C60 in Water: Aggregation Characterization, Reactivity and Behavior

Industrial scale production, coupled with unique material properties, underpin rising concerns of nano-scale materials inadvertently impacting the health and function of natural systems. Fullerenes, C60 in particular, have been proposed for a variety of applications and are soon expected to be produced in multi-ton quantities. Understanding how these materials behave in natural matrixes, specifically aqueous systems, is needed for accurate risk assessment and to manage waste disposal practices appropriately. Research presented here addresses outstanding questions and expands upon current knowledge regarding C60 nano-scale aggregation in water (nano-C60). Four areas of focus are: 1.) Aggregate formation, composition, and stability 2.) Reactivity with a dissolved reactant (ozone) 3.) Association with mineral surfaces and 4.) Interaction with selected biological systems. Results indicate that aggregates are crystalline in order and remain as underivatized C60 throughout the formation/stabilization process. The aggregate suspensions readily react with dissolved ozone resulting in a molecularly soluble, highly oxidized fullerene. Furthermore, nano-C60 associates with mineral surfaces as a function of surface charge and is observed to accumulate at the cell wall of a fungal culture. Taken together, results indicate that nano-scale, fullerene aggregates must be considered appropriately, as they deviate from predictions based on bulk and molecular property estimates

Protective Effects of the Launch/Entry Suit (LES) and the Liquid Cooling Garment(LCG) During Re-entry and Landing After Spaceflight

Heart rate and arterial pressure were measured during shuttle re-entry, landing and initial standing in crewmembers with and without inflated anti-g suits and with and without liquid cooling garments (LCG). Preflight, three measurements were obtained seated, then standing. Prior to and during re-entry, arterial pressure and heart rate were measured every five minutes until wheels stop (WS). Then crewmembers initiated three seated and three standing measurements. In subjects without inflated anti-g suits, SBP and DBP were significantly lower during preflight standing (P = 0.006; P = 0.001 respectively) and at touchdown (TD) (P = 0.001; P = 0.003 respectively); standing SBP was significantly lower after WS. on-LeG users developed significantly higher heart rates during re-entry (P = 0.029, maxG; P = 0.05, TD; P = 0.02, post-WS seated; P = 0.01, post-WS standing) than LCG users. Our data suggest that the anti-g suit is effective, but the combined anti-g suit with LCG is more effective

Measuring the Grafting Density of Nanoparticles in Solution by Analytical Ultracentrifugation and Total Organic Carbon Analysis

Many of the solution phase properties of nanoparticles, such as their colloidal stability and hydrodynamic diameter, are governed by the number of stabilizing groups bound to the particle surface (i.e., grafting density). Here, we show how two techniques, analytical ultracentrifugation (AUC) and total organic carbon analysis (TOC), can be applied separately to the measurement of this parameter. AUC directly measures the density of nanoparticle–polymer conjugates while TOC provides the total carbon content of its aqueous dispersions. When these techniques are applied to model gold nanoparticles capped with thiolated poly(ethylene glycol), the measured grafting densities across a range of polymer chain lengths, polymer concentrations, and nanoparticle diameters agree to within 20%. Moreover, the measured grafting densities correlate well with the polymer content determined by thermogravimetric analysis of solid conjugate samples. Using these tools, we examine the particle core diameter, polymer chain length, and polymer solution concentration dependence of nanoparticle grafting densities in a gold nanoparticle–poly(ethylene glycol) conjugate system

Real-Time Measurements of Engine-Out Trace Elements: Application of a Novel Soot Particle Aerosol Mass Spectrometer for Emissions Characterization

Lubricant-derived trace element emissions are the largest contributors to the accumulation of incombustible ash in diesel particulate filters (DPF), eventually leading to filter plugging and an increase in engine fuel consumption. Particulate trace element emissions also pose adverse health effects and are the focus of increasingly stringent air quality regulations. To date, the rates and physical and chemical properties of lubricant-derived additive emissions are not well characterized, largely due to the difficulties associated with conducting the measurements. This work investigated the potential for conducting real-time measurements of lubricant-derived particle emissions. The experiment used the Soot Particle Aerosol Mass Spectrometer (SP-AMS) developed by Aerodyne Research to measure the size, mass and composition of submicron particles in the exhaust. Results confirm the ability of the SP-AMS to measure engine-out emissions of calcium, zinc, magnesium, phosphorous, and sulfur. Further, emissions of previously difficult to detect elements, such as boron, and low-level engine wear metals, such as lead, were also measured. This paper provides an overview of the results obtained with the SP-AMS, and demonstrates the utility of applying real-time techniques to engine-out and tailpipe-out trace element emissions. Application of the SP-AMS for engine exhaust characterization followed a two-part approach: (1) measurement validation, and (2) measurement of engine-out exhaust. Measurement validation utilized a diesel burner with precise control of lubricant consumption. Results showed a good correlation between CJ-4 oil consumption and measured levels of lubricant-derived trace elements in the particle phase. Following measurement validation, the SP-AMS measured engine-out emissions from a medium-duty diesel engine, operated over a standard speed/load matrix. This work demonstrates the utility of state-of-the-art online techniques (such as the SP-AMS) to measure engine-out emissions, including trace species derived from lubricant additives. Results help optimize the combined engine-lubricant-aftertreatment system and provide a real-time characterization of emissions. As regulations become more stringent and emission controls more complex, advanced measurement techniques with high sensitivity and fast time response will become an increasingly important part of engine characterization studies.United States. Environmental Protection Agency (Grant RD834560

Elemental ratio measurements of organic compounds using aerosol mass spectrometry: characterization, improved calibration, and implications

Elemental compositions of organic aerosol (OA) particles provide useful constraints on OA sources, chemical evolution, and effects. The Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) is widely used to measure OA elemental composition. This study evaluates AMS measurements of atomic oxygen-to-carbon (O : C), hydrogen-to-carbon (H : C), and organic mass-to-organic carbon (OM : OC) ratios, and of carbon oxidation state ([bar over OS][subscript C]) for a vastly expanded laboratory data set of multifunctional oxidized OA standards. For the expanded standard data set, the method introduced by Aiken et al. (2008), which uses experimentally measured ion intensities at all ions to determine elemental ratios (referred to here as "Aiken-Explicit"), reproduces known O : C and H : C ratio values within 20% (average absolute value of relative errors) and 12%, respectively. The more commonly used method, which uses empirically estimated H[subscript 2]O[superscript +] and CO[superscript +] ion intensities to avoid gas phase air interferences at these ions (referred to here as "Aiken-Ambient"), reproduces O : C and H : C of multifunctional oxidized species within 28 and 14% of known values. The values from the latter method are systematically biased low, however, with larger biases observed for alcohols and simple diacids. A detailed examination of the H[subscript 2]O[superscript +], CO[superscript +], and CO[subscript 2][superscript +] fragments in the high-resolution mass spectra of the standard compounds indicates that the Aiken-Ambient method underestimates the CO[superscript +] and especially H[subscript 2]O[superscript +] produced from many oxidized species. Combined AMS–vacuum ultraviolet (VUV) ionization measurements indicate that these ions are produced by dehydration and decarboxylation on the AMS vaporizer (usually operated at 600 °C). Thermal decomposition is observed to be efficient at vaporizer temperatures down to 200 °C. These results are used together to develop an "Improved-Ambient" elemental analysis method for AMS spectra measured in air. The Improved-Ambient method uses specific ion fragments as markers to correct for molecular functionality-dependent systematic biases and reproduces known O : C (H : C) ratios of individual oxidized standards within 28% (13%) of the known molecular values. The error in Improved-Ambient O : C (H : C) values is smaller for theoretical standard mixtures of the oxidized organic standards, which are more representative of the complex mix of species present in ambient OA. For ambient OA, the Improved-Ambient method produces O : C (H : C) values that are 27% (11%) larger than previously published Aiken-Ambient values; a corresponding increase of 9% is observed for OM : OC values. These results imply that ambient OA has a higher relative oxygen content than previously estimated. The [bar over OS][subscript C] values calculated for ambient OA by the two methods agree well, however (average relative difference of 0.06 [bar over OS][subscript C] units). This indicates that [bar over OS][subscript C] is a more robust metric of oxidation than O : C, likely since [bar over OS][subscript C] is not affected by hydration or dehydration, either in the atmosphere or during analysis.National Science Foundation (U.S.) (CHE-1012809)National Science Foundation (U.S.) (ATM-1238109

An Innovative Option for Venous Reconstruction After Pancreaticoduodenectomy: the Left Renal Vein

INTRODUCTION: Pancreatic ductal adenocarcinoma has a high mortality rate with limited treatment options. One option is pancreaticoduodenectomy, although complete resection may require venous resection. Pancreaticoduodenectomy with venous resection and reconstruction is becoming a more common practice with many choices for venous reconstruction. We describe the technique of using the left renal vein as a conduit for venous reconstruction during pancreaticoduodenectomy. METHODS: The technique for use of the left renal vein as an interposition graft for venous reconstruction during pancreaticoduodenectomy is described as well as outcomes for nine patients that have undergone the procedure. RESULTS: Nine patients, seven men, with a mean age of 57 years, have undergone the operation. There were eight interposition grafts and one patch graft. Mean operating time was 7.8 hours, and mean tumor size was 3.4 cm. Eight patients had node-positive disease, and six had involvement of the vein. Mean hospital stay was 14 days and perioperative morbidity included a superficial wound infection, delayed gastric emptying, ascites, and gastrointestinal bleeding in one patient each. Creatinine ranged from 0.8–1.1 mg/dl preoperatively and from 0.7–1.3 mg/dl at discharge. Mean follow-up was 6.8 months with normal creatinine values noted through the follow-up period. Two patients had died during follow-up from recurrent disease at 8.3 and 18.2 months after the operation. CONCLUSIONS: The left renal vein provides an additional choice for an autologous graft during pancreaticoduodenectomy with venous resection. The ease of harvesting the graft and maintenance of renal function distinguish its use

Offspring sex and risk of epithelial ovarian cancer: a multinational pooled analysis of 12 case-control studies

While childbearing protects against risk of epithelial ovarian cancer (EOC), few studies have explored the impact on maternal EOC risk of sex of offspring, which may affect the maternal environment during pregnancy. We performed a pooled analysis among parous participants from 12 case–controls studies comprising 6872 EOC patients and 9101 controls. Odds ratios (ORs) and 95% confidence intervals (CIs) were calculated using multivariable logistic regression for case–control associations and polytomous logistic regression for histotype-specific associations, all adjusted for potential confounders. In general, no associations were found between offspring sex and EOC risk. However, compared to bearing only female offspring, bearing one or more male offspring was associated with increased risk of mucinous EOC (OR = 1.45; 95% CI = 1.01-2.07), which appeared to be limited to women reporting menarche before age 13 compared to later menarche (OR = 1.71 vs 0.99; P-interaction = 0.02). Bearing increasing numbers of male offspring was associated with greater risks of mucinous tumors (OR = 1.31, 1.84, 2.31, for 1, 2 and 3 or more male offspring, respectively; trend-p = 0.005). Stratifying by hormonally-associated conditions suggested that compared to bearing all female offspring, bearing a male offspring was associated with lower risk of endometrioid cancer among women with a history of adult acne, hirsutism, or polycystic ovary syndrome (OR = 0.49, 95% CI = 0.28-0.83) but with higher risk among women without any of those conditions (OR = 1.64 95% CI = 1.14–2.34; P-interaction = 0.003). Offspring sex influences the childbearing-EOC risk relationship for specific histotypes and conditions. These findings support the differing etiologic origins of EOC histotypes and highlight the importance of EOC histotype-specific epidemiologic studies. These findings also suggest the need to better understand how pregnancy affects EOC ris

Search for first generation leptoquark pair production in the electron + missing energy + jets final state

We present a search for the pair production of first generation scalar leptoquarks (LQ) in data corresponding to an integrated luminosity of 5.4 fb$^{-1}$ collected with the D0 detector at the Fermilab Tevatron Collider in ppbar collisions at $\sqrt{s}=1.96$ TeV. In the channel $LQ \bar{LQ} \rightarrow e\nu_e qq'$, where q, q' are u or d quarks, no significant excess of data over background is observed, and we set a 95% C.L. lower limit of 326 GeV on the leptoquark mass, assuming equal probabilities of leptoquark decays to eq and $\nu_e q'$.Comment: 7 pages, 6 figures, submitted to PRD-R