Controlled amine functionality in self-assembled monolayers via the hidden amine route: chemical and electronic tunability.

A synthetic strategy for fabricating a dense amine functionalized self-assembled monolayer (SAM) on hydroxylated surfaces is presented. The assembly steps are monitored by X-ray photoelectron spectroscopy, Fourier transform infrared- attenuated total reflection, atomic force microscopy, variable angle spectroscopic ellipsometry, UV-vis surface spectroscopy, contact angle wettability, and contact potential difference measurements. The method applies alkylbromide-trichlorosilane for the fabrication of the SAM followed by surface transformation of the bromine moiety to amine by a two-step procedure: S(N)2 reaction that introduces the hidden amine, phthalimide, followed by the removal of the protecting group and exposing the free amine. The use of phthalimide moiety in the process enabled monitoring the substitution reaction rate on the surface (by absorption spectroscopy) and showed first-order kinetics. The simplicity of the process, nonharsh reagents, and short reaction time allow the use of such SAMs in molecular nanoelectronics applications, where complete control of the used SAM is needed. The different molecular dipole of each step of the process, which is verified by DFT calculations, supports the use of these SAMs as means to tune the electronic properties of semiconductors and for better synergism between SAMs and standard microelectronics processes and devices.

Efficient parametric uncertainty analysis within the hybrid Finite Element/Statistical Energy Analysis method

This paper is concerned with the development of efficient algorithms for propagating parametric uncertainty within the context of the hybrid Finite Element/Statistical Energy Analysis (FE/SEA) approach to the analysis of complex vibro-acoustic systems. This approach models the system as a combination of SEA subsystems and FE components; it is assumed that the FE components have fully deterministic properties, while the SEA subsystems have a high degree of randomness. The method has been recently generalised by allowing the FE components to possess parametric uncertainty, leading to two ensembles of uncertainty: a non-parametric one (SEA subsystems) and a parametric one (FE components). The SEA subsystems ensemble is dealt with analytically, while the effect of the additional FE components ensemble can be dealt with by Monte Carlo Simulations. However, this approach can be computationally intensive when applied to complex engineering systems having many uncertain parameters. Two different strategies are proposed: (i) the combination of the hybrid FE/SEA method with the First Order Reliability Method which allows the probability of the non-parametric ensemble average of a response variable exceeding a barrier to be calculated and (ii) the combination of the hybrid FE/SEA method with Laplace's method which allows the evaluation of the probability of a response variable exceeding a limit value. The proposed approaches are illustrated using two built-up plate systems with uncertain properties and the results are validated against direct integration, Monte Carlo simulations of the FE and of the hybrid FE/SEA models. © 2013 Elsevier Ltd.

Kinetic study of the 2-methyl-3-methoxy-4-phenylbutanoic acid produced by oxidation of microcystin in aqueous solutions

Microcystins (MCs) are a family of related cyclic hepatotoxic heptapeptides, of which more than 70 types have been identified. The chemically unique nature of the C20 beta-amino acid, (2S, 3S, 8S, 9S)-3-amino-9-methoxy-2,6,8-trimethyl-10-phenyldeca4,6-dienoic acid (Adda), portion of the MCs has been exploited to develop a strategy to analyze the entirety. Oxidation of MCs causes the cleavage of MC Adda to form 2-methyl-3-methoxy-4-phenylbutanoic acid (MMPB). In the present study, we investigated the kinetics of MMPB produced by oxidation of the most-often-studied MC variant, MC-LR (L = leucine, R = arginine), with permanganate-periodate. This investigation allowed insight regarding the influence of the reaction conditions (concentration of the reactants, temperature, and pH) on the conversion rate. The results indicated that the reaction was second order overall and first order with respect to both permanganate and MC-LR. The second-order rate constant ranged from 0.66 to 1.35 M/s at temperatures from 10 to 30 degrees C, and the activation energy was 24.44 kJ/mol. The rates of MMPB production can be accelerated through increasing reaction temperature and oxidant concentration, and sufficient periodate is necessary for the formation of MMPB. The initial reaction rate under alkaline and neutral conditions is higher than that under acidic conditions, but the former decreases faster than the latter except under weakly acidic conditions. These results provided new insight concerning selection of the permanganate-periodate concentration, pH, and temperature needed for the oxidation of MCs with a high and stable yield of MMPB.

Studies on the adsorption equilibrium and kinetics of pentachlorophenol on suspended particulate matter of Donghu Lake water

In this paper, the adsorption equilibrium and kinetic behaviors of pentachlorophenol (PCP) on suspended particulate matter (SPM) in Donghu Lake water were investigated. The Langmuir and Freundlich adsorption models were applied to describe the equilibrium isotherms and their constants were evaluated. The results indicated that the adsorption of PCP on Donghu Lake SPM followed the Freundlich isotherm. Furthermore, the first order Lagergren rate equation and the pseudo-second order rate equation were used to describe the kinetic behaviors of PCP adsorption on Donghu Lake SPM, the rate constants were determined, and the kinetic process of the adsorption of PCP on Donghu Lake SPM followed the second order kinetic model.

Enzymatic activities in constructed wetlands and di-n-butyl phthalate (DBP) biodegradation

The bioaccumulation of phthalate acid esters (PAEs) from industrial products and their mutagenic action has been suggested to be a potential threat to human health. The effects of the most frequently identified PAE, Di-n-butyl phthalate (DBP), and its biodegradation, were examined by comparison of two small scale plots (SSP) of integrated vertical-flow constructed wetlands. The influent DBP concentration was 9.84 mg l(-1) in the treatment plot and the control plot received no DBP. Soil enzymatic activities of dehydrogenase, catalase, protease, phosphatase, urease, cellulase, beta-glucosidase, were measured in the two SSP after DBP application for 1 month and 2 months, and 1 month after the final application. Both treatment and control had significantly higher enzyme activity in the surface soil than in the subsurface soil (P < 0.001) and greater enzyme activity in the down-flow chamber than in the up-flow chamber (P < 0.05). In the constructed wetlands, DBP enhanced the activities of dehydrogenase, catalase, protease, phosphatase and inhibited the activities of urease, cellulase and beta-glucosidase. However, urease, cellulase, beta-glucosidase activities were restored 1 month following the final DBP addition. Degradation of DBP was greater in the surface soil and was reduced in sterile soil, indicating that this process may be mediated by aerobic microorgansims. DBP degradation fitted a first-order model, and the kinetic equation showed that the rate constant was 0.50 and 0.17 d(-1), the half-life was 1.39 and 4.02 d, and the r(2) was 0.99 and 0.98, in surface and subsurface soil, respectively. These results indicate that constructed wetlands are able to biodegrade organic PA-Es such as DBP. (c) 2005 Elsevier Ltd. All rights reserved.

Kinetics of the oxidation of MCRR by potassium permanganate

The occurrence of the microcystins in the water bodies, especially in drinking water resources, has received considerable attentions. In situ chemical oxidation is a promising cost-effective treatment method to remove MC from water body. This research investigated the reaction kinetics of the oxidation of MCRR by permanganate. Experimental results indicate that the reaction is second order overall and first order with respect to both permanganate and MCRR, and has an activation energy of 18.9 kJ/mol. The second-order rate constant ranges from 0.154 to 0.225 l/mg/min at temperature from 15 to 30 degrees C. The MCRR degradation rates can be accelerated through increasing reaction temperature and oxidant concentration. The reaction under acid conditions was slightly faster than under alkaline conditions. The half-life of the reaction was less than 1 min, and more than 99.5% of MCRR was degraded within 10 min. (c) 2005 Elsevier Ltd. All rights reserved.

Photodegradation dynamics of pure microcystin variants with illumination of fixed wavelength UV-lights

Photolysis of microcystins by UV irradiation and the effects of different environmental factors on efficiency of UV degradation were studied. The results indicated that the rates of the photolytical degradation reactions of microcystin-LR and RR-follow pseudo-first-order kinetic process. The results also showed that the concentrations of two microcystin variants decreased significantly by UV-C Irradiation; the wavelength and intensitiy of UV irradiation are two very important factors affecting the rate of degradation; temperature and pH value could also affect the half life of degradation rates. When irradiated by weaker UV-Iight, isomerization could be detected in the course of photolytical degradation. The concentrations of two isomers transformed from microcystin-LR reached its maximum at the third minute and decreased with the time afterwards. To simulate photolysis of microcystins in the field water body, microcystins with low concentration were used. It was found that UV-C illumination was capable of decomposing over 95% of microcystins within 40 min. In the presence of humic substances the photodecomposition slowed down to a certain extent. These results are valuable in using UV irradiation for elimination microcystins from raw water.

Control of the lasing wavelength by a sampled grating in a complex-coupled DFB laser

The lasing wavelength of a complex-coupled DFB laser is controlled by a sampled grating. The key concepts of the approach are to utilize the -1st order (negative first order) reflection of a sampled grating for laser single mode operation, and use conventional holographic exposure combined with the usual photolithography to fabricate the sampled grating. The typical threshold current of the sampled grating based DFB laser is 32 mA, and the optical output is about 10 mW at an injected current of 100 mA. The lasing wavelength of the device is 1.5356 mu m, which is the -1st order wavelength of the sampled grating.

Raman scattering of non-planar graphite: arched edges, polyhedral crystals, whiskers and cones

Planar graphite has been extensively studied by Raman scattering for years. A comparative Raman study of several different and less common non-planar graphitic materials is given here. New kinds of graphite whiskers and tubular graphite cones (synthetic and natural) have been introduced. Raman spectroscopy has been applied to the characterization of natural graphite crystal edge planes, an individual graphite whisker graphite polyhedral crystals and tubular graphite cones. Almost all of the observed Raman modes were assigned according to the selection rules and the double-resonance Raman mechanism. The polarization properties related to the structural features, the line shape of the first-order dispersive mode and its combination modes, the frequency variation of some modes in different carbon materials and other unique Raman spectral features are discussed here in detail.

A novel design of grating couplers for efficient broadband coupling between silicon-on-insulator nanophotonic waveguides and fibres

A novel design of out-of-plane grating couplers is proposed for coupling between silicon-on-insulator nanophotonic waveguides and single-mode fibres. The coupler with the first-order diffraction coupling to the optical fibre is actually a second-order reflected grating with two times of period of the first-order grating. To enhance outcoupled power, a back hole is designed to form in the silicon substrate and a kind of metals is placed on the top acting as a reflection layer. The coupler is optimized using coupled-mode- based simulations, showing that, the coupling efficiency to and from tapered optical fibre can be as high as 85% with 1 dB bandwidth about 23nm.

Structural, photoluminescence, and field emission properties of vertically well-aligned ZnO nanorod arrays

The self-assembled growth of vertically well-aligned ZnO nanorod arrays with uniform length and diameter on Si substrate has been demonstrated via thermal evaporation and vapor-phase transport. The structural, photoluminescence (PL), and field emission properties of the as-prepared nanorod arrays were investigated. The PL spectrum at 10 K shows a strong and sharp near-band gap emission (NBE) peak ( full width at half-maximum (FWHM) = 4.7 meV) and a weak neglectable deep-level emission (DL) peak (I-NBE/I-DL= 220), which implies its good crystallinity and high optical quality. The room-temperature NBE peak was deduced to the composition of free exciton and its first-order replicas emissions by temperature-dependent PL spectra. The field emission measurements indicate that, with a vacuum gap of 400 Am, the turn-on field and threshold field is as low as 2.3 and 4.2 V/mu m. The field enhancement factor beta and vacuum gap d follows a universal equation.

Equilateral-triangle-resonator injection lasers with directional emission

Equilateral-triangle-resonator (ETR) lasers with an output waveguide jointed at one vertex of the resonator are fabricated on (100) GaInAsP-InP wafers using photolithography and a two-step inductively coupled plasma (ICP) etching technique. Distinct peaks with the mode spacing of longitudinal mode intervals are observed in the luminescence spectra at room temperature. Furthermore, some minor peaks appear in the middle of the main peaks, which can be attributed to the first-order transverse modes as predicted in the theoretical results. CW directional lasing emissions are achieved for ETR lasers with side lengths ranging from 15 to 30 pm up to 200 K. The temperature dependences of the threshold current and lasing wavelength are measured for an ETR laser with the side length of 20 mu m from 80 to 200 K. The observed threshold current rapidly increases as temperature increases over 170 K.

Mode-coupling analysis of three-dimensional microdisk resonators by the finite-difference time-domain technique

Quality factor enhancement due to mode coupling is observed in a three-dimensional microdisk resonator. The microdisk, which is vertically sandwiched between air and a substrate, with a radius of 1 mu m, a thickness of 0.2 mu m, and a refractive index of 3.4, is considered in a finite-difference time-domain (FDTD) numerical simulation. The mode quality factor of the fundamental mode HE71 decreases with an increase of the refractive index of the substrate, n(sub), from 2.0 to 3.17. However, the mode quality factor of the first-order mode HE72 reaches a peak value at n(sub) = 2.7 because of the mode coupling between the fundamental and the first-order modes. The variation of mode field distributions due to the mode coupling is also observed. This mechanism may be used to realize high-quality-factor modes in microdisks with high-refractive-index substrates. (c) 2006 Optical Society of America.

Raman scattering of nanocrystalline silicon embedded in SiO2

Raman scattering of nanocrystalline silicon embedded in SiO2 matrix is systematically investigated. It is found that the Raman spectra can be well fitted by 5 Lorentzian lines in the Raman shift range of 100-600 cm(-1). The two-phonon scattering is also observed in the range of 600-1100 cm(-1) The experimental results indicate that the silicon crystallites in the films consist of nanocrystalline phase and amorphous phase; both can contribute to the Raman scattering. Besides the red-shift of the first order optical phonon modes with the decreasing size of silicon nanocrystallites, we have also found an enhancement effect on the second order Raman scattering, and the size effect on their Raman shift.

Crystallographic and magnetic properties of hydride R3Fe29-xTxHy (R=Y, Ce, Nd, Sm, Gd, Tb and Dy; T=V and Cr)

The crystallographic and intrinsic magnetic properties of hydride R3Fe29-xTxHy (R=Y, Ce, Nd, Sm, Gd, Tb, and Dy; T=V and Cr) have been investigated. The lattice constants and the unit cell volume of R3Fe29-xTxHy decrease with increasing R atomic number from Nd to Dy, except for Ce, reflecting the lanthanide contraction. Regular anisotropic expansions, mainly along the a- and b-axis rather than along the c-axis, are observed for all the compounds upon hydrogenation. Hydrogenation leads to an increase in Curie temperature. First-order magnetization processes (FOMP) occur in magnetic fields of around 1.5 T and 4.0 T at 4.2 K for Nd3Fe24.5Cr4.5H5.0 and Tb(3)Fc(27.0)Cr(2.0)H(2.8), and around 1.4 T at room temperature for Gd3Fe28.0Cr1.0H4.2 Abnormal crystallographic and magnetic properties of Ce3Fe29-xTxHy suggest that the Ce ion is non-triply ionized.