Catalytic role of pre-adsorbed CO in platinum-based catalysts : the reduction of SO 2 by CO on Pt l Au m (CO) n

Using density functional theory, we have investigated the catalytic properties of bimetallic complex catalysts PtlAum(CO)n (l + m = 2, n = 1–3) in the reduction of SO2 by CO. Due to the strong coupling between the C-2p and metal 5d orbitals, pre-adsorption of CO molecules on the PtlAum is found to be very effective in not only reducing the activation energy, but also preventing poisoning by sulfur. As result of the coupling, the metal 5d band is broadened and down-shifted, and charge is transferred from the CO molecules to the PtlAum. As SO2 is adsorbed on the catalyst, partial charge moves to the anti-σ bonding orbitals between S and O in SO2, weakening the S–O bond strength. This effect is enhanced by pre-adsorbing up to three CO molecules, therefore the S–O bonds become vulnerable. Our results revealed the mechanism of the excellent catalytic properties of the bimetallic complex catalysts.

Catalytic reduction of SO2 by CO over Pt l Au m (CO) n: a first-principles investigation

The catalytic activities, to the reduction of SO2 by CO, of clusters PtlAum (l + m = 2) with or without preadsorbing CO molecules are investigated using first-principles density functional theory. We find that the PtAu(CO)n (n = 1–3) clusters show more excellent catalytic properties than either pure metallic catalysts. Preadsorption of CO to the catalysts could effectively avoid platinum-based catalyst sulfur poisoning; as more CO molecules preadsorbed to the catalysts, the energy barriers for the carbonyl sulfide (COS) molecule’s desorption from the catalyst are remarkably decreased. We propose an ideal catalytic cycle to simultaneously get rid of SO2 and CO over the catalysts PtAu(CO)3.

Low-temperature assembly of ordered carbon nanotip arrays in low-frequency, high-density inductively coupled plasmas

High-density inductively coupled plasma (ICP)-assisted self-assembly of the ordered arrays of various carbon nanostructures (NS) for the electron field emission applications is reported. Carbon-based nano-particles, nanotips, and pyramid-like structures, with the controllable shape, ordering, and areal density are grown under remarkably low process temperatures (260-350 °C) and pressures (below 0.1 Torr), on the same Ni-based catalyst layers, in a DC bias-controlled floating temperature regime. A high degree of positional and directional ordering, elevated sp2 content, and a well-structured graphitic morphology are achieved without the use of pre-patterned or externally heated substrates.

Synthesis and characterization of ternary AL-C-N compound

Efficient hydrogenated diamond-like carbon (DLC) film deposition in a plasma reactor that features both the capacitive and inductively coupled operation regimes is reported. The hydrogenated DLC films have been prepared on silicon wafers using a low-frequency (500 kHz) inductively coupled plasma (LF ICP) chemical vapor deposition (CVD) system. At low RF powers, the system operates as an asymmetric capacitively coupled plasma source, and the film deposition process is undertaken in the electrostatic (E) discharge regime. The films deposited in the electrostatic mode feature graphite-like structure. Above the mode transition threshold, the high-density inductively coupled plasma is produced in the electromagnetic (H) discharge regime. Raman spectrometry suggests the possibility to control relative proportions of sp2 and sp3 hybridized carbon. Variation of the DC substrate bias results in dramatic modification of the film structure from the polymeric (unbiased substrates) to the diamond-like (optimized bias). It has been shown that the deposition rate and hardness of the DLC film are much higher in the H-mode deposition regime. For a 20 m Torr H-mode CH4+Ar gas mixture discharge, the DLC film exhibits mechanical hardness of 18 GPa, Young's modulus of 170 GPa, and compressive stress of 1.3 GPa.

Characterization of a DC-driven microplasma between a capillary tube and water surface

A microplasma generated between a stainless-steel capillary and water surface in ambient air with flowing argon as working gas appears as a bright spot at the tube orifice and expands to form a larger footprint on the water surface, and the dimensions of the bell-shaped microplasma are all below 1 mm. The electron density of the microplasma is estimated to be ranging from 5.32 × 109 cm−3 to 2.02 × 1014 cm−3 for the different operating conditions, which is desirable for generating abundant amounts of reactive species. A computational technique is adopted to fit the experimental emission from the N2 second positive system with simulation results. It is concluded that the vibrational temperature (more than 2000 K) is more than twice the gas temperature (more than 800 K), which indicates the non-equilibrium state of the microplasma. Both temperatures showed dependence on the discharge parameters (i.e., gas flow and discharge current). Such a plasma device could be arranged in arrays for applications utilizing plasmainduced liquid chemistry.

Mitigation of harmonics of DFIGs in DC-Microgrids

During the last few years, there has been an increased attention paid on the developments of DC microgrids (DCMGs) and their applications. For economical and more flexible wind power generation, doubly fed induction generator (DFIG) is regarded as a most commonly used generator in wind farms. This paper presents a configuration and operation method for a DCMG connected with DFIGs, in which the controller of the DFIG is designed for maximum power point tracking (MPPT). The generation of harmonics and their effects on the generator in this configuration are analyzed and a harmonic compensation method is proposed. Furthermore, the simulation results are presented to show that the DFIG can be operated effectively in DCMGs and harmonic currents can be reduced.

Nitrous oxide emissions from fertilized, irrigated cotton (Gossypium hirsutum L.) in the Aral Sea Basin, Uzbekistan : influence of nitrogen applications and irrigation practices

Nitrous oxide emissions were monitored at three sites over a 2-year period in irrigated cotton fields in Khorezm, Uzbekistan, a region located in the arid deserts of the Aral Sea Basin. The fields were managed using different fertilizer management strategies and irrigation water regimes. N2O emissions varied widely between years, within 1 year throughout the vegetation season, and between the sites. The amount of irrigation water applied, the amount and type of N fertilizer used, and topsoil temperature had the greatest effect on these emissions. Very high N2O emissions of up to 3000 μg N2O-N m−2 h−1 were measured in periods following N-fertilizer application in combination with irrigation events. These “emission pulses” accounted for 80–95% of the total N2O emissions between April and September and varied from 0.9 to 6.5 kg N2O-N ha−1.. Emission factors (EF), uncorrected for background emission, ranged from 0.4% to 2.6% of total N applied, corresponding to an average EF of 1.48% of applied N fertilizer lost as N2O-N. This is in line with the default global average value of 1.25% of applied N used in calculations of N2O emissions by the Intergovernmental Panel on Climate Change. During the emission pulses, which were triggered by high soil moisture and high availability of mineral N, a clear diurnal pattern of N2O emissions was observed, driven by daily changes in topsoil temperature. For these periods, air sampling from 8:00 to 10:00 and from 18:00 to 20:00 was found to best represent the mean daily N2O flux rates. The wet topsoil conditions caused by irrigation favored the production of N2O from NO3− fertilizers, but not from NH4+ fertilizers, thus indicating that denitrification was the main process causing N2O emissions. It is therefore argued that there is scope for reducing N2O emission from irrigated cotton production; i.e. through the exclusive use of NH4+ fertilizers. Advanced application and irrigation techniques such as subsurface fertilizer application, drip irrigation and fertigation may also minimize N2O emission from this regionally dominant agro-ecosystem.

Ectopic overexpression of a mungbean vacuolar Na+/H+ antiporter gene (VrNHX1) leads to increased salinity stress tolerance in transgenic Vigna unguiculata L. Walp

Salinity is a major threat to sustainable agriculture worldwide. Plant NHX exchangers play an important role in conferring salt tolerance under salinity stress. In this study, a vacuolar Na+/H+ antiporter gene VrNHX1 (Genbank Accession No. JN656211.1) from mungbean (Vigna radiata) was introduced into cowpea (Vigna unguiculata) by the Agrobacterium tumefaciens-mediated transformation method. Polymerase chain reaction and Southern blot hybridization confirmed the stable integration of VrNHX1 into the cowpea genome. Comparative expression analysis by semi-quantitative RT-PCR revealed higher expression of VrNHX1 in transgenic cowpea plants than wild-type. Under salt stress conditions, T2 transgenic 35S:VrNHX1 cowpea lines exhibited higher tolerance to 200 mM NaCl treatment than wild-type. Furthermore, T2 transgenic 35S:VrNHX1 lines maintained a higher K+/Na+ ratio in the aerial parts under salt stress and accumulated higher [Na+] in roots than wild-type. Physiological analysis revealed lower levels of lipid peroxidation, hydrogen peroxide and oxygen radical production but higher levels of relative water content and proline, ascorbate and chlorophyll contents in T2 transgenic 35S:VrNHX1 lines.

A novel dc-link voltage regulation method for single source hybrid multilevel inverters

This paper presents a novel dc-link voltage regulation technique for a hybrid inverter system formed by cascading two 3-level inverters. The two inverters are named as “bulk inverter” and “conditioning inverter”. For the hybrid system to act as a nine level inverter, conditioning inverter dc link voltage should be maintained at one third of the bulk inverter dc link voltage. Since the conditioning inverter is energized by two series connected capacitors, dc-link voltage regulation should be carried out by controlling the capacitor charging/discharging times. A detailed analysis of conditioning inverter capacitor charging/discharging process and a simplified general rule, derived from the analysis, are presented in this paper. Time domain simulations were carried out to demonstrate efficacy of the proposed method on regulating the conditioning inverter dc-link voltage under various operating conditions.

Biolistic transformation of elite indica rice (Oryza sativa L.) cultivars through semi-solid and liquid medium selection systems

Following microprojectile mediated delivery of a plasmid construct (pAHC-25) encoding bar (bialophos resistance) gene into five-day-old scutellar calli derived from mature embryos, the effectiveness of selection procedure for bar-gene expressing tissue was compared for two indica rice cultivars (IR-64 and Karnal Local). While IR-64 transformants could be selected through the generally used semi-solid selection medium, the same procedure was not effective in the basmati cultivar Karnal Local. In the latter case, while lower concentrations (2–4 mg 1−1) of the selective agent phosphinothricin (PPT) yielded only escapes, higher concentrations (6–8 mg l���1) inhibited proliferation of transformed as well as untransformed sectors. For Karnal Local, a liquid medium based selection system was successfully utilized for recovering transformed sectors and, eventually, regenerants. The study demonstrates the generation of transformants of two elite indica cultivars using the environment-independent system of mature embryos from seeds.

Author response to : Brough et al. in response to the recently published article : Lottering,N., MacGregor,D.M.,Barry,M.D.,Reynolds,M.S., Gregory,L.S., 2014. Introducing standardized protocols for anthropological measurement of virtual sub-adult crania using computed tomography 2(1),34–38

Firstly, we would like to thank Ms. Alison Brough and her colleagues for their positive commentary on our published work [1] and their appraisal of our utility of the “off-set plane” protocol for anthropometric analysis. The standardized protocols described in our manuscript have wide applications, ranging from forensic anthropology and paleodemographic research to clinical settings such as paediatric practice and orthopaedic surgical design. We affirm that the use of geometrically based reference tools commonly found in computer aided design (CAD) programs such as Geomagic Design X® are imperative for more automated and precise measurement protocols for quantitative skeletal analysis. Therefore we stand by our recommendation of the use of software such as Amira and Geomagic Design X® in the contexts described in our manuscript...

Synthesis and toxicological evaluation of a chitosan‑L���leucine conjugate for pulmonary drug delivery applications

Herein are reported the synthesis of a conjugate of chitosan with L-leucine, the preparation of nanoparticles from both chitosan and the conjugate for use in pulmonary drug delivery, and the in vitro evaluation of toxicity and inflammatory effects of both the polymers and their nanoparticles on the bronchial epithelial cell line, BEAS-2B. The nanoparticles, successfully prepared both from chitosan and the conjugate, had a diameter in the range of 10−30 nm. The polymers and their nanoparticles were tested for their effects on cell viability by MTT assay, on trans-epithelial permeability by using sodium fluorescein as a fluid phase marker, and on IL-8 secretion by ELISA. The conjugate nanoparticles had a low overall toxicity (IC50 = 2 mg/mL following 48 h exposure; no induction of IL-8 release at 0.5 mg/mL concentration), suggesting that they may be safe for pulmonary drug delivery applications.

Pharmacokinetics and tumor disposition of PEGylated, methotrexate conjugated poly-l-lysine dendrimers

Dendrimers have potential for delivering chemotherapeutic drugs to solid tumours via the enhanced permeation and retention (EPR) effect. The impact of conjugation of hydrophobic anticancer drugs to hydrophilic PEGylated dendrimer surfaces, however, has not been fully investigated. The current study has therefore characterised the effect on dendrimer disposition of conjugating α-carboxyl protected methotrexate (MTX) to a series of PEGylated 3H-labelled poly-L-lysine dendrimers ranging in size from generation 3 (G3) to 5 (G5) in rats. Dendrimers contained 50% surface PEG and 50% surface MTX. Conjugation of MTX generally increased plasma clearance when compared to conjugation with PEG alone. Conversely, increasing generation reduced clearance, increased metabolic stability and reduced renal elimination of the administered radiolabel. For constructs with molecular weights >20 kDa increasing the molecular weight of conjugated PEG also reduced clearance and enhanced metabolic stability but had only a minimal effect on renal elimination. Tissue distribution studies revealed retention of MTX conjugated smaller (G3-G4) PEG570 dendrimers (or their metabolic products) in the kidneys. In contrast, the larger G5 dendrimer was concentrated more in the liver and spleen. The G5 PEG1100 dendrimer was also shown to accumulate in solid Walker 256 and HT1080 tumours and comparative disposition data in both rats (1 to 2% dose/g in tumour) and mice (11% dose/g in tumour) are presented. The results of this study further illustrate the potential utility of biodegradable PEGylated poly-L-lysine dendrimers as long circulating vectors for the delivery and tumour-targeting of hydrophobic drugs.

Circulating fragments of N-Terminal Pro-B-Type Natriuretic Peptides in plasma of heart failure patients

BACKGROUND: The use of nonstandardized N-terminal pro-B-type natriuretic peptide (NT-proBNP) assays can contribute to the misdiagnosis of heart failure (HF). Moreover, there is yet to be established a common consensus regarding the circulating forms of NT-proBNP being used in current assays. We aimed to characterize and quantify the various forms of NT-proBNP in the circulation of HF patients. METHODS: Plasma samples were collected from HF patients (n = 20) at rest and stored at -80 degrees C. NT-proBNP was enriched from HF patient plasma by use of immunoprecipitation followed by mass spectrometric analysis. Customized homogeneous sandwich AlphaLISA (R) immunoassays were developed and validated to quantify 6 fragments of NT-proBNP. RESULTS: Mass spectrometry identified the presence of several N- and C-terminally processed forms of circulating NT-proBNP, with physiological proteolysis between Pro2-Leu3, Leu3-Gly4, Pro6-Gly7, and Pro75-Arg76. Consistent with this result, AlphaLISA immunoassays demonstrated that antibodies targeting the extreme N or C termini measured a low apparent concentration of circulating NT-proBNP. The apparent circulating NT-proBNP concentration was increased with antibodies targeting nonglycosylated and nonterminal epitopes (P < 0.05). CONCLUSIONS: In plasma collected from HF patients, immunoreactive NT-proBNP was present as multiple N- and C-terminally truncated fragments of the full length NT-proBNP molecule. Immunodetection of NT-proBNP was significantly improved with the use of antibodies that did not target these terminal regions. These findings support the development of a next generation NT-proBNP assay targeting nonterminal epitopes as well as avoiding the central glycosylated region of this molecule. (c) 2013 American Association for Clinical Chemistry