Boron and nitrogen functionalized diamondoids: A first principles investigation

Chemically functionalized adamantane molecules have been investigated by first principles total energy calculations. Boron and nitrogen functionalized molecules were found to be very stable, consistent with available experimental data. Two hypothetical molecular crystals, involving functionalized adamantane, were investigated. These molecular crystals presented direct electronic bandgaps and large bulk moduli, which suggested a possible road for molecular self-assembly using functionalized diamondoids. (C) 2010 Elsevier B.V. All rights reserved.

Anodic stripping voltammetric determination of copper(II) using a functionalized carbon nanotubes paste electrode modified with crosslinked chitosan

The development and application of a functionalized carbon nanotubes paste electrode (CNPE) modified with crosslinked chitosan for determination of Cu(II) in industrial wastewater, natural water and human urine samples by linear scan anodic stripping voltammetry (LSASV) are described. Different electrodes were constructed using chitosan and chitosan crosslinked with glutaraldehyde (CTS-GA) and epichlorohydrin (CTS-ECH). The best voltammetric response for Cu(II) was obtained with a paste composition of 65% (m/m) of functionalized carbon nanotubes, 15% (m/m) of CTS-ECH, and 20% (m/m) of mineral oil using a solution of 0.05 mol L(-1) KNO(3) with pH adjusted to 2.25 with HNO(3), an accumulation potential of 0.3V vs. Ag/AgCl (3.0 mol L(-1) KCl) for 300 s and a scan rate of 100 mV s(-1). Under these optimal experimental conditions, the voltammetric response was linearly dependent on the Cu(II) concentration in the range from 7.90 x 10(-8) to 1.60 x 10(-5) mol L(-1) with a detection limit of 1.00 x 10(-8) mol L(-1). The samples analyses were evaluated using the proposed sensor and a good recovery of Cu(II) was obtained with results in the range from 98.0% to 104%. The analysis of industrial wastewater, natural water and human urine samples obtained using the proposed CNPE modified with CTS-ECH electrode and those obtained using a comparative method are in agreement at the 95% confidence level. (C) 2009 Elsevier B. V. All rights reserved.

Dynamics of Dissolved Forms of Carbon and Inorganic Nitrogen in Small Watersheds of the Coastal Atlantic Forest in Southeast Brazil

Based on the fact that streamwater quality reflects landscape conditions, the objectives of this study were: to investigate nitrogen (N), carbon (C), and major ion concentrations in six streams crossing minimally disturbed Atlantic Forest areas, with similar geomorphological characteristics; to determine N and C fluxes in one of these pristine streams (Indaia); and assess the impact of human activity on the biogeochemistry of two other streams in the same region, crossing urbanized areas. The distribution pattern of carbon and inorganic nitrogen dissolved forms, as well as the major ion and biogenic gas concentrations in the streamwater, was similar in pristine streams, indicating that the C and N dynamics were determined by influence of some factors, such as climate, atmospheric deposition, geology, soil type, and land covering, which were analogous in the forested watersheds. The urban streams were significantly different from the pristine streams, showing low dissolved oxygen concentrations, high respiration rates, and high concentrations of carbon dioxide, dissolved inorganic nitrogen, dissolved inorganic carbon, and major ion. These differences were attributed to anthropogenic impact on water quality, especially domestic sewage discharge. Additionally, in the Indaia stream, it was possible to observe the importance of rainfall over temporal dynamics of dissolved carbon forms, and also, the obtained specific flux of dissolved inorganic nitrogen was relatively elevated (approximately 11 kg ha(-1) year(-1)). These results reveal the influence of human activity over the biogeochemistry of coastal streams and also indicate the importance N export of Atlantic Forest to the ocean.

Functionalized adamantane: Building blocks for nanostructure self-assembly

We report first-principles calculations on the electronic and structural properties of chemically functionalized adamantane molecules, either in isolated or crystalline forms. Boron and nitrogen functionalized molecules, aza-, tetra-aza-, bora-, and tetra-bora-adamantane, were found to be very stable in terms of energetics, consistent with available experimental data. Additionally, a hypothetical molecular crystal in a zincblende structure, involving the pair tetra-bora-adamantane and tetra-aza-adamantane, was investigated. This molecular crystal presented a direct and large electronic band gap and a bulk modulus of 20 GPa. The viability of using those functionalized molecules as fundamental building blocks for nanostructure self-assembly is discussed.

Spin filtering and disorder-induced magnetoresistance in carbon nanotubes: Ab initio calculations

Nitrogen-doped carbon nanotubes can provide reactive sites on the porphyrin-like defects. It is well known that many porphyrins have transition-metal atoms, and we have explored transition-metal atoms bonded to those porphyrin-like defects inN-doped carbon nanotubes. The electronic structure and transport are analyzed by means of a combination of density functional theory and recursive Green's function methods. The results determined the heme B-like defect (an iron atom bonded to four nitrogens) is the most stable and has a higher polarization current for a single defect. With randomly positioned heme B defects in nanotubes a few hundred nanometers long, the polarization reaches near 100%, meaning they are effective spin filters. A disorder-induced magnetoresistance effect is also observed in those long nanotubes, and values as high as 20 000% are calculated with nonmagnectic eletrodes.

Realistic calculations of carbon-based disordered systems

Carbon nanotubes rank amongst potential candidates for a new family of nanoscopic devices, in particular for sensing applications. At the same time that defects in carbon nanotubes act as binding sites for foreign species, our current level of control over the fabrication process does not allow one to specifically choose where these binding sites will actually be positioned. In this work we present a theoretical framework for accurately calculating the electronic and transport properties of long disordered carbon nanotubes containing a large number of binding sites randomly distributed along a sample. This method combines the accuracy and functionality of ab initio density functional theory to determine the electronic structure with a recursive Green`s functions method. We apply this methodology on the problem of nitrogen-rich carbon nanotubes, first considering different types of defects and then demonstrating how our simulations can help in the field of sensor design by allowing one to compute the transport properties of realistic nanotube devices containing a large number of randomly distributed binding sites.

Designing real nanotube-based gas sensors

Using a combination of density functional theory and recursive Green's functions techniques, we present a full description of a large scale sensor, accounting for disorder and different coverages. Here, we use this method to demonstrate the functionality of nitrogen-rich carbon nanotubes as ammonia sensors as an example. We show how the molecules one wishes to detect bind to the most relevant defects on the nanotube, describe how these interactions lead to changes in the electronic transport properties of each isolated defect, and demonstrate that there are significative resistance changes even in the presence of disorder, elucidating how a realistic nanosensor works.

Ex Vivo Lung Perfusion: Early Report of Brazilian Experience

Introduction. Only about 15% of the potential candidates for lung donation are considered suitable for transplantation. A new method for ex vivo lung perfusion (EVLP) can be used to evaluate and recondition ""marginal,"" nonacceptable lungs. We have herein described an initial experience with ex vivo perfusion of 8 donor lungs deemed nonacceptable. Materials and Methods. After harvesting, the lungs were perfused ex vivo with Steen Solution, an extracellular matrix with high colloid osmotic pressure. A membrane oxygenator connected to the circuit received gas from a mixture of nitrogen and carbon dioxide, maintaining a normal mixed venous blood gas level in the perfusate. The lungs were gradually rewarmed, reperfused, and ventilated for evaluation through analyses of oxygenation capacity, pulmonary vascular resistance (PVR), lung compliance (LC), and biopsy. Results. The arterial oxygen pressure (with inspired oxygen fraction of 100%) increased from a mean of 206 mm Hg in the organ donor at the referring hospital to a mean of 498 mm Hg during the ex vivo evaluation. After 1 hour of EVLP, PVR varied from 440-1454 dynes/sec/cm(5); LC was in the range of 26-90 mL/cmH(2)O. There was no histological deterioration after 10 hours of cold ischemia and 1 hour of EVLP. Conclusions. The ex vivo evaluation model can improve oxygenation capacity of ""marginal"" lungs rejected for transplantation. It has great potential to increase lung donor availability and, possibly, reduce time on the waiting list.

Chemical abundance analysis of the Be star HD 171054

In this work the results of a spectroscopic study of the southern field narrow-line Be star HD 171054 are presented. High dispersion and signal-to-noise ratio spectra allowed the estimation of the fundamental photospheric parameters such as the projected rotational velocity, effective temperature and superficial gravity from non-LTE stellar atmosphere models. From these parameters and microturbulence, the abundances of He, C, N, O, Mg, Al and Si for this object are estimated. Results show that C is depleted whereas N is overabundant compared with the sun and OB stars in the solar vicinity. Oxygen and helium are close to the solar value. Magnesium is down by 0.43 dex and aluminium and silicon are overabundant. (C) 2010 Elsevier B.V. All rights reserved.

Isotopic view of vegetation and carbon and nitrogen cycles in a cerrado ecosystem, southeastern Brazil

Carbon and nitrogen biogeochemical cycles in savannas are strongly regulated by the seasonal distribution of precipitation and pulses of nutrients released during the wetting of the dry soil and are critical to the dynamics of microorganisms and vegetation. The objective of this study was to investigate the spatial and temporal variability of C and N isotope ratios as indicators of the cycling of these elements in a cerrado sensu stricto area, within a protected area in a State Park in the state of São Paulo, Brazil. The foliar δ13C and δ15N values varied from -33.6 to -24.4 ‰ and -2.5 to 4.5 ‰, respectively. The δ13C values showed a consistent relationship with canopy height, revealing the importance of structure of the canopy over the C isotopic signature of the vegetation. Carbon isotopic variations associated with the length of the dry season indicated the importance of recent fixed C to the integrated isotopic signature of the leaf organic C. The studied Cerrado species showed a depleted foliar δ15N, but a wide range of foliar Nitrogen with no difference among canopy heights. However, seasonal variability was observed, with foliar δ15N values being higher in the transition period between dry and rainy seasons. The variation of the foliar C and N isotope ratios presented here was consistent with highly diverse vegetation with high energy available but low availability of water and N.

Stable isotopes of bulk organic matter to trace carbon and nitrogen dynamics in an estuarine ecosystem in Babitonga Bay (Santa Catarina, Brazil)

The biogeochemical processes affecting the transport and cycling of terrestrial organic carbon in coastal and transition areas are still not fully understood One means of distinguishing between the sources of organic materials contributing to particulate organic matter (POM) in Babitonga Bay waters and sediments is by the direct measurement of delta(13)C of dissolved inorganic carbon (DIC) and delta(13)C and delta(15)N in the organic constituents. An isotopic survey was taken from samples collected in the Bay in late spring of 2004. The results indicate that the delta(13)C and delta(15)N compositions of OM varied from -21.7 parts per thousand to -26 2 parts per thousand. and from + 9 2 parts per thousand. to -0 1 parts per thousand, respectively. delta(13)C from DIC ranges from +0.04 parts per thousand to -12.7 parts per thousand The difference in the isotope compositions enables the determination of three distinct end-members terrestrial, marine and urban Moreover, the evaluation of source contribution to the particulate organic matter (POM) in the Bay, enables assessment of the anthropogenic impact. Comparing the depleted values of delta(13)C(DIC) and delta(13)C(POC) it is possible to further understand the carbon dynamic within Babitonga Bay (C) 2010 Elsevier BV All rights reserved

Frozen Chicken for Wild Fish: Nutritional Transition in the Brazilian Amazon Region Determined by Carbon and Nitrogen Stable Isotope Ratios in Fingernails

Objectives: Amazonian populations are experiencing dietary changes characteristic of the nutrition transition. However, the degree of change appears to vary between urban and rural settings. To investigate this process, we determined carbon and nitrogen stable isotope ratios in fingernails and dietary intake of Amazonian populations living along a rural to urban continuum along the Solimoes River in Brazil. Methods: Carbon and nitrogen stable isotope ratios were analyzed from the fingernails of 431 volunteer subjects living in different settings ranging from rural villages, small towns to urban centers along the Solimoes River. Data from 200 dietary intake surveys were also collected using food frequency questionnaires and 24-h recall interviews in an effort to determine qualitative aspects of diet composition. Results: Fingernail delta(13)C values (mean standard deviation) were -23.2 +/- 1.3, 20.2 +/- 1.5, and 17.4 +/- 1.3 parts per thousand and delta(15)N values were 11.8 +/- 0.6, 10.4 +/- 0.8, and 10.8 +/- 0.7 parts per thousand for those living in rural villages, small towns, and major cities, respectively. We found a gradual increase in the number of food items derived from C(4) plant types (meat and sugar) and the replacement of food items derived from C(3) plant types (fish and manioc flour) with increasing size of urban centers. Conclusion: Increasing urbanization in the Brazilian Amazon is associated with a significant change in food habits with processed and industrialized products playing an increasingly important role in the diet and contributing to the nutrition transition in the region. Am. J. Hum. Biol. 23:642-650, 2011. (C) 2011 Wiley-Liss, Inc.

Nitrogen removal in a sequencing batch biofilm reactor with liquid circulation: Effect of feed strategy and carbon source in the denitrifying step

Ammonium nitrogen removal from a synthetic wastewater by nitrification and denitrification processes were performed in a sequencing batch biofilm reactor containing immobilized biomass on polyurethane foam with circulation of the liquid-phase. It was analyzed the effect of four external carbon sources (ethanol, acetate, carbon synthetic medium and methanol) acting as electron donors in the denitrifying process. The experiments were conducted with intermittent aeration and operated at 30+/-1 degrees C in 8-h cycles. The synthetic wastewater (100 mgCOD/L and 50 mgNH(4)(+)-N/L) was added batch-wise, while the external carbon sources were added fed-batch-wise during the periods where aeration was suspended. Ammonium nitrogen removal efficiencies obtained were 95.7, 94.3 and 97.5% for ethanol, acetate and carbon synthetic medium, respectively. As to nitrite, nitrate and ammonium nitrogen effluent concentrations, the results obtained were, respectively: 0.1, 5.7 and 1.4 mg/L for ethanol; 0.2, 4.1 and 1.8 mg/L for acetate and 0.2, 6.7 and 0.8 for carbon synthetic medium. On the other hand using methanol, even at low concentrations (50% of the stoichiometric value calculated for complete denitrification), resulted in increasing accumulation of nitrate and ammonium nitrogen in the effluent over time.

BIOLOGICAL NITROGEN REMOVAL OVER NITRITATION/DENITRITATION USING PHENOL AS CARBON SOURCE

A laboratory scale activated sludge sequencing batch reactor was operated in order to obtain total removal of influent ammonia (200; 300 and 500 mg NH(3)-N.L(-1)) with sustained nitrite accumulation at the end of the aerobic stages with phenol (1,000 mg C(6)H(5)OH.L(-1)) as the carbon source for denitrifying microorganisms during the anoxic stages. Ammonia removal above 95% and ratios of (NO(2)(-)-N / (NO(2)(-)-N + NO(3)(-)-N)) ranging from 89 to 99% were obtained by controlling the dissolved oxygen concentration (1.0 mg O(2).L(-1)) and the pH value of 8.3 during the aerobic stages. Phenol proved to be an adequate source of carbon for nitrogen removal via nitrite with continuous feeding throughout part of the anoxic stage. Nitrite concentrations greater than 70.0 mg NO(2)(-)-N.L(-1) inhibited the biological denitritation process.

Carbon and nitrogen cycling in a tropical Brazilian soil cropped with sugarcane and irrigated with wastewater

Carbon (C) and nitrogen (N) dynamics in agro-systems can be altered as a consequence of treated sewage effluent (TSE) irrigation. The present study evaluated the effects of TSE irrigation over 16 months on N concentrations in sugarcane (leaves, stalks and juice), total soil carbon (TC), total soil nitrogen (TN), NO(3)(-)-N in soil and nitrate (NO(3)(-)) and dissolved organic carbon (DOC) in soil solution. The soil was classified as an Oxisol and samplings were carried out during the first productive crop cycle, from February 2005 (before planting) to September 2006 (after sugarcane harvest and 16 months of TSE irrigation). The experiment was arranged in a complete block design with five treatments and four replicates. Irrigated plots received 50% of the recommended mineral N fertilization and 100% (T100), 125% (T125), 150% (T150) and 200% (T200) of crop water demand. No mineral N and irrigation were applied to the control plots. TSE irrigation enhanced sugarcane yield but resulted in total-N inputs(804-1622 kg N ha(-1)) greater than exported N (463-597 kg N ha(-1)). Hence, throughout the irrigation period, high NO(3)(-) concentrations (up to 388 mg L(-1) at T200) and DOC (up to 142 mg L(-1) at T100) were measured in soil solution below the root zone, indicating the potential of groundwater contamination. TSE irrigation did not change soil TC and TN. (C) 2009 Elsevier B.V. All rights reserved.