % and 8.6 %. The method is simple, rapid, and inexpensive. The thermal stability of the fiber and the high relative recovery make this method superior to conventional methods of extraction.

The highly porous silica-supported tungstophosphoric acid nanocluster material is found to be capable of efficiently extracting PAHs from aqueous sample solutions. The prepared nanomaterial was immobilized onto a stainless steel wire for fabrication of the SPME fiber. Following thermal desorption, the PAHs were quantified by GC-MS.     

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     

Determination of the Avrami exponent of partially crystallized polymers by DSC- (DTA-) analyses

This paper presents a new method for a rapid determination of the Avrami exponentn by nonisothermal thermoanalytic analysis (DSC and DTA, resp.). Contrary to conventional techniques this method can be used in the entire temperature range and therefore it is applicable to polymers crystallizing from the melt. The proposed technique is applied to injection moulded low density polyethylene (LDPE), injection moulded high density polyethylene (HDPE), unpigmented extruded polypropylene (PP_unpigm.) and pigmented extruded polypropylene (PP_pigm.). The resulting values for the Avrami exponentsn _LDPE～2.9,n _HDPE～1.3, \(n_{PP_{unpigm} }\) ～2.2 and \(n_{PP_{pigm} }\) ～ 2.1 derived by crystallization from the melt were compared with isothermal measurements and with results given by other authors.     

A novel high efficiency benzophenone based polymeric photoinitiator from ring-opening polymerization of benzoxazine

A novel polymeric photoinitiator based on benzoxazine was synthesized by introducing 4-hydroxy benzophenone, diglycolamine and paraformaldehyde into the macromolecular chain. Its molecular structure was characterized by ¹H NMR, FTIR, and UV-Vis spectroscopy. Photopolymerization of tripropylene glycol diacrylate and trimethylolpropane triacrylate initiated by polybenzoxazine, benzoxazine, and benzophenone was studied by real time FTIR spectroscopy. The results obtained are discussed.     

Laser diode thermal desorption atmospheric pressure chemical ionization tandem mass spectrometry applied for the ultra-fast quantitative analysis of BKM120 in human plasma

A sensitive and ultra-fast method utilizing the laser diode thermal desorption ion source using atmospheric pressure chemical ionization coupled to tandem mass spectrometry (LDTD-APCI-MS/MS) was developed for the quantitative analysis of BKM120, an investigational anticancer drug in human plasma. Samples originating from protein precipitation (PP) followed by salting-out assisted liquid-liquid extraction (SALLE) were spotted onto the LazWell? plate prior to their thermal desorption and detection by tandem mass spectrometry in positive mode. The validated method described in this paper presents a high absolute extraction recovery (>90 %) for BKM120 and its internal standard (ISTD) [D₈]BKM120, with precision and accuracy meeting the acceptance criteria. Standard curves were linear over the range of 5.00 to 2000 ng mL^?1 with a coefficient of determination (R ²) >0.995. The method specificity was demonstrated in six different batches of human plasma. Intra- and inter-run precision as well as accuracy within ±20 % at the lower limit of quantification (LLOQ) and ±15 % (other levels) were achieved during a three-run validation for quality control (QC) samples. The post-preparative stability on the LazWell? plate at room temperature was 72 h and a 200-fold dilution of spiked samples was demonstrated. The method was applied successfully to three clinical studies (n?=?847) and cross-checked with the validated LC-ESI-MS/MS reference method. The sample analysis run time was 10 s as compared to 4.5 min for the current validated LC-ESI-MS/MS method. The resultant data were in agreement with the results obtained using the validated reference LC-ESI-MS/MS assay and the same pharmacokinetic (PK) parameters were calculated for both analytical assays. This work demonstrates that LDTD-APCI-MS/MS is a reliable method for the ultra-fast quantitative analysis of BKM120 which can be used to speed-up and support its bioanalysis in the frame of the clinical trials.     

Adsorption of polyprotic acid at the water/air interface

A rigorous thermodynamic treatment appropriate for surface adsorption from mixed aqueous solution of alkali and polyprotic acid was derived. Those equations were applied to mixed aqueous solution/air systems of alkali metal hydroxide and Fe^III complex with ethylenediamine- N, N, N′,N′-tetraacetate (Fe-EDTA). Surface density of each species arising from Fe-EDTA was separately evaluated, and thus, surface activity of Fe-EDTA was studied, especially its dependence on pH and how it is influenced by the counter cations. Fe-EDTA was positively adsorbed at the water/air interface at very low pHs and negatively at high pHs. The pH range of positive adsorption of Fe-EDTA with potassium ion, as a counter ion, was wider than that with sodium ion. Thus, potassium ion, a structure breaker, tended to smooth surface adsorption of Fe-EDTA at the water/air interface, whereas sodium ion, a structure maker, tended to withdraw Fe-EDTA from the interfacial region.     

Detection of trace levels of atrazine using surface-enhanced Raman scattering and information visualization

The detection of trace amounts of pesticides is essential for the quality control of waters, particularly with their inevitable increasing use with the growing demand for food. In this study, we report on the detection of atrazine, a highly toxic herbicide, down to 5?×?10^?12 M, which is sufficient to monitor the quality of drinking water even according to the most stringent international regulations. Such detection was performed with surface-enhanced Raman scattering (SERS) in atrazine incorporated into silver nanoparticles (AgNPs) colloids, with the SERS spectra being treated with Sammon’s mapping, an information visualization technique. In addition to providing a fingerprint of the atrazine molecules, SERS is advantageous in comparison with impedance spectroscopy and cyclic voltammetry applied to a sensor array of units made with layer-by-layer (LbL) films containing AgNPs and AuNPs. The combined use of SERS and information visualization methods is promising for monitoring water quality with regard to other pesticides, which may even approach single molecule detection.     

Synthesis,Colloidal Properties and Cytotoxicity of Biopolymer Nanoparticles

To characterize the physicochemical and biological stability of nanodevices suitable for biomedical applications, polylactic acid (PLA) nanoparticles (NPs) of 112?±?6 nm and polyhydroxy butyrate (PHB) of 15?±?5 nm size were prepared by standardizing the suitable method for each. Morphology of NPs was studied by scanning and transmission electron microscopy and temperature stability by thermogravimetric analysis. Their stability in biological fluids (simulated gastrointestinal and saliva) and tolerance against 0.5 mM NaCl were analyzed. PHB NPs remained stable in all fluids, while after 24 h treatment, the PLA NPs showed the beginning of disintegration with intestinal fluid mimic. In addition to the preparation of polyethylene glycol (PEG) surface-coated NPs, PLA–PEG–PLA triblock copolymer (MW?～?7,366 Da) was also chemically synthesized and characterized. Cytotoxicity of all forms of nanoparticles was tested by MTT assay and by annexin pi staining.     

Kinetics and possible mechanism of hydrogen chloride oxidation over supported copper-containing salt catalysts: II. Kinetics of HCl oxidation in the deacon and methane oxychlorination reactions over the CuCl2-KCl-LaCl3 catalyst

The kinetics of HCl oxidation at 350–425°C over the supported CuCl₂-KCl-LaCl₃ catalyst has been investigated using a gradientless technique. The HCl oxidation kinetics in the Deacon and methane oxychlorination reactions has been studied in order to substantially extend the \(Cl_2 \left( {P_{Cl_2 } } \right)\) partial pressure variation range. When the reaction rate is independent of P _HCl, HCl oxidation on the copper-potassium catalysts is described by the same rate equation, irrespective of whether the catalyst contains lanthanum or not. The introduction of lanthanum chloride increases the HCl oxidation rate by one order of magnitude. The rate equation obtained has significant advantages over the equation corresponding to the Kenney-Slama equation. The kinetic features of HCl oxidation over the lanthanum-containing catalyst, whether the process depends on P _HCl or not, can be explained in terms of the superposition of the Kenney-Slama dissociative mechanism and the catalytic mechanism suggested here. The role of lanthanum chloride in both HCl oxidation pathways is considered.