Energy dispersive spectroscopy‐scanning transmission electron microscope observations of free radical production in human polymorphonuclear leukocytes phagocytosing non‐opsonized Tannerella forsythia

We investigated the association between human polymorphonuclear leukocytes (PMNs) and non‐opsonized Tannerella forsythia ATCC 43037 displaying a serum‐resistant surface layer (S‐layer). When PMNs were mixed with T. forsythia in suspension, the cells phagocytosed T. forsythia cells. Nitro blue tetrazolium (NBT) reduction, indicative of production, was observed by light microscopy; cerium (Ce) perhydroxide deposition, indicative of H₂O₂ production, was observed by electron microscopy. We examined the relationship between high‐molecular‐weight proteins of the S‐layer and Ce reaction (for T. forsythia phagocytosis) using electron microscopic immunolabeling. Immunogold particles were localized within the PMNs and on cell surfaces, labelling at the same Ce‐reacted sites where the S‐layer was present. We then used energy dispersive spectroscopy (EDS)‐scanning transmission electron microscope (STEM) to perform Ce and nitrogen (N) (for S‐layer immunocytochemistry) elemental analysis on the phagocytosed cells. That is, the elemental mapping and analysis of N by EDS appeared to reflect the presence of the same moieties detected by the 3,3′‐diaminobenzidine‐tetrahydrochloride (DAB) reaction with horseradish peroxidase (HRP)‐conjugated secondary antibodies, instead of immunogold labeling. We focused on the use of EDS‐STEM to visualize the presence of N resulting from the DAB reaction. In a parallel set of experiments, we used EDS‐STEM to perform Ce and gold (Au; from immunogold labeling of the S‐layer) elemental analysis on the same phagocytosing cells.     

Anti wear and anti friction characteristics of tribochemical films of alkyl octa‐decenoates and their derivatives

The wear, friction and film forming characteristic of ethyl octadecenoate and methyl 12‐hydroxy ocatadecenoates, their thio and thiopyrophosphoro derivatives have been studied on HFRR friction and wear machine. The structural characteristics of chemisorbed films formed on the iron surfaces by these derivatives have been investigated using various analytical techniques such FT‐IR, Microreflectance Absorption and Proton Magnetic Resonance. It has been inferred that these films are primarily organic in nature. The constituents of these films are hydroxy alkyl and aryl ethers, unsaturated and condensed ring hydroxy ketones, aromatic hydroxy quinones and highly condensed aromatic structures chemically linked to iron sufaces through hydroxy, oxy, thia, oxyphosphoro and thiophosphoro moieties forming chelated and coordinated complexes. The antiwear and antifriction characteristic of alkyl octadecenoates increase with increasing polar linkages in the alkyl ocatadecenoate backbone. This is primarily due to the increase in number of sites amenable to chemisorption on the surfaces and consequently their reactivity. The antiwear and antifriction characteristic of derivatives of ethyl octadecenoates are inferior to the corresponding 12‐hydroxy methyl octadecenoates derivatives. This can be attributed to increased reactivity of 12‐hydroxy methyl octadecenoates derivatives at the surfaces due to an additional hydroxyl moiety. The films formed are highly condensed ring aromatic layered structures coordinating to iron atoms of the surface particularly in case of thiopyrophosphoro derivatives of methyl 12‐hydroxy octadecenoates. These films, as a consequence, provide lower wear and friction characteristics as compared to other types of organic films. These studies have led to much clear evidence of the intimate relationship between the chemical structure of the additives and their film forming characteristics. Copyright © 2006 John Wiley & Sons, Ltd.     

Spectroscopic characterization of glycidyl methacrylate with acrylonitrile copolymers and monomer reactivity ratios

We report herein that copolymers containing glycidyl methacrylate (GMA) with acrylonitrile (AN) units were synthesized by free radical solution polymerization technique using benzoyl peroxide as a free radical initiator and 1,4‐dioxane as a solvent at 70°C. The copolymerization behavior was studied in different composition with the mole fractions of GMA ranging from 0.20 to 0.80 in the feed and under 10% copolymer conversion. The copolymers were characterized by Fourier transform infrared spectroscopy, gel permeation chromatography, and scanning electron microscopy techniques. The thermogravimetric analysis of the copolymers suggest an overall decrease in the thermal stability of the copolymer with decreasing content of GMA in the copolymers. Thermal decomposition activation energies are calculated by the Ozawa method. The copolymer composition was determined by the application of elemental analysis method. The monomer reactivity ratios were estimated by the application of conventional linearization methods, such as Kelen–Tudos (K‐T), Fineman–Ross (F‐R) methods, and a nonlinear error in variable model (RREVM) method using a computer program, and all results were discussed and compared with the literature.     

The application of heat‐deproteinization to the morphological study of cortical bone: A contribution to the knowledge of the osteonal structure

Observation of heat‐deproteinized cortical bone specimens in incident light enabled the high definition documentation of the osteonal pattern of diaphyseal Haversian bone. This prompted a study to compare these images with those revealed by polarized light microscopy, carried out either on decalcified or thin, undecalcified, resin‐embedded sections. Different bone processing methods can reveal structural aspects of the intercellular matrix, depending on the light diffraction mode: birefringency in decalcified sections can be ascribed to the collagen fibrils orientation alone; in undecalcified sections, to both the ordered layout of collagen and the inorganic phase; in the heat‐deproteinized samples, exclusively to the hydroxyapatite crystals aggregation mode. The elemental chemical analysis documented low content of carbon and hydrogen, no detectable levels of nitrogen and significantly higher content of calcium and phosphorus in heat‐deproteinized samples, as compared with dehydrated controls. In both samples, the X‐ray diffraction (XRD) pattern did not show any significant difference in pattern of hydroxyapatite, with no peaks of any possible decomposition phases. Scanning electron microscopic (SEM) morphology of heat‐deproteinized samples could be documented with the fracturing technique facilitated by the bone brittleness. The structure of crystal aggregates, oriented in parallel and with marks of time periods, was documented. Comparative study of deproteinized and undecalcified samples showed that the matrix inorganic phase did not undergo a coarse grain thermal conversion until it reached 500°C, maintaining the original crystals structure and orientation. Incident light stereomicroscopy, combined with SEM analysis of deproteinized bone fractured surfaces, is a new enforceable technique which can be used in morphometric studies to improve the understanding of the osteonal dynamics. Microsc. Res. Tech. 79:691–699, 2016. © 2016 Wiley Periodicals, Inc.     

The influence of oxidation on the tribological performance of diester lubricant

The oxidative degradation test of di‐2‐ethylhexyl sebacate (DEHS) was carried out by a sealed stainless steel reactor. Fourier transform infrared spectroscopy and gas chromatography–mass spectrometry (GC–MS) were utilised to characterise the chemical composition and molecular structure of the oxidation products. The results revealed that 2‐ethyl‐1‐hexanol and mono(2‐ethylhexyl)sebacate were major degradation products in the liquid phase. Tribological behaviour was measured using a four‐ball tester. Scanning electron microscopy was employed to investigate the morphologies of the worn surface. Tribological results showed that anti‐wear and friction‐reducing performances of DEHS were highly dependent on the chemical composition of the oxidation products generated during the test. The hydroperoxides formed during the initial oxidation process could deteriorate lubrication properties of DEHS. However, certain amount of highly polar degradation products (acids and alcohols) generated could significantly improve the friction‐reducing performance of DEHS by the formation of boundary adsorption films on the rubbing surfaces. Copyright © 2013 John Wiley & Sons, Ltd.     

C/Al-40%Cu复合材料的原位热解-热压法制备及微观结构

以聚乙烯醇缩丁醛为碳源,采用原位热解-热压法制备C/Al-40%Cu(体积分数)复合材料,研究了该复合材料的物相组成、微观结构以及界面反应特性。结果表明:复合材料主要由铝相、铜相、原位生成的碳材料以及少量残留的高分子材料组成,碳材料连续存在于铝、铜相颗粒之间,有效抑制了Al2Cu和Al4Cu9等金属间化合物的生成;复合材料的实测密度接近于理论密度,组织中未见明显孔洞,致密程度较高;复合材料界面结合良好,铝相和铜相、铝相和碳材料层之间均发生了元素互扩散,形成了厚度分别为2.0~3.5μm和1.0~1.5μm的扩散层,铜相和碳材料层之间以机械结合方式连接。     

The tribochemical performance of nano/micrometre borate modified by an N‐containing compound as an oil additive

An N‐modified nano / micrometre borate (MNMB) as an oil additive was synthesised by an ultrasonic dispersion and emulsion reaction in the microemulsion phase. The particles of the MNMB additive were between 20 and 500 nm in diameter. The tribological properties of the MNMB as an oil additive were investigated using a four‐ball tester. The results reveal that the MNMB possesses good tribological properties. When the boron concentration is 0. 05 wt. %, the wear‐scar diameter is smallest and the seizure load is highest. The antiwear and extreme‐pressure properties of the MNMB were best at a viscosity of 65. 3 mms2. Small‐area X‐ray photoelectron spectroscopy (XPS) and electron probe microanalysis (EPMA) indicate that the MNMB additive can form a tribological mixed reaction film containing C, O, B, N, and Na on a rubbing surface. The elemental boron exists in four different chemical states, but is mainly present in the form of BN on the rubbing surface.     

Tribological performances of heterocyclic‐containing ether and/or thioether as additives in the synthetic diester

The load‐carrying capacity, wear and friction properties of 2‐octoxyl methylthio‐benzothiazole (DEOY) and 2‐dodecylthio methylthio‐benzothiazole (DEMB) added to a synthetic lubricant (diester) were evaluated using a four‐ball test machine. The results indicate that the two compounds added to the diester possess good load‐carrying capacities and excellent anti‐wear and friction reduction properties. The thermal stability of the two compounds under nitrogen atmosphere was investigated by thermogravimetric analysis (TGA). It was found that the compounds DEOY and DEMB possess excellent thermal stability. The surface topography of the rubbed surface was investigated with scanning electron microscopy, the elemental chemical nature of the anti‐wear films generated on steel counterface were investigated with X‐ray photoelectron spectroscopy. Copyright © 2009 John Wiley & Sons, Ltd.     

Tribological performance of sulfonamide derivatives as lubricating oil additives in the diester

The load‐carrying capacity, anti‐wear and friction reduction properties of two sulfonamide derivatives added to a synthetic lubricant (diester) were evaluated using a four‐ball test machine. The results indicate that both additives possess good load‐carrying capacities and excellent anti‐wear and friction reduction properties. The surface topography of the rubbed surface was investigated by scanning electron microscopy, and the chemical nature of the anti‐wear films generated on the steel counter‐face was investigated by X‐ray photoelectron spectroscopy. Surface analysis results show that a stable lubricating film consisting of the reaction layer and adsorption layer was formed on the worn surface. Copyright © 2006 John Wiley & Sons, Ltd.     

Microstructure and interfacial chemistry of pure and La‐doped BiFeO3 thin films

We report on the microstructure and interfacial chemistry of thin films of pure and La‐doped multiferroic bismuth ferrite (Bi_1‐xLa_xFeO₃ or BLFO), synthesized on Indium Tin Oxide‐coated glass substrates by solution‐deposition technique and studied using scanning transmission electron microscopy. Our results show that undoped and La‐doped thin films are polycrystalline with distorted rhombohedral structure without any presence of any line or planar defect in the films. In addition, the films with La doping did not show any structural change and maintain the equilibrium structure. Cross section compositional analysis using X‐ray energy dispersive spectrometry did not reveal either any interdiffusion of chemical species or formation of reaction product at the film‐substrate interface. However, a closer examination of the microstructure of the films shows tiny pores along with the presence of ～2–3 nm thin amorphous layers, which may have significant influence on the functional properties of such films. Microsc. Res. Tech. 76:1304–1309, 2013. © 2013 Wiley Periodicals, Inc.     

Characterisation,by the PIXE Method,of Trace Elements During Physicochemical Reactions at the Periphery of Bioactive Glass Pastilles in Contact with Biological Fluids

Abstract

The prerequisite for bioactive glasses to bond to living bone is the formation of biologically active apatites on their surface in the body. Reactions and bioactivity mechanisms between bioactive glasses and bone depend on the glass composition. We study a glass in the SiO₂‐Na₂O‐CaO‐P₂O₅‐K₂O‐Al₂O₃‐MgO system. To characterise physicochemical reactions at the materials periphery, we immersed the glass pastilles into biological fluids for periods of 5, 10, and 20 days. The surface changes were studied at the micrometer scale by a Particle Induced X‐ray Emission (PIXE) method associated with Rutherford Backscattering Spectroscopy (RBS). After 20 days of immersion, elemental maps showed the formation of a calcium‐phosphate layer at the surface of the glass pastilles. The thickness of this layer was around 15 µm. Thanks to the PIXE method, we demonstrated the presence of traces of Mg in this layer. The glass doped with MgO leads to the formation of an apatite which incorporates magnesium. Formation of this Ca‐P‐Mg layer represents the bioactive properties of the studied glass. This biologically active layer improves the properties of the glass and will permit a chemical bond between the ceramic and bone.     

Electrochemical study of the interaction between fatty acid and oxidized copper

Boundary lubrication involving reactions between the metal oxide layers and adsorbed polar species has been reported by several authors. In this study, the effect of an oxide layer on the mechanism of boundary lubrication during copper wire drawing was examined by electrochemical and surface analysis techniques. The minimum oxide thickness to initiate chemical and electrochemical reactions, and the oxide growth rate were determined by electrochemical methods. The oxide formed prior to chemical reaction with a fatty acid during boundary lubrication, and the chemical products were analyzed by electron spectroscopy for chemical analysis (ESCA) and Auger electron spectroscopy (AES). The properties of adsorbed layers were characterized by AC impedance spectroscopy. Optimum boundary lubrication can only be achieved during copper deformation, if the oxide thickness exceeds the minimum thickness of 60 Å and is cornposed of cuprous oxide.     

Synthesis and properties of cyclotriphosphazene and perfluoropolyether‐based lubricant with polar functional groups

A novel hard disk lubricant IDL2 was synthesised by reacting sodium 4‐((2,2‐dimethyl‐1,3‐dioxolan‐4‐yl)methoxy)phenoate with hexachlorocyclotriphosphazene, followed by treatment with 1H,1H‐perfluoro‐3,6,9‐trioxatridecan‐1‐ol in the presence of sodium hydride and subsequent hydrolysis using sulfuric acid. The chemical structure of IDL2 was confirmed by proton nuclear magnetic resonance (¹H NMR), phosphorus‐31 (³¹P) NMR spectroscopy and mass spectrometer. The thermal property of IDL2 was analysed using thermal gravimetric analysis (TGA) and it shows better thermal stability than two commercial lubricants Z‐DOL and Z‐Tetraol with two and four terminal hydroxy groups, respectively. IDL2 was found to have comparable hydrophobicity to commercial lubricants Z‐DOL, A20H and Z‐Tetraol with water contact angles in the range of 78 – 85°, revealing that IDL2 has analogous surface energy to these commercial lubricants. IDL2 exhibits comparable friction coefficient to A20H and Z‐Tetraol, but much lower than Z‐DOL. More interestingly, it has a much high bonding ratio when compared with commonly used commercial lubricants under the same testing conditions due to the presence of two polar hydroxy groups, which enhance the interaction between lubricant and substrate. These promising properties of IDL2 show that it would be very potential for real application as a hard disk drive lubricant. Copyright © 2016 John Wiley & Sons, Ltd.     

Mapping of ELNES on a nanometre scale by electron spectroscopic imaging

The amorphous interfacial layer between Si substrates and diamond films grown by plasma-assisted chemical vapour deposition has been studied by electron spectroscopic imaging. The amorphous layer consists mainly of carbon, which can only be distinguished from the diamond film by analysis of the near-edge structure (ELNES) of the carbon K edge. Series of electron spectroscopic images were acquired across the carbon K edge and were analysed in order to reveal the presence of the π*- and σ*-excitations. After background removal from the corresponding images, phase maps for the distribution of sp² and sp³ hybridized carbon can be obtained. From the whole series of images, electron energy-loss spectra can be extracted for any given area in the images. The results show that the amorphous layer covers large areas along the interface and that regions with only 1–2 nm layer thickness can clearly be analysed. The results obtained with the electron spectroscopic imaging technique will be compared with results obtained on a field emission gun scanning transmission electron microscope.     

Compositional analysis of mixed–cation-anion III–V semiconductor interfaces using phase retrieval high-resolution transmission electron microscopy

Employing exit‐plane wave function (EPWF) reconstruction in high‐resolution transmission electron microscopy (HRTEM), we have developed an approach to atomic scale compositional analysis of III‐V semiconductor interfaces, especially suitable for analyzing quaternary heterostructures with intermixing in both cation and anion sub‐lattices. Specifically, we use the focal‐series reconstruction technique, which retrieves the complex‐valued EPWF from a thru‐focus series of HRTEM images. A study of interfaces in Al_0.4Ga_0.6As–GaAs and In_0.25Ga_0.75Sb–InAs heterostructures using focal‐series reconstruction shows that change in chemical composition along individual atomic columns across an interface is discernible in the phase image of the reconstructed EPWF. To extract the interface composition profiles along the cation and anion sub‐lattices, quantitative analysis of the phase image is performed using factorial analysis of correspondence. This enabled independent quantification of changes in the In–Ga and As–Sb contents across ultra‐thin interfacial regions (approximately 0.6 nm wide) with true atomic resolution, in the In_0.25Ga_0.75Sb–InAs heterostructure. The validity of the method is demonstrated by analyzing simulated HRTEM images of an InAs–GaSb–InAs model structure with abrupt and graded interfaces. Our approach is general, permitting atomic‐level compositional analysis of heterostructures with two species per sub‐lattice, hitherto unfeasible with existing HRTEM methods.     

Combining FIB milling and conventional Argon ion milling techniques to prepare high‐quality site‐specific TEM samples for quantitative EELS analysis of oxygen in molten iron

This paper reports a procedure to combine the focused ion beam micro‐sampling method with conventional Ar‐milling to prepare high‐quality site‐specific transmission electron microscopy cross‐section samples. The advantage is to enable chemical and structural evaluations of oxygen dissolved in a molten iron sample to be made after quenching and recovery from high‐pressure experiments in a laser‐heated diamond anvil cell. The evaluations were performed by using electron energy‐loss spectroscopy and high‐resolution transmission electron microscopy. The high signal to noise ratios of electron energy‐loss spectroscopy core‐loss spectra from the transmission electron microscopy thin foil, re‐thinned down to 40 nm in thickness by conventional Argon ion milling, provided us with oxygen quantitative analyses of the quenched molten iron phase. In addition, we could obtain lattice‐fringe images using high‐resolution transmission electron microscopy. The electron energy‐loss spectroscopy analysis of oxygen in Fe_0.94O has been carried out with a relative accuracy of 2%, using an analytical procedure proposed for foils thinner than 80 nm. Oxygen K‐edge energy‐loss near‐edge structure also allows us to identify the specific phase that results from quenching and its electronic structure by the technique of fingerprinting of the spectrum with reference spectra in the Fe‐O system.     

双层辉光等离子渗金属技术制备TiN渗层及其耐NaOH溶液腐蚀性能

采用双层辉光等离子渗金属技术在Q235钢表面上制备了TiN渗层;对渗层的组织、硬度、成分和相结构及其耐NaOH溶液腐蚀性能进行了研究.结果表明:该渗层是由TiN颗粒均匀分布的扩散层及表面TiN沉积层组成的梯度结构;渗层表面形貌为胞状组织,颗粒致密均匀,表面为金黄色,渗层厚度可达16μm,与基体实现了冶金结合;渗层表面钛...     

The effect of basic nitrogen compounds on the tribological performance of sulphurised olefin

The effect of the molecular structure of basic nitrogen compounds on the lubricating properties of sulphurised olefin has been investigated using a Timken tester. X-ray Photoelectron Spectroscopy (XPS) and Energy Dispersive X-ray Analysis (EDAX) were used to study the chemical states of sulphur and nitrogen on the rubbed surfaces and the reaction rates of sulphur and iron separately. It was found that the antiwear and friction reduction properties of sulphurised olefin are greatly influenced by the different molecular structures of the basic nitrogen compounds. A composite additive package containing basic nitrogen compounds with sulphurised olefin can produce either synergistic or antagonistic effects, due to the influence of the different molecular structures of the basic nitrogen compounds. XPS analysis revealed that a tribochemical protective film containing nitrogen and sulphur was formed on the rubbed surface. EDAX analysis indicated that the reaction rates between elemental sulphur and iron were influenced by the different molecular structures of the basic nitrogen compounds. It was found that the apparent reaction rates of elemental sulphur and iron are related to the tribological characteristics of the additive package.     

ICP-MS相关联用技术在食品元素形态分析中的应用及进展

电感耦合等离子体质谱（ICP-MS）技术凭借其低检出限、多元素同时分析等优点,广泛应用于食品中的元素分析。随着分析技术的发展,以及元素的不同形态在物理、化学、营养、毒理等方面的显著差异,元素形态分析已经引起分析工作者的广泛关注。本工作对近年来ICP-MS技术与各种分离手段联用,在食品中砷、硒及锡等元素形态分析中的应用进行了综述,指出了ICP-MS 相关联用技术应用于食品元素形态分析时存在的问题,并对其未来的发展趋势进行了展望。     

Red-shifted fluorescent proteins monitor enzymatic activity in live HT-1080 cells with fluorescence lifetime imaging microscopy (FLIM)

Membrane type 1 matrix metalloproteinase (MT1‐MMP) is a membrane‐tethered collagenase primarily involved in the mechanical destruction of extracellular matrix proteins. MT1‐MMP has also been shown to be upregulated in several types of cancers. Many coordinated functions of MT1‐MMP during migration and invasion remain to be determined. In this paper, live cells from the invasive cell line HT‐1080 were imaged using an intracellular Förster resonance energy transfer‐based biosensor specific for MT1‐MMP; a substrate specific for MT1‐MMP was hybridized with the mOrange2 and mCherry fluorescent proteins to form the Förster resonance energy transfer‐based sensor. The configuration of the biosensor was determined with fluorescence lifetime‐resolved imaging microscopy using both a polar plot‐based analysis and a rapid data acquisition modality of fluorescence lifetime‐resolved imaging microscopy known as phase suppression. Both configurations of the biosensor (with or without cleavage by MT1‐MMP) were clearly resolvable in the same cell. Changes in the configuration of the MT1‐MMP biosensor were observed primarily along the edge of the cell following the removal of the MMP inhibitor GM6001. The intensities highlighted by phase suppression correlated well with the fractional intensities derived from the polar plot.