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.

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.

Effects of GaN Capping on the Structural and the Optical Properties of InN Nanostructures Grown by Using MOCVD

InN nanostructures with and without GaN capping layers were grown by using metal-organic chemical vapor deposition. Morphological, structural, and optical properties were systematically studied by using atomic force microscopy, X-ray diffraction (XRD) and temperature-dependent photoluminescence (PL). XRD results show that an InGaN structure is formed for the sample with a GaN capping layer, which will reduce the quality and the IR PL emission of the InN. The lower emission peak at similar to 0.7 eV was theoretically fitted and assigned as the band edge emission of InN. Temperature-dependent PL shows a good quantum efficiency for the sample without a GaN capping layers; this corresponds to a lower density of dislocations and a small activation energy.

Raman scattering of folded acoustic phonons in self-assembled Si/Ge dot superlattices

Self-assembled Si/Ge dot multilayers with small, uncorrelated dots fabricated by molecular beam epitaxy in the Stranski-Krastanov growth mode are studied by Raman scattering of folded longitudinal acoustic (FLA) modes. The FLA Raman spectra are analyzed and modeled with respect to mode frequencies and the spectral envelope of mode intensities. The deduced average superlattice properties are consistent with results from atomic force microscopy. The simple Rytov model used for Si/Ge layer structures reproduces very well the frequencies of the FLA modes up to 150 cm(-1). The nonlinearity of phonon dispersion curves in bulk Si for large momenta, however, becomes important for modeling the higher frequencies of observed FLA modes up to 22nd order. The effective dot layer width and an activation energy for thermal intermixing of 2.1+/-0.2 eV are determined from the spectral envelopes of FLA mode intensities of as-grown and annealed Si/Ge dot multilayers. (C) 2004 American Institute of Physics.

Effect of SiO2 encapsulation on the nitrogen reorganization in a GaNAs/GaAs single quantum well

Effects of SiO2 encapsulation and rapid thermal annealing on the optical properties of a GaNAs/GaAs single quantum well (SQW) are studied by low-temperature photoluminescence (LTPL). After annealing at 800degreesC for 30s, a blueshift of the LTPL peak energy for the SiO2-capped region is 25meV and that for the bare region is 0.8meV. The results can attribute to the nitrogen reorganization in the GaNAs/GaAs SQW. It is also shown that the nitrogen reorganization can be obviously enhanced by SiO2 cap-layer. A simple model is used to describe the SiO2-enhanced blueshift of the LTPL peak energy. The estimated activation energy of the N atomic reorganization for the samples annealing with and without SiO2 cap-layer are 2.9eV and 3.1eV, respectively.

Temperature-induced switching-over of the luminescence transitions in GaInNAs/GaAs quantum wells

Photoluminescence (PL) spectra of the GaInNAs/GaAs single quantum well (SQW) with different N compositions are carefully studied in a range of temperatures and excitation power densities. The anomalous S-shape temperature dependence of the PL peak is analysed based on the competition and switching-over between the peaks related to N-induced localized states and the peak related to interband excitonic recombination. It is found that with increasing N composition, the localized energy increases and the turning point of the S-shape temperature dependence occurs at higher temperature, where the localized carriers in the bandtail states obtain enough thermal activation energy to be dissociated and delocalized. The rapid thermal annealing (RTA) effectively reduces the localized energy and causes a decrease of the switching-over temperature.

Photoluminescence study of InGaN/GaN quantum dots grown on passivated GaN surface

We have measured photoluminescence (PL) and time-resolve photoluminescence (TRPL) from InGaN/GaN quantum dots (QDs) grown on passivated GaN surfaces by metalorganic chemical vapor deposition (MOCVD). Strong PL emission was observed from the QDs structure even at room temperature. By comparing the PL and TRPL dependence on temperature, a significant difference between the QD and wetting layer emissions was revealed. The QD emission is characterized by a strong exciton localization effect, which leads to a larger thermal activation energy, a nearly constant radiative lifetime independent of temperature and an unusual temperature behavior of the PL peak energy. (C) 2003 Elsevier B.V. All rights reserved.

Study on the thermal stability of InN by in-situ laser reflectance system

The thermal stability of InN in the growth environment in metalorganic chemical vapor deposition was systematically investigated in situ by laser reflectance system and ex situ by morphology characterization, X-ray diffraction and X-ray photoelectron spectroscopy. It was found that InN can withstand isothermal annealing at temperature as high as 600 degrees C in NH3 ambient. While in N-2 atmosphere, it will decompose quickly to form In-droplets at least at the temperature around 500 degrees C, and the activation energy of InN decomposition was estimated to be 2.1 +/- 0.1 eV. Thermal stability of InN when annealing in NH3 ambient during temperature altering would be very sensitive to ramping rate and NH3 flow rate, and InN would sustain annealing process at small ramping rate and sufficient supply of reactive nitrogen radicals. Whereas In-droplets formation was found to be the most frequently encountered phenomenon concerning InN decomposition, annealing window for conditions free of In-droplets was worked out and possible reasons related are discussed. In addition, InN will decompose in a uniform way in the annealing window, and the decomposition rate was found to be in the range of 50 and 100 nm/h. Hall measurement shows that annealing treatment in such window will improve the electrical properties of InN. (c) 2005 Elsevier B.V. All rights reserved.

Frequency dependence of junction capacitance of GaN p-i-n UV detectors

In this paper frequency dependence of small-signal capacitance of p-i-n UV detectors, which were fabricated on GaN grown on sapphire substrate by metalorganic chemical vapor deposition, has been studied. The Schibli-Milnes model was used to analyze the capacitance-frequency characteristics. According to high frequency C-V measurements, the deep level mean concentration is about 2.98 x 10(20) cm(-3). The deep level is caused by the un-ionised Mg dopant. The calculated Mg activation energy is 260 meV and the hole thermal capture cross section of the deep level is about 2.73 x 10(-22) cm(2). The applicability of the Schibli-Milnes model is also discussed when the concentration of deep levels exceeds that of the heavily doped n-side. It is concluded that the analytic expression of the Schibli-Milnes model can still be used to describe the capacitance-frequency characteristics of GaN p-i-n UV detectors in good agreement with experiment. (c) 2005 Elsevier Ltd. All rights reserved.

Deposition of p-type nc-SiC : H thin films with subtle carbon incorporation for applications in p-i-n solar cells

This paper presents a detailed study on the effects of carbon incorporation and substrate temperature on structural, optical, and electrical properties of p-type nanocrystalline amorphous silicon films. A p-nc-SiC: H thin film with optical gap of 1.92 eV and activation energy of 0.06 eV is obtained through optimizing the plasma parameters. By using this p-type window layer, single junction diphasic nc-SiC : H/a-Si : H solar cells have been successfully prepared with a V-oc of 0.94 eV.

Nanostructure in the p-layer and its impacts on amorphous silicon solar cells

The open circuit voltage (V-oc) of n-i-p type hydrogenated amorphous silicon (a-Si:H) solar cells has been examined by means of experimental and numerical modeling. The i- and p-layer limitations on V-oc are separated and the emphasis is to identify the impact of different kinds of p-layers. Hydrogenated protocrystalline, nanocrystalline and microcrystalline silicon p-layers were prepared and characterized using Raman spectroscopy, high resolution transmission electron microscopy (HRTEM), optical transmittance and activation energy of dark-conductivity. The n-i-p a-Si:H solar cells incorporated with these p-layers were comparatively investigated, which demonstrated a wide variation of V-oc from 1.042 V to 0.369 V, under identical i- and n-layer conditions. It is found that the nanocrystalline silicon (nc-Si:H) p-layer with a certain nanocrystalline volume fraction leads to a higher V-oc. The optimum p-layer material for n-i-p type a-Si:H solar cells is not found at the onset of the transition between the amorphous to mixed phases, nor is it associated with a microcrystalline material with a large grain size and a high volume fraction of crystalline phase. (c) 2006 Elsevier B.V. All rights reserved.

Heterojunction solar cells with n-type nanocrystalline silicon emitters on p-type c-Si wafers

Hydrogenated nanocrystalline silicon (nc-Si:H) n-layers have been used to prepare heterojunction solar cells on flat p-type crystalline silicon (c-Si) wafers. The nc-Si:H n-layers were deposited by radio-frequency (RF) plasma enhanced chemical vapor deposition (PECVD), and characterized using Raman spectroscopy, optical transmittance and activation energy of dark-conductivity. The nc-Si:H n-layers obtained comprise fine grained nanocrystallites embedded in amorphous matrix, which have a wider bandgap and a smaller activation energy. Heterojunction solar cells incorporated with the nc-Si n-layer were fabricated using configuration of Ag (100 nm)/1T0 (80 nm)/n-nc-Si:H (15 nm)/buffer a-Si:H/p-c-Si (300 mu m)/Al (200 nm), where a very thin intrinsic a-Si:H buffer layer was used to passivate the p-c-Si surface, followed by a hydrogen plasma treatment prior to the deposition of the thin nanocrystalline layer. The results show that heterojunction solar cells subjected to these surface treatments exhibit a remarkable increase in the efficiency, up to 14.1% on an area of 2.43 cm(2). (c) 2006 Elsevier B.V. All rights reserved.

Electrical properties of B-doped polycrystalline silicon thin films prepared by rapid thermal chemical vapour deposition

In this paper, about 30 mu m thick B-doped polycrystalline silicon (poly-Si) thin films were deposited on quartz substrates, n-type single crystalline silicon wafers and p(++)-type poly-Si ribbons by a rapid thermal chemical vapour deposition system in a temperature range from 1000 to 1150 degrees C. Activation energy measurement and room temperature/temperature dependent Hall effect measurement were performed on the poly-Si thin films prepared on the former two kinds of substrates, respectively. It seems that the electrical properties of as-prepared poly-Si thin films could be qualitatively explained by Seto's grain boundary (GB) trapping theory although there is a big difference between our samples and Seto's in gain size and film thickness etc. The experimental results reconfirm that GB itself is a kind of most effective recombination center with trapping level near the midgap and trapping state density in the order of 1012 cm(-2) magnitude. Electron beam induced current measurements on the poly-Si thin films prepared on the poly-Si ribbons also show that severe recombination occurs at the positions of GBs. (c) 2005 Elsevier B.V All rights reserved.

Photoluminescence of Mg-doped GaN grown by metalorganic chemical vapor deposition

Two Mg-doped GaN films with different doping concentrations were grown by a metalorganic chemical vapor deposition technique. Photoluminescence (PL) experiments were carried out to investigate the optical properties of these films. For highly Mg-doped GaN, the PL spectra at 10 K are composed of a blue luminescence (BL) band at 2.857 eV and two excitonic luminescence lines at 3.342 eV and 3.282 eV, in addition to a L2 phonon replica at 3.212 eV. The intensity of the L1 line decreases monotonously with an increase,in temperature. However, the intensity of the L2 line first slowly increases at first, and then decreases quickly with an increase in temperature. The two lines are attributed to bound excitonic emissions at extended defects. The BL band is most likely due to the transition from deep donor Mg-V-N complex to Mg shallow acceptor. From the temperature dependence of the luminescence peak intensity of the BL band, the activation energy of acceptor Mg was found to be 290 meV. (C) 2003 American Vacuum Society.

Study of GaN thin films grown on vicinal SiC (0001) substrates by molecular beam epitaxy

A detailed study of the characteristics of undoped GaN films, grown on either vicinal or nominal flat SiC (0001) substrates by molecular beam epitaxy, has been carried out using photoluminescence and Raman scattering techniques. The I I K photoluminescence spectra of the GaN film grown on the vicinal SiC (0001) substrate show a strong and sharp near-bandgap peak (full width at half maximum (FWHM) similar to 16 meV). This feature contrasts with that of the GaN film grown on the nominal flat SiC (0001) substrate where the I I K photoluminescence spectra exhibit the near-bandgap peak (FWHM similar to 25 meV) and the intensity is approximately seven times weaker than that of the vicinal film sample. The redshift of the near-bandgap peak associated with excitons bound to shallow donors is related to the stress caused by both the lattice mismatch and the thermal expansion coefficient difference between GaN and SiC substrates. The measured thermal activation energy of the shallow donor of 33.4 meV is determined by using an Arrhenius plot of the near-bandgap luminescence versus I IT from the slope of the graph at high temperature. The temperature dependence of the FWHM of the near-bandgap luminescence has also been studied. The Raman scattering measurements from the vicinal film reveal that the E-2 phonon peak is strengthened and the A(1)(LO) phonon peak is shifted towards the low-frequency side with enhanced intensity, in comparison to that from the nominal flat film, suggesting a reduction in the density of defects and a lower free carrier concentration in the vicinal GaN film.