Origin of Enantioselection in Chiral Alcohol Oxidation Catalyzed by Pd[(-)-sparteine]Cl2

A kinetic investigation into the origin of enantioselectivity for the Pd[(-)-sparteine]Cl2-catalyzed aerobic oxidative kinetic resolution (OKR) is reported. A mechanism to account for a newly discovered chloride dissociation from Pd[(-)-sparteine]Cl2 prior to alcohol binding is proposed. The mechanism includes (1) chloride dissociation from Pd[(-)-sparteine]Cl2 to form cationic Pd(-)-sparteine]Cl, (2) alcohol binding, (3) deprotonation of Pd-bound alcohol to form a Pd-alkoxide, and (4) â-hydride elimination of Pd-alkoxide to form ketone product and a Pd-hydride. Utilizing the addition of (-)-sparteine HCl to control the [Cl-] and [H+] and the resulting derived rate law, the key microscopic kinetic and thermodynamic constants were extracted for each enantiomer of sec-phenethyl alcohol. These constants allow for the successful simulation of the oxidation rate in the presence of exogenous (-)-sparteine HCl. A rate law for oxidation of the racemic alcohol was derived that allows for the successful prediction of the experimentally measured krel values when using the extracted constants. Besides a factor of 10 difference between the relative rates of â-hydride elimination for the enantiomers, the main enhancement in enantiodetermination results from a concentration effect of (-)-sparteine HCl and the relative rates of reprotonation of the diastereomeric Pd-alkoxides

The auxiliary use of LANDSAT data in estimating crop acreages: Results of the 1975 Illinois crop-acreage experiment

The author has identified the following significant results. It was found that classifier performance was influenced by a number of temporal, methodological, and geographical factors. Best results were obtained when corn was tasselled and near the dough stage of development. Dates earlier or later in the growing season produced poor results. Atmospheric effects on results cannot be independently measured or completely separated from the effects due to the maturity stage of the crops. Poor classifier performance was observed in areas where considerable spectral confusion was present

Avoiding catastrophic failure in correlated networks of networks

Networks in nature do not act in isolation but instead exchange information, and depend on each other to function properly. An incipient theory of Networks of Networks have shown that connected random networks may very easily result in abrupt failures. This theoretical finding bares an intrinsic paradox: If natural systems organize in interconnected networks, how can they be so stable? Here we provide a solution to this conundrum, showing that the stability of a system of networks relies on the relation between the internal structure of a network and its pattern of connections to other networks. Specifically, we demonstrate that if network inter-connections are provided by hubs of the network and if there is a moderate degree of convergence of inter-network connection the systems of network are stable and robust to failure. We test this theoretical prediction in two independent experiments of functional brain networks (in task- and resting states) which show that brain networks are connected with a topology that maximizes stability according to the theory.Comment: 40 pages, 7 figure

Nitrogen and oxygen isotope constraints on the origin of atmospheric nitrate in coastal Antarctica

Throughout the year 2001, aerosol samples were collected continuously for 10 to 15 days at the French Antarctic Station Dumont d'Urville (DDU) (66°40' S, l40°0' E, 40 m above mean sea level). The nitrogen and oxygen isotopic ratios of particulate nitrate at DDU exhibit seasonal variations that are among the most extreme observed for nitrate on Earth. In association with concentration measurements, the isotope ratios delineate four distinct periods, broadly consistent with previous studies on Antarctic coastal areas. During austral autumn and early winter (March to mid-July), nitrate concentrations attain a minimum between 10 and 30 ng m^−3 (referred to as Period 2). Two local maxima in August (55 ng m^−3) and November/December (165 ng m^−3) are used to assign Period 3 (mid-July to September) and Period 4 (October to December). Period 1 (January to March) is a transition period between the maximum concentration of Period 4 and the background concentration of Period 2. These seasonal changes are reflected in changes of the nitrogen and oxygen isotope ratios. During Period 2, which is characterized by background concentrations, the isotope ratios are in the range of previous measurements at mid-latitudes: δ¹⁸O_vsmow=(77.2±8.6)‰; Δ¹⁷O=(29.8±4.4)‰; δ¹⁵N_air=(−4.4±5.4)‰ (mean ± one standard deviation). Period 3 is accompanied by a significant increase of the oxygen isotope ratios and a small increase of the nitrogen isotope ratio to δ¹⁸O_vsmow=(98.8±13.9)‰; Δ¹⁷O=(38.8±4.7)‰ and δ¹⁵N_air=(4.3±8.20‰). Period 4 is characterized by a minimum ¹⁵N/¹⁴N ratio, only matched by one prior study of Antarctic aerosols, and oxygen isotope ratios similar to Period 2: δ¹⁸O_vsmow=(77.2±7.7)‰; Δ¹⁷O=(31.1±3.2)‰; δ¹⁵N_air=(−32.7±8.4)‰. Finally, during Period 1, isotope ratios reach minimum values for oxygen and intermediate values for nitrogen: δ¹⁸O_vsmow=63.2±2.5‰; Δ¹⁷O=24.0±1.1‰; δ¹⁵N_air=−17.9±4.0‰). Based on the measured isotopic composition, known atmospheric transport patterns and the current understanding of kinetics and isotope effects of relevant atmospheric chemical processes, we suggest that elevated tropospheric nitrate levels during Period 3 are most likely the result of nitrate sedimentation from polar stratospheric clouds (PSCs), whereas elevated nitrate levels during Period 4 are likely to result from snow re-emission of nitrogen oxide species. We are unable to attribute the source of the nitrate during periods 1 and 2 to local production or long-range transport, but note that the oxygen isotopic composition is in agreement with day and night time nitrate chemistry driven by the diurnal solar cycle. A precise quantification is difficult, due to our insufficient knowledge of isotope fractionation during the reactions leading to nitrate formation, among other reasons

The Early Sociocognitive Battery: a clinical tool for early identification of children at risk for social communication difficulties and ASD?

BACKGROUND: A substantial proportion of preschool children referred to speech and language therapy (SLT) services have social communication difficulties and/or autistic spectrum disorders (SC&/ASD) that are not identified until late childhood. These 'late' diagnosed children miss opportunities to benefit from earlier targeted interventions. Prior evidence from a follow-up clinical sample showed that preschool performance on the Early Sociocognitive Battery (ESB) was a good predictor of children with social communication difficulties 7-8 years later. AIMS: The aims were three-fold: (1) to determine the impact of child/demographic factors on ESB performance in a community sample of young children; (2) to assess the ESB's concurrent validity and test-retest reliability; and (3) to use cut-offs for 'low' ESB performance derived from the community sample data to evaluate in a clinical sample the predictiveness of the ESB at 2-4 years for outcomes at 9-11 years, including parent-reported SC&/ASD diagnosis. METHODS & PROCEDURES: A community sample of 205 children aged 2-4 years was assessed on the ESB and a receptive vocabulary test. A subsample (n = 20) was retested on the ESB within 2 weeks. Parents completed a questionnaire providing background child/demographic information. The clinical sample from our previous study comprised 93 children assessed on the ESB at 2;6 to < 4;0 whose parents completed the Social Responsiveness Scale (SRS), our measure of social communication, when the children were 9-11 years. Cut-offs for 'low' ESB performance derived from the community sample were used to determine the predictive validity of 'low' ESB scores for social communication outcomes and parent-reported SC&/ASD diagnosis according to age of ESB assessment. OUTCOME & RESULTS: Findings from the community sample confirmed the ESB as psychometrically robust, sensitive to age and language delay, and, in contrast to the receptive vocabulary measure, unaffected by bilingualism. While overall associations between ESB performance and later social communication difficulties in the clinical sample were particularly strong for the youngest age group (2;6 to < 3;0; r = .71, p < .001), 'low' ESB performance was equally predictive across age groups and overall identified 89% of children with 'late' SC&/ASD diagnoses (sensitivity), and 75% of those without (specificity). CONCLUSIONS & IMPLICATIONS: Results indicate that the ESB is a valid preschool assessment suitable for use with children from diverse language backgrounds. It identifies deficits in key sociocognitive skills and is predictive of social communication difficulties in school-age children that had not been identified in preschool clinical assessment, supporting earlier targeted interventions for these children

Enzyme-level interconversion of nitrate and nitrite in the fall mixed layer of the Antarctic Ocean

In the Southern Ocean, the nitrogen (N) isotopes of organic matter and the N and oxygen (O) isotopes of nitrate (NO_3^−) have been used to investigate NO_3^− assimilation and N cycling in the summertime period of phytoplankton growth, both today and in the past. However, recent studies indicate the significance of processes in other seasons for producing the annual cycle of N isotope changes. This study explores the impact of fall conditions on the ^(15)N/^(14)N (δ^(15)N) and ^(18)O/^(16)O (δ^(18)O) of NO_3^− and nitrite (NO_2^−) in the Pacific Antarctic Zone using depth profiles from late summer/fall of 2014. In the mixed layer, the δ^(15)N and δ^(18)O of NO_3^− + NO_2^− increase roughly equally, as expected for NO_3^− assimilation; however, the δ^(15)N of NO_3^−-only (measured after NO_2− removal) increases more than does NO_3^− -only δ^(18)O. Differencing indicates that NO_2^− has an extremely low δ^(15)N, often < −70‰ versus air. These observations are consistent with the expression of an equilibrium N isotope effect between NO_3^− and NO_2^−, likely due to enzymatic NO_3^- - NO_2^− interconversion. Specifically, we propose reversibility of the nitrite oxidoreductase (NXR) enzyme of nitrite oxidizers that, having been entrained from the subsurface during late summer mixed layer deepening, are inhibited by light. Our interpretation suggests a role for NO_3^- - NO_2^− interconversion where nitrifiers are transported into environments that discourage NO_2^− oxidation. This may apply to surface regions with upwelling, such as the summertime Antarctic. It may also apply to oxygen-deficient zones, where NXR-catalyzed interconversion may explain previously reported evidence of NO_2^− oxidation

Helping and Cooperation in Children with Autism

Helping and cooperation are central to human social life. Here, we report two studies investigating these social behaviors in children with autism and children with developmental delay. In the first study, both groups of children helped the experimenter attain her goals. In the second study, both groups of children cooperated with an adult, but fewer children with autism performed the tasks successfully. When the adult stopped interacting at a certain moment, children with autism produced fewer attempts to re-engage her, possibly indicating that they had not formed a shared goal/shared intentions with her. These results are discussed in terms of the prerequisite cognitive and motivational skills and propensities underlying social behavior

Foraminiferal isotope evidence of reduced nitrogen fixation in the ice age Atlantic Ocean

Fixed nitrogen (N) is a limiting algal nutrient in the low latitude ocean, and the oceanic N inventory has been suggested to increase during ice ages so as to lower atmospheric CO_2. In organic matter within planktonic foraminifera shells in Caribbean Sea sediments, the ^(15)N/^(14)N from the last ice age is higher than that from the current interglacial, indicating higher nitrate ^(15)N/^(14)N in the Caribbean thermocline. This and species-specific differences are best explained by less N fixation in the Atlantic during the last ice age. The fixation decrease was most likely a response to a known ice age reduction in ocean N loss, and it would have worked to balance the ocean N budget and to curb ice age-to-interglacial change in the N inventory