Laterally-corrugated ridge-waveguide distributed feedback lasers at 980 nm

The paper presents a simulation-based analysis of laterally-corrugated ridge-waveguide distributed feedback semiconductor lasers emitting at 980 nm. The simulations were performed using software developed in-house and the PICS3D software package from Crosslight Software Inc. The effects of the corrugation geometry, phase-shift section, and mirror reflectivities on single longitudinal mode operation are discussed. The lasers, designed along the guidelines derived from the simulation results, were fabricated by using molecular beam epitaxy for wafer growth and low-cost nano-imprint lithography. They exhibited stable single-mode operation with up to 50 dB side-mode suppression ratio.     

Core level studies of calcite and dolomite

Conventional X‐ray photoelectron spectroscopy (XPS) and synchrotron‐based X‐ray photoelectron spectroscopy (HRXPS) have been used to study Iceland spar calcite (CaCO₃) and dolomite (CaMg(CO₃)₂). The obtained full widths at half maximum (FWHMs) are mostly narrower than in the previous results, which together with the symmetry of the fitted peaks indicate effective neutralisation of surface charging. Some previously unidentified features observed in the Ca 2p, C 1s and O 1s spectra of calcite have been suggested to be bulk plasmons. Also, surface core level shifts in Ca 2p (in calcite) and Mg 2p (in dolomite) spectra have been obtained and found to be consistent between XPS and HRXPS measurements. A peak attributed to carbide (CaC₂) has been suggested to indicate beam‐assisted interaction with hydrocarbons found on the surface. Copyright © 2014 John Wiley & Sons, Ltd.     

Layer-by-layer electrostatic self-assembly of single-wall carbon nanotube polyelectrolytes

We have used anionic and cationic single-wall carbon nanotube polyelectrolytes (SWNT-PEs), prepared by the noncovalent adsorption of ionic naphthalene or pyrene derivatives on nanotube sidewalls, for the layer-by-layer self-assembly to prepare multilayers from carbon nanotubes with polycations, such as poly(diallyldimethylammonium) or poly(allylamine hydrochloride) (PDADMA or PAH, respectively), and polyanions (poly(styrenesulfonate), PSS). This is a general and powerful technique for the fabrication of thin carbon nanotube films of arbitrary composition and architecture and allows also an easy preparation of all-SWNT (SWNT/SWNT) multilayers. The multilayers were characterized with vis-near-IR spectroscopy, X-ray photoelectron spectroscopy (XPS), surface plasmon resonance (SPR) measurements, atomic force microscopy (AFM), and imaging ellipsometry. The charge compensation in multilayers is mainly intrinsic, which shows the electrostatic nature of the self-assembly process. The multilayer growth is linear after the initial layers, and in SWNT/polyelectrolyte films it can be greatly accelerated by increasing the ionic strength in the SWNT solution. However, SWNT/SWNT multilayers are much more inert to the effect of added electrolyte. In SWNT/SWNT multilayers, the adsorption results in the deposition of 1-3 theoretical nanotube monolayers per adsorbed layer, whereas the nominal SWNT layer thickness is 2-3 times higher in SWNT/polyelectrolyte films prepared with added electrolyte. AFM images show that the multilayers contain a random network of nanotube bundles lying on the surface. Flexible polyelectrolytes (e.g., PDADMA, PSS) probably surround the nanotubes and bind them together. On macroscopic scale, the surface roughness of the multilayers depends on the components and increases with the film thickness.     

Effect of Power Density on the Electrochemical Properties of Undoped Amorphous Carbon (a‐C) Thin Films

Undoped a‐C thin films were deposited with varying power density from 10 to 25 W/cm² using unbalanced closed‐field magnetron sputtering (CFUBMS). The effect of power density on the physical and electrochemical properties was investigated by experimental characterization methods and atomistic simulations. XPS indicated that the films were composed mostly of sp²‐bonded carbon (55–58 at.%) with a small amount of oxygen (8–9 at.%) in the surface region. The films appeared completely amorphous in XRD. The I_D/I_G ratio obtained by Raman spectroscopy indicated an increase from 1.76 to 2.34 with power density. The experimental and simulated data suggested a possible ordering and/or clustering of the sp² phase with power density as the cause of the improved electrical properties of the a‐C films. The electrochemical properties of a‐C were between those of glassy carbon and tetrahedral amorphous carbon with potential windows ranging from 2.77 to 2.93 V and double‐layer capacitance values around 0.90 μF cm^?2. Electron transfer for Ru(NH₃)₆^3+/2+ and FcMeOH^+1/0 was reversible whereas that for IrCl₆^2?/3? was quasi‐reversible. Peak potential separation of dopamine and oxidation potential of ascorbic acid decreased with power density, correlating with the structural and electrical changes of the films. The a‐C thin films deposited by CFUBMS are inherently conductive and their physical properties can be adjusted by varying the deposition parameters to a wide range of electrochemical applications.     

Detection of microcystins with protein phosphatase inhibition assay, high-performance liquid chromatography-UV detection and enzyme-linked immunosorbent assay: Comparison of methods

A colorimetric protein phosphatase inhibition assay (PPI assay), a commercial enzyme-linked immunosorbent assay (ELISA) test and different HPLC methods using UV detection were compared for the detection of cyanobacterial hepatotoxins, microcystins (MCYST) and nodularin. The suitability of the methods to detect different toxin variants was evaluated by using pure toxins and laboratory cultures as well as water and bloom samples of toxic cyanobacteria. The emphasis of the study was on the analysis of polar demethyl microcystin variants that are common in nature but for which there exist no commercial standards. The IC₅₀ values of MCYST-LR for the PPI assay and the ELISA test were 2.2-2.5 and 0.26-0.38 μg l⁻¹, respectively. The most important factors that decreased toxin recovery in sample treatment were the use of C₁₈ cartridges and polypropylene containers. Good recoveries of toxins were obtained by using hydrophilic-lipophilic balanced (Oasis HLB, Waters) cartridges for concentrating the samples. The results obtained with the PPI assay, the ELISA test and HPLC correlated quantitatively well with the exception of [d-Asp³] microcystins. Concentrations of [d-Asp³]MCYST-RR measured with the PPI assay were only 5% of those obtained by the ELISA test and HPLC. Concentrations of hydrophobic microcystin variants were lower when analysed with ELISA than with the other methods. The World Health Organisation (WHO) has set a guideline value of 1 μg l⁻¹ for the world-wide most common microcystin variant, MCYST-LR in drinking water. Since the quantitative ranges of the PPI assay and the ELISA test are within microcystin concentrations in natural waters, and both tests are easy to perform, they show potential for routine use in the screening and monitoring of microcystins from drinking water supplies and from recreational waters.     

Reduction of 6/7-substituted 3-phenyltrop-3-en-2-ones: stereoselectivity and conformational analysis of the products

Reduction of 6/7-carboethoxy-3-phenyltrop-3-en-2-ones with H₂/Pd/C and NaBH₄ was studied in order to find a stereoselective route to the corresponding 3-phenyltropan-2-ones and 2α/2β-hydroxy-3-phenyltropanes. The 6/7-exo-carboethoxy-3-phenyltrop-3-en-2-ones were selectively reduced by Pd/C to 3β-phenyltropan-2-ones and 2α-hydroxy-3β-phenyltropanes. The corresponding 2β-hydroxy-3β-phenyl analogues were synthesized using NaBH₄, with a yield of 40%. Reduction of 6-endo-carboethoxy-3-phenyltrop-3-en-2-one yielded several products. The corresponding 7-endo-substituted analogue was selectively reduced with both Pd/C and NaBH₄ to 7-endo-carboethoxy-3β-phenyltropin-2-one. Analysis of stereochemically important ¹H NMR spectroscopy parameters was performed for all the products and used for conformational analysis in solution. X-ray analysis was performed for selected compounds.     

ToF‐SIMS study of 1‐dodecanethiol adsorption on Au,Ag, Cu and Pt surfaces

Time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) has been used to perform a chemical analysis of long‐chain thiol (CH₃(CH₂)₁₁SH)‐treated gold, silver, copper and platinum surfaces. All the mass peaks from positive and negative ion spectra within the range m/z = 0–2000 u are studied. ToF‐SIMS data revealed that on gold, silver and copper substrates 1‐dodecanethiol form dense standing‐up phases, but on platinum being a catalytically active substrate, we were able to identify also surface‐aligned parallel lying molecules in addition to a standing thiolate layer. Our study shows that when ToF‐SIMS spectra are analyzed, not only the existence of oligomers but also metal + hydrocarbon fragments give information about the order of SAM. Copyright © 2008 John Wiley & Sons, Ltd.     

Electrochemical Generation of Hot Electrons in Fully Aqueous Solutions at Tetrahedral Amorphous Carbon Thin Film Electrodes and Electrochemiluminescence Immunoassay of Serum Amyloid A

Electrochemistry of hot electrons in fully aqueous solutions at tetrahedral amorphous carbon thin film electrodes is discussed. The generation of these highly reducing chemical species was confirmed by normal pulse voltammetry and several electrochemiluminescent systems. Electron transfer into pre-existing solvent cavities was observed at approximately −2.65 V vs. Ag/AgCl (sat.). Electrogenerated hot electrons were utilized as chemiluminescent mediators in heterogeneous sandwich immunoassay of Serum Amyloid A. The calibration curve was linear over four orders of magnitude and the detection limit was 85 ng L⁻¹ that demonstrates the efficiency of hot electron generation at this electrode material.     

Fast and Tunable Phosphorescence from Organic Ionic Crystals

Crystalline diphosphonium iodides [MeR₂P-spacer-R₂Me]I with phenylene ( 1 , 2 ), naphthalene ( 3 , 4 ), biphenyl ( 5 ) and anthracene ( 6 ) as aromatic spacers, are photoemissive under ambient conditions. The emission colors (λ_em values from 550 to 880 nm) and intensities (Φ_em reaching 0.75) are defined by the composition and substitution geometry of the central conjugated chromophore motif, and the anion-π interactions. Time-resolved and variable-temperature luminescence studies suggest phosphorescence for all the titled compounds, which demonstrate observed lifetimes of 0.46–92.23 μs at 297 K. Radiative rate constants k_r as high as 2.8×10⁵ s⁻¹ deduced for salts 1 – 3 were assigned to strong spin-orbit coupling enhanced by an external heavy atom effect arising from the anion-π charge-transfer character of the triplet excited state. These rates of anomalously fast metal-free phosphorescence are comparable to those of transition metal complexes and organic luminophores that utilize triplet excitons via a thermally activated delayed fluorescence mechanism, making such ionic luminophores a new paradigm for the design of photofunctional and responsive molecular materials.     

Characterisation of dolomites before and after reactivity measurement with HCl solution

The aim of this study was to compare different types of dolomites through batch reactivity experiments between HCl and dolomite powders, and ex‐situ characterisation of the particles before and after dissolution. Sedimentary dolomites were observed to have higher initial reactivities than metamorphic ones with sufficiently low calcite concentrations (<6% according to our regression model). In addition, the initial reactivities of the metamorphic dolomites were dependent on calcite concentration and could exceed those of the sedimentary dolomites. A regression model is presented for the dependence of initial reactivity on mineral composition and type of origin (sedimentary/metamorphic). The samples with the highest initial reactivities had also the largest BET (Brunauer, Emmet, Teller) surface areas obtained with nitrogen physisorption. Yet our data indicates that mineral composition of the dolomite has a greater influence on the initial reactivity than the BET surface area. Furthermore, it was found that the surface of sedimentary dolomites, unlike the surface of metamorphic dolomites, becomes porous during dissolution. Copyright © 2014 John Wiley & Sons, Ltd.