High resolution solid state NMR in paramagnetic metal-organic frameworks.

We study the metal-organic framework (MOF) ZIF-67 with 1H and 13C nuclear magnetic resonance (NMR). In addition to the usual orbital chemical shifts, we observe spinning sideband manifolds in the NMR spectrum due to hyperfine interactions of the paramagnetic cobalt with 1H and 13C. Both orbital and paramagnetic chemical shifts are in good agreement with values calculated from first principles, allowing high-confidence assignment of the observed peaks to specific sites within the MOF. Our measured resonance shifts, line shapes, and spin lattice relaxation rates are also consistent with calculated values. We show that molecules in the pores of the MOF can exhibit high-resolution NMR spectra with fast spin lattice relaxation rates due to dipole-dipole couplings to the Co2+ nodes in the ZIF-67 lattice, showcasing NMR spectroscopy as a powerful tool for identification and characterization of "guests" that may be hosted by the MOF in electrochemical and catalytic applications.

Dual Task Performance Is Associated with Amyloidosis in Cognitively Healthy Adults.

BACKGROUND: Preclinical Alzheimer's disease (AD) provides an opportunity for the study and implementation of interventions and strategies aimed at delaying, mitigating, and preventing AD. While this preclinical state is an ideal target, it is difficult to identify efficiently and cost-effectively. Recent findings have suggested that cognitive-motor dual task paradigms may provide additional inference. OBJECTIVES: Investigate the relationship between dual task performance and amyloidosis, suggestive of preclinical Alzheimer's disease and whether dual task performance provides additional information beyond a cognitive composite, to help in the identification of amyloidosis. DESIGN: Cross-sectional. SETTING: Outpatient specialty brain health clinical research institution in the United States. PARTICIPANTS: 52 cognitively healthy adults. MEASUREMENTS: The data included demographics, amyloid standardized uptake value ratio obtained via florbetapir-PET, neuropsychological testing, apolipoprotien E genotype, and dual task performance measures. Data were analyzed via hierarchal multiple linear regression or logistic regression, controlling for age, education, and apolipoprotien E genotype. Receiver operating characteristic curves were plotted, and sensitivity and specificity calculated via 2x2 contingency tables. RESULTS: There was a moderate relationship (rs>.30) between motor and cognitive dual task effects and amyloid standardized uptake value ratio (ps<.042). A strong relationship (r=.58) was found between combined dual task effect, a measure of automaticity derived from dual task performance, and amyloid standardized uptake value ratio (p<.001). Additionally, combined dual task effect showed promise in its unique contributions to amyloid standardized uptake value ratio, accounting for 7.8% of amyloid standardized uptake value ratio variance beyond cognitive composite scores (p=.018). Additionally, when incorporated into the cognitive composite, combined dual task effect resulted in improved diagnostic accuracy for determining elevated amyloid standardized uptake value ratio, and increased the sensitivity and specificity of the cognitive composite. CONCLUSSION: Dual task performance using the combined dual task effect, a measure of automaticity, was a moderate predictor of cerebral amyloidosis, which suggests that it has utility in the screening and diagnosis of individuals for preclinical AD. Additionally, when combined with the cognitive composite, the combined dual task effect improves diagnostic accuracy. Further research is warranted.

Improved Constraints on Global Methane Emissions and Sinks Using δ 13C-CH4.

We study the drivers behind the global atmospheric methane (CH4) increase observed after 2006. Candidate emission and sink scenarios are constructed based on proposed hypotheses in the literature. These scenarios are simulated in the TM5 tracer transport model for 1984-2016 to produce three-dimensional fields of CH4 and δ 13C-CH4, which are compared with observations to test the competing hypotheses in the literature in one common model framework. We find that the fossil fuel (FF) CH4 emission trend from the Emissions Database for Global Atmospheric Research 4.3.2 inventory does not agree with observed δ 13C-CH4. Increased FF CH4 emissions are unlikely to be the dominant driver for the post-2006 global CH4 increase despite the possibility for a small FF emission increase. We also find that a significant decrease in the abundance of hydroxyl radicals (OH) cannot explain the post-2006 global CH4 increase since it does not track the observed decrease in global mean δ 13C-CH4. Different CH4 sinks have different fractionation factors for δ 13C-CH4, thus we can investigate the uncertainty introduced by the reaction of CH4 with tropospheric chlorine (Cl), a CH4 sink whose abundance, spatial distribution, and temporal changes remain uncertain. Our results show that including or excluding tropospheric Cl as a 13 Tg/year CH4 sink in our model changes the magnitude of estimated fossil emissions by ∼20%. We also found that by using different wetland emissions based on a static versus a dynamic wetland area map, the partitioning between FF and microbial sources differs by 20 Tg/year, ∼12% of estimated fossil emissions.

Astronomical time-of-flight photon speedometer.

A dual-band, fiber-optic, photon time-of-flight instrument was developed. Its design was optimized for measuring the velocity of visible photons emanating from relatively dim astronomical sources (apparent magnitude m>12), such as distant galaxies and quasars. We report the first direct photon group velocity measurements for extragalactic objects. The photon group velocity is found to be 3.00±0.03×108 ms-1 and is invariant, within experimental error, over the range of redshifts measured (0≤z≤1.33). This measurement provides additional validation of general relativity and is consistent with the Friedmann-Lemaître-Robertson-Walker and hyperbolic anti-de Sitter metrics but not with the elliptical de Sitter metric.

Intravitreal aflibercept for macular oedema secondary to central retinal vein occlusion in patients with prior treatment with bevacizumab or ranibizumab.

PurposeTo report the visual and anatomic outcomes in eyes with macular oedema (MO) secondary to central retinal vein occlusion (CRVO) that were switched from either intravitreal bevacizumab or ranibizumab to intravitreal aflibercept.MethodsTwo-center retrospective chart review. Eyes with MO secondary to CRVO that received a minimum of three intravitreal injections of bevacizumab or ranibizumab and were switched to intravitreal aflibercept for persistent or recurrent MO not responding to either bevacizumab and/or ranibizumab.ResultsIn all 42 eyes of 42 patients were included in the study. The median visual acuity before the switch was 20/126, 1 month after the first injection of aflibercept 20/89 (P=0.0191), and at the end of the follow-up 20/100 (P=0.2724). The median CRT before the switch was 536 µm, 1 month after the first injection of aflibercept 293.5 µm (P=0.0038), and at the end of the follow-up 279 µm (P=0.0013 compared to before the switch). The median number of weeks between injections before the switch was 5.6 and after the switch was 7.6 (P<0.0001).ConclusionConverting eyes with refractory MO due to CRVO to aflibercept can result in stabilization of the vision, improved macular anatomy, and extension of the injection interval.

Drought sensitivity of Amazonian carbon balance revealed by atmospheric measurements.

Feedbacks between land carbon pools and climate provide one of the largest sources of uncertainty in our predictions of global climate. Estimates of the sensitivity of the terrestrial carbon budget to climate anomalies in the tropics and the identification of the mechanisms responsible for feedback effects remain uncertain. The Amazon basin stores a vast amount of carbon, and has experienced increasingly higher temperatures and more frequent floods and droughts over the past two decades. Here we report seasonal and annual carbon balances across the Amazon basin, based on carbon dioxide and carbon monoxide measurements for the anomalously dry and wet years 2010 and 2011, respectively. We find that the Amazon basin lost 0.48 ± 0.18 petagrams of carbon per year (Pg C yr(-1)) during the dry year but was carbon neutral (0.06 ± 0.1 Pg C yr(-1)) during the wet year. Taking into account carbon losses from fire by using carbon monoxide measurements, we derived the basin net biome exchange (that is, the carbon flux between the non-burned forest and the atmosphere) revealing that during the dry year, vegetation was carbon neutral. During the wet year, vegetation was a net carbon sink of 0.25 ± 0.14 Pg C yr(-1), which is roughly consistent with the mean long-term intact-forest biomass sink of 0.39 ± 0.10 Pg C yr(-1) previously estimated from forest censuses. Observations from Amazonian forest plots suggest the suppression of photosynthesis during drought as the primary cause for the 2010 sink neutralization. Overall, our results suggest that moisture has an important role in determining the Amazonian carbon balance. If the recent trend of increasing precipitation extremes persists, the Amazon may become an increasing carbon source as a result of both emissions from fires and the suppression of net biome exchange by drought.

Increase in observed net carbon dioxide uptake by land and oceans during the past 50 years.

One of the greatest sources of uncertainty for future climate predictions is the response of the global carbon cycle to climate change. Although approximately one-half of total CO(2) emissions is at present taken up by combined land and ocean carbon reservoirs, models predict a decline in future carbon uptake by these reservoirs, resulting in a positive carbon-climate feedback. Several recent studies suggest that rates of carbon uptake by the land and ocean have remained constant or declined in recent decades. Other work, however, has called into question the reported decline. Here we use global-scale atmospheric CO(2) measurements, CO(2) emission inventories and their full range of uncertainties to calculate changes in global CO(2) sources and sinks during the past 50 years. Our mass balance analysis shows that net global carbon uptake has increased significantly by about 0.05 billion tonnes of carbon per year and that global carbon uptake doubled, from 2.4 ± 0.8 to 5.0 ± 0.9 billion tonnes per year, between 1960 and 2010. Therefore, it is very unlikely that both land and ocean carbon sinks have decreased on a global scale. Since 1959, approximately 350 billion tonnes of carbon have been emitted by humans to the atmosphere, of which about 55 per cent has moved into the land and oceans. Thus, identifying the mechanisms and locations responsible for increasing global carbon uptake remains a critical challenge in constraining the modern global carbon budget and predicting future carbon-climate interactions.

Spray desorption collection of free fatty acids onto a solid phase microextraction fiber for trap grease analysis in biofuel production.

Spray desorption collection (SDC) is a sample collection and preparation method that allows for the collection of soluble chemical compounds directly from solid surfaces. Here the analysis of trap grease, a potential biofuel feedstock, is demonstrated by combining SDC with solid phase micro-extraction (SPME) collection followed by direct GC-MS analysis. The SPME fiber collects droplets of solvent, which has picked up analytes from the solid sample surface. It is found that the SDC-SPME combination is a simple and convenient method to collect sample components from surfaces when they are less volatile than heptanoic acid, while the collection efficiency of highly volatile compounds is increasingly reduced due to the purging effect of the nebulising gas. In a real trap grease analysis the SDC-SPME method was able to analyze both the longer chain fatty acids in the sample, important for energy production evaluation of the sample, as well as volatile sample components down to pentanoic acid, which may add to off-odours produced during biofuel use.

Quasi-particle properties from tunneling in the v = 5/2 fractional quantum Hall state.

Quasi-particles with fractional charge and statistics, as well as modified Coulomb interactions, exist in a two-dimensional electron system in the fractional quantum Hall (FQH) regime. Theoretical models of the FQH state at filling fraction v = 5/2 make the further prediction that the wave function can encode the interchange of two quasi-particles, making this state relevant for topological quantum computing. We show that bias-dependent tunneling across a narrow constriction at v = 5/2 exhibits temperature scaling and, from fits to the theoretical scaling form, extract values for the effective charge and the interaction parameter of the quasi-particles. Ranges of values obtained are consistent with those predicted by certain models of the 5/2 state.

Contribution of anthropogenic and natural sources to atmospheric methane variability.

Methane is an important greenhouse gas, and its atmospheric concentration has nearly tripled since pre-industrial times. The growth rate of atmospheric methane is determined by the balance between surface emissions and photochemical destruction by the hydroxyl radical, the major atmospheric oxidant. Remarkably, this growth rate has decreased markedly since the early 1990s, and the level of methane has remained relatively constant since 1999, leading to a downward revision of its projected influence on global temperatures. Large fluctuations in the growth rate of atmospheric methane are also observed from one year to the next, but their causes remain uncertain. Here we quantify the processes that controlled variations in methane emissions between 1984 and 2003 using an inversion model of atmospheric transport and chemistry. Our results indicate that wetland emissions dominated the inter-annual variability of methane sources, whereas fire emissions played a smaller role, except during the 1997-1998 El Niño event. These top-down estimates of changes in wetland and fire emissions are in good agreement with independent estimates based on remote sensing information and biogeochemical models. On longer timescales, our results show that the decrease in atmospheric methane growth during the 1990s was caused by a decline in anthropogenic emissions. Since 1999, however, they indicate that anthropogenic emissions of methane have risen again. The effect of this increase on the growth rate of atmospheric methane has been masked by a coincident decrease in wetland emissions, but atmospheric methane levels may increase in the near future if wetland emissions return to their mean 1990s levels.

Unexpected changes to the global methane budget over the past 2000 years.

We report a 2000-year Antarctic ice-core record of stable carbon isotope measurements in atmospheric methane (delta13CH4). Large delta13CH4 variations indicate that the methane budget varied unexpectedly during the late preindustrial Holocene (circa 0 to 1700 A.D.). During the first thousand years (0 to 1000 A.D.), delta13CH4 was at least 2 per mil enriched compared to expected values, and during the following 700 years, an about 2 per mil depletion occurred. Our modeled methane source partitioning implies that biomass burning emissions were high from 0 to 1000 A.D. but reduced by almost approximately 40% over the next 700 years. We suggest that both human activities and natural climate change influenced preindustrial biomass burning emissions and that these emissions have been previously understated in late preindustrial Holocene methane budget research.

Liver histopathology and liver and serum alanine aminotransferase and alkaline phosphatase activities in epileptic dogs receiving phenobarbital.

Phenobarbital (PB) therapy is frequently associated with elevated serum alanine aminotransferase (ALT) and alkaline phosphatase (AP) activities in dogs without clinical signs of liver disease. The goal of this study was to determine if increased serum ALT and AP activities in clinically healthy PB-treated epileptic dogs are due to hepatic enzyme induction or to subclinical liver injury. Liver biopsies were obtained from 12 PB-treated dogs without clinical signs of liver disease but with elevated serum ALT and/or AP activities or both. Liver biopsies were obtained from eight healthy control dogs not receiving PB. Biopsies were evaluated histopathologically (all dogs) and liver homogenates were assayed for ALT (all dogs) and AP (six treated dogs, all controls) activities. As a positive control, liver cytochrome P4502B, an enzyme known to be induced by PB, was measured by benzyloxyresorufin-O-dealkylase activity and immunoblotting (five treated dogs, all controls). Serum AP isoenzyme analyses were performed. Results showed that ALT and AP activities in liver homogenates were not increased in treated dogs compared with controls, whereas the positive control for induction, CYP2B, was dramatically increased in treated dogs. Histopathological examination of liver biopsies revealed more severe and frequent abnormalities in treated dogs compared to controls, but similar types of abnormalities were found in both groups. Serum AP isoenzyme analyses in treated dogs demonstrated increased corticosteroid-induced and liver isoenzyme activities compared to controls. Results do not support induction of ALT or AP in the liver as the cause of elevated serum activities of these enzymes due to PB.

14N magnetic resonance for materials detection in the field.

Nitrogen is prevalent in many materials, both naturally occurring and man-made. In particular, it is found in many explosives and other contraband materials. One technique for the detection of such materials in the field is the use of the magnetic resonance signal from the nearly 100% abundant, spin-1, 14N nuclei. Some of the difficulties with such measurements in the field include spurious signals from acoustic resonances, radio-frequency interference, and generally low signal-to-noise ratios. A summary of recent work by the authors to help mitigate these difficulties is presented.

Gate-controlled spin-orbit quantum interference effects in lateral transport.

In situ control of spin-orbit coupling in coherent transport using a clean GaAs/AlGaAs two-dimensional electron gas is realized, leading to a gate-tunable crossover from weak localization to antilocalization. The necessary theory of 2D magnetotransport in the presence of spin-orbit coupling beyond the diffusive approximation is developed and used to analyze experimental data. With this theory the Rashba contribution and linear and cubic Dresselhaus contributions to spin-orbit coupling are separately estimated, allowing the angular dependence of spin-orbit precession to be extracted at various gate voltages.

Spin-orbit coupling, antilocalization, and parallel magnetic fields in quantum dots.

We investigate antilocalization due to spin-orbit coupling in ballistic GaAs quantum dots. Antilocalization that is prominent in large dots is suppressed in small dots, as anticipated theoretically. Parallel magnetic fields suppress both antilocalization and also, at larger fields, weak localization, consistent with random matrix theory results once orbital coupling of the parallel field is included. In situ control of spin-orbit coupling in dots is demonstrated as a gate-controlled crossover from weak localization to antilocalization.

Quantitative amino acid analysis using a Beckman system gold HPLC 126AA analyzer.

BACKGROUND: The Beckman 6300/7300 analyzer, which was widely used for amino acid (AA) analysis, is no longer commercially available. METHODS: To set up an affordable AA analysis program, a Beckman system gold HPLC 126AA analyzer and Pickering Laboratories reagents were used. Two quantitative AA analysis programs were developed. One was an 18-min short program quantitating seven AAs from plasma and dried blood spots (DBS) specimens using Lithium eluents Li-365 and Li-375 at 70 degrees C column temperature. The short program could be used for diagnosis and follow-up dietary management for phenylketonuria (PKU), maple syrup urine disease (MSUD), tyrosinemia and homocystinuria patients. The second program was a 118-min long AA screening panel quantitating 40 AAs using Lithium eluents Li-275, Li-365 and Li-375 at 32, 48 and 72 degrees C column temperatures from plasma and urine specimens. RESULTS: The values obtained from DBS specimens were in good agreement with certified results from the Centers for Disease Control and Prevention. The values obtained from plasma and urine samples were in good correlation with those obtained from Beckman 6300 analyzer (0.9076 < or = r < or = 0.999). CONCLUSIONS: Amino acid quantitation from physiological samples using a Beckman 126AA Analyzer and Pickering Laboratories reagents was useful for clinical diagnosis and monitoring of aminoacidopathies.

A longitudinal study of salivary sialic acid in preterm infants: Comparison of human milk-fed versus formula-fed infants.

We found that the saliva of preterm infants fed human milk contains twice the level of sialic acid as that in infants fed commercial formulas. The higher sialic acid level suggests greater viscosity and enhanced protection of the mucosal surfaces in breast-fed infants. Human milk itself is a rich source of sialylated oligosaccharides.