Chemiluminescence evidence supporting the selective role of ligands in the permanganate oxidation of micropollutants

The selective increase in the oxidation rate of certain organic compounds with permanganate in the presence of environmental "ligands" and reduced species has been ascribed to the different reactivity of the target compounds toward Mn(III), which bears striking similarities to recent independent investigations into the use of permanganate as a chemiluminescence reagent. In spite of the importance of Mn(III) in the light-producing pathway, the dependence of the oxidation mechanism for any given compound on this intermediate could not be determined solely through the emission intensity. However, target compounds susceptible to single-electron oxidation by Mn(III) (such as bisphenol A and triclosan) can be easily distinguished by the dramatic increase in chemiluminescence intensity when a permanganate reagent containing high, stable concentrations of Mn(III) is used. The differences are accentuated under the low pH conditions that favor the chemiluminescence emission due to the greater reactivity of Mn(III) and the greater influence of complexing agents. This study supports the previously postulated selective role of ligands and reducing agents in permanganate oxidations and demonstrates a new approach to explore the chemistry of environmental manganese redox processes.

Dual responsive chemosensors for anions : the combination of fluorescent PET (Photoinduced Electron Transfer) and colorimetric chemosensors in a single molecule

The design and synthesis of two novel fluorescent PET anion sensors is described, based on the principle of ‘fluorophore-spacer-(anion)receptor’. The sensors 1 and 2 employ simple diaromatic thioureas as anion receptors, and the fluorophore is a naphthalimide moiety that absorbs in the visible part of the spectrum and emits in the green. Upon recognition of anions such as F⁻ and AcO⁻ in DMSO, the fluorescence emission of 1 and 2 was ‘switched off’, with no significant changes in the UV–vis spectra. This recognition shows a 1:1 binding between the receptor and the anions. In the case of F⁻, further additions of the anion, gave rise to large changes in the UV–vis spectra, where the λ_max at 455 nm was shifted to 550 nm. These changes are thought to be due to the deprotonation of the 4-amino moiety of the naphthalimide fluorophore. This was in fact found to be the case, using simple naphthalimide derivatives such as 6. Sensors 1 and 2 can thus display dual sensing action; where at low concentrations, the fluorescence emission is quenched, and at higher concentrations the absorption spectra are modulated.

Cryo-electron microscopy and single molecule fluorescent microscopy detect CD4 receptor induced HIV size expansion prior to cell entry

Viruses are often thought to have static structure, and they only remodel after the viruses have entered target cells. Here, we detected a size expansion of virus particles prior to viral entry using cryo-electron microscopy (cryo-EM) and single molecule fluorescence imaging. HIV expanded both under cell-free conditions with soluble receptor CD4 (sCD4) targeting the CD4 binding site on the HIV-1 envelope protein (Env) and when HIV binds to receptor on cellular membrane. We have shown that the HIV Env is needed to facilitate receptor induced virus size expansions, showing that the 'lynchpin' for size expansion is highly specific. We demonstrate that the size expansion required maturation of HIV and an internal capsid core with wild type stability, suggesting that different HIV compartments are linked and are involved in remodelling. Our work reveals a previously unknown event in HIV entry, and we propose that this pre-entry priming process enables HIV particles to facilitate the subsequent steps in infection.

Deformation and annealing of (011)[011] oriented A1 single crystals

High purity Al single crystals of the (011)[011] orientation have been deformed in plane strain compression in a channel die. Deformation was carried out at a strain rate of 0.01 s−1 to true strains of 0.5 and 1.0, and at temperatures of 25, 200 and 300 °C. The as-deformed microstructure has been characterized using electron backscattered diffraction (EBSD) and X-ray diffraction (XRD). No recrystallization was detected after deformation, and the deformation texture analysis showed that the stability of the orientation decreased with increasing temperature, contrary to reports for other orientations.

Annealing was carried out for various times at 300 °C. Nucleation of recrystallization exhibited periodicity, with distinct bands of recrystallized grains forming parallel to the transverse direction. This recrystallized microstructure has been examined using EBSD. A model is proposed to account for the origin of the periodicity of nucleation and the retention of rods or cylinders of unrecrystallized material after significant annealing times.

Seeding of single crystal superalloys--Role of seed melt-back on casting defects

Single crystal seeds of the nickel-base superalloy CMSX-4 have been partially melted in a temperature gradient and then quenched. Small islands of random orientation are observed throughout the melted-back semi-solid. These random orientations appear to be pinched-off secondary dendrite arms, but there is no evidence that they are transported ahead of the dendrite tips to nucleate stray grains during directional solidification.

Nucleation sites for ultrafine ferrite produced by deformation of austenite during single-pass strip rolling

An austenitic Ni-30 wt pct Fe alloy, with a stacking-fault energy and deformation characteristics similar to those of austenitic low-carbon steel at elevated temperatures, has been used to examine the defect substructure within austenite deformed by single-pass strip rolling and to identify those features most likely to provide sites for intragranular nucleation of ultrafine ferrite in steels. Samples of this alloy and a 0.095 wt pct C-1.58Mn-0.22Si-0.27Mo steel have been hot rolled and cooled under similar conditions, and the resulting microstructures were compared using transmission electron microscopy (TEM), electron diffraction, and X-ray diffraction. Following a single rolling pass of ∼40 pct reduction of a 2mm strip at 800 °C, three microstructural zones were identified throughout its thickness. The surface zone (of 0.1 to 0.4 mm in depth) within the steel comprised a uniform microstructure of ultrafine ferrite, while the equivalent zone of a Ni-30Fe alloy contained a network of dislocation cells, with an average diameter of 0.5 to 1.0 µm. The scale and distribution and, thus, nucleation density of the ferrite grains formed in the steel were consistent with the formation of individual ferrite nuclei on cell boundaries within the austenite. In the transition zone, 0.3 to 0.5 mm below the surface of the steel strip, discrete polygonal ferrite grains were observed to form in parallel, and closely spaced “rafts” traversing individual grains of austenite. Based on observations of the equivalent zone of the rolled Ni-30Fe alloy, the ferrite distribution could be correlated with planar defects in the form of intragranular microshear bands formed within the deformed austenite during rolling. Within the central zone of the steel strip, a bainitic microstructure, typical of that observed after conventional hot rolling of this steel, was observed following air cooling. In this region of the rolled Ni-30Fe alloy, a network of microbands was observed, typical of material deformed under plane-strain conditions.

Transmission electron microscopy characterization of the bake-hardening behavior of transformation-induced plasticity and dual-phase steels

The effect of prestraining (PS) and bake hardening (BH) on the microstructures and mechanical properties has been studied in transformation-induced plasticity (TRIP) and dual-phase (DP) steels after intercritical annealing. The DP steel showed an increase in the yield strength and the appearance of the upper and lower yield points after a single BH treatment as compared with the as-received condition, whereas the mechanical properties of the TRIP steel remained unchanged. This difference appears to be because of the formation of plastic deformation zones with high dislocation density around the “as-quenched” martensite in the DP steel, which allowed carbon to pin these dislocations, which, in turn, increased the yield strength. It was found for both steels that the BH behavior depends on the dislocation rearrangement in ferrite with the formation of cell, microbands, and shear band structures after PS. The strain-induced transformation of retained austenite to martensite in the TRIP steel contributes to the formation of a complex dislocation structure.

Demonstration of the advantages of using bamboo-like nanotubes for electrochemical biosensor applications compared with single walled carbon nanotubes

The modification of glassy carbon electrodes with random dispersions of nanotubes is currently the most popular approach to the preparation of carbon nanotube modified electrodes. The performance of glassy carbon electrodes modified with a random dispersion of bamboo type carbon nanotubes was compared with single walled carbon nanotubes modified glassy carbon electrodes and bare glassy carbon electrodes. The electrochemical performance of all three types for electrode were compared by investigating the electrochemistry with solution species and the oxidation of guanine and adenine bases of surface adsorbed DNA. The presence of edge planes of graphene at regular intervals along the walls of the bamboo nanotubes resulted in superior electrochemical performance relative to SWNT modified electrodes from two aspects. Firstly, with solution species the peak separation of the oxidation and reduction waves were smaller indicating more rapid rates of electron transfer. Secondly, a greater number of electroactive sites along the walls of the bamboo-carbon nanotubes (BCNTs) resulted in larger current signals and a broader dynamic range for the oxidation of DNA bases.

Effect of orientation stability on recrystallization textures of deformed aluminium single crystals

High purity Al single crystals of the Cube (0 0 1)[1 0 0] and rotated Cube (0 1 1)[0 1 ¯ 1] orientations have been deformed in plane strain compression in a channel die. Deformation was carried out at temperatures between 25 and 600 8C up to strains of 1.2. The as-deformed microstructure has been characterised using electron microscopy and electron backscattered diffraction (EBSD).
Annealing was carried out for various times and temperatures. The recrystallized microstructure has been studied using electron microscopy, and the orientation of recrystallized grains determined using EBSD. After cold deformation and annealing both orientations exhibited a random recrystallization texture component. After hot deformation both orientations retained a similar annealing texture to their starting deformation texture. The annealing texture of deformed single crystals was found to be more sensitive to the temperature of deformation than the stability of the orientation.

A surface characterisation and microstructural study by scanning electron microscopy of the N-methyl-n-alkylpyrrolidinium tetrafluoroborate organic salts

A microstructural characterisation of the family of N-methyl-N-alkylpyrrolidinium tetrafluoroborate organic salts was carried out by observation of powder surface morphologies with the aim of extending the microstructure-property correlation. Inherent difficulties limiting extensive studies of organic solids by SEM, including volatility under vacuum, charging due to electron beam irradiation, and air-sensitivity were overcome with the use of a Field Emission SEM and cryostage attachment. This technique, providing considerable improvements in image quality at low accelerating voltages, enabled direct observation of complex microstructural features in samples exhibiting high temperature plastic crystalline phases (N,N-dimethylpyrrolidinium tetrafluoroborate [P11BF4]; N-methyl-N-ethylpyrrolidinium tetrafluoroborate [P12BF4]; N-methyl-N-propylpyrrolidinium tetrafluoroborate [P13BF4]). Extensive lattice imperfections including grain boundaries, slip planes and dislocation pits were observed within particles of approximately 200 mgrm diameter. The N-methyl-N-butylpyrrolidinium tetrafluoroborate (P14BF4) sample in this series revealed columnar single crystals with high aspect ratios. The origin of plastic flow properties is discussed using single crystal and polycrystalline slip observations and a relationship proposed between defect characteristics and transport properties.

Large-scale synthesis and growth mechanism of single-crystal Se nanobelts

Single-crystal trigonal (t) Se nanobelts have been synthesized on a large scale by reducing SeO2 with glucose at 160 °C. Electron microscopy images show that the nanobelts are 80 nm in diameter, 25 nm in thickness, and up to several hundreds of micrometers in length. HRTEM images prove that the nanobelts are single crystals and preferentially grow along the [001] direction. The time-dependent TEM images revealed that the formation and growth of t-Se nanobelts were governed by a solid−solution−solid growth mechanism. The redox reaction directly produced amorphous (α) Se nanoparticles under hydrothermal conditions. t-Se nanobelts were formed by dissolution and recrystallization of the initial α-Se nanoparticles under the functional capping of poly(vinylpyrrolidone) (PVP). The nanobelts obtained exhibit a quantum size effect in optical properties, showing a blue shift of the band gap and direct transitions relative to the values of bulk t-Se.

Single cell stiffness measurement at various humidity conditions by nanomanipulation of a nano-needle

This paper presents a method for single cell stiffness measurement based on a nano-needle and nanomanipulation. The nano-needle with a buffering beam was fabricated from an atomic force microscope cantilever by the focused ion beam etching technique. Wild type yeast cells (W303) were prepared and placed on the sample stage inside an environmental scanning electron microscope (ESEM) chamber. The nanomanipulator actuated the nano-needle to press against a single yeast cell. As a result, the deformation of the cell and nano-needle was observed by the ESEM system in real-time. Finally, the stiffness of the single cell was determined based on this deformation information. To reveal the relationship between the cell stiffness and the environmental humidity conditions, the cell stiffness was measured at three different humidity conditions, i.e. 40, 70 and 100%, respectively. The results show that the stiffness of a single cell is reduced with increasing humidity.

Neisseria meningitidis and Neisseria gonorrhoeae are differently adapted in the regulation of denitrification: single nucleotide polymorphisms that enable species-specific tuning of the aerobic–anaerobic switch

The closely related pathogenic Neisseria species N. meningitidis and N. gonorrhoeae are able to respire in the absence of oxygen, using nitrite as an alternative electron acceptor. aniA (copper-containing nitrite reductase) is tightly regulated by four transcriptional regulators: FNR (fumarate and nitrate reductase), NarP, FUR (Ferric uptake regulator) and NsrR. The four regulators control expression of aniA in N. meningitidis by binding to specific and distinct regions of the promoter. We show in the present study that FUR and NarP are both required for the induction of expression of aniA in N. meningitidis, and that they bind adjacent to one another in a non-co-operative manner. Activation via FUR/NarP is dependent on their topological arrangement relative to the RNA polymerase-binding site. Analysis of the sequence of the aniA promoters from multiple N. meningitidis and N. gonorrhoeae strains indicates that there are species-specific single nucleotide polymorphisms, in regions predicted to be important for regulator binding. These sequence differences alter both the in vitro DNA binding and the promoter activation in intact cells by key activators FNR (oxygen sensor) and NarP (which is activated by nitrite in N. meningitidis). The weak relative binding of FNR to the N. gonorrhoeae aniA promoter (compared to N. meningitidis) is compensated for by a higher affinity of the gonococcal aniA promoter for NarP. Despite containing nearly identical genes for catalysing and regulating denitrification, variations in the promoter for the aniA gene appear to have been selected to enable the two pathogens to tune differentially their responses to environmental variables during the aerobic–anaerobic switch.

Synthesis of single-crystalline LiFePO4 with rhombus-like morphology

In this investigation, carbon-coated LiFePO4 cathode materials were synthesized with a facile hydrothermal method. The structure and electrochemical properties of the materials were investigated by X-ray diffraction (XRD), Roman, transmission electron microscopy-energy dispersive spectroscopy (TEM-EDS), and electrochemical impedance spectroscopy (EIS). By adjusting the mixing concentration of starting materials, a single-crystalline LiFePO4 with an anisotropic rhombus morphology (Space Group: Pmnb No. 62) were successfully synthesized. In addition, the carbon coated on the surface of LiFePO4 material prepared has a lower ID/IG (0.80), which indicates an optimized carbon structure with an increased amount of sp2-type carbon. Electrochemical performance test shows that the carbon-coated LiFePO4 cathode materials have an initial discharge capacity of 146 mAh g−1 at 0.2C.