Nitrogen-Doped Starbons®: Methodology Development and Carbon Dioxide Capture Capability.

Five nitrogen sources (glycine, ß-alanine, urea, melamine and nicotinamide) and three heating methods (thermal, monomodal microwave and multimodal microwave) are used to prepare nitrogen-doped Starbons® derived from starch. The materials are initially produced at 250-300 °C (SNx 300y ), then heated in vacuo to 800 °C to produce nitrogen-doped SNx 800y 's. Melamine gives the highest nitrogen incorporation without destroying the Starbon® pore structure and the microwave heating methods give higher nitrogen incorporations than thermal heating. The carbon dioxide adsorption capacities of the nitrogen-doped Starbons® determined gravimetrically, in many cases exceed those of S300 and S800. The carbon dioxide, nitrogen and methane adsorption isotherms of the most promising materials are measured volumetrically. Most of the nitrogen-doped materials show higher carbon dioxide adsorption capacities than S800, but lower methane and nitrogen adsorption capacities. As a result, the nitrogen-doped Starbons® exhibit significantly enhanced carbon dioxide versus nitrogen and methane versus nitrogen selectivities compared to S800.

Biomass Derived, Hierarchically Porous, Activated Starbons® as Adsorbents for Volatile Organic Compounds.

The use of potassium hydroxide activated Starbons® derived from starch and alginic acid as adsorbents for 29 volatile organic compounds (VOCs) was investigated. In every case, the alginic acid derived Starbon (A800K2) was found to be the optimal adsorbent, significantly outperforming both commercial activated carbon and starch derived, activated Starbon (S800K2). The saturated adsorption capacity of A800K2 depends on both the size of the VOC and the functional groups it contains. The highest saturated adsorption capacities were obtained with small VOCs. For VOC's of similar size, the presence of polarizable electrons in lone pairs or π-bonds within non-polar VOCs was beneficial. Analysis of porosimetry data suggests that the VOC's are being adsorbed within the pore structure of A800K2 rather than just on its surface. The adsorption was completely reversible by thermal treatment of the saturated Starbon under vacuum.

General Approach to Silica-Supported Salens and Salophens and Their Use as Catalysts for the Synthesis of Cyclic Carbonates from Epoxides and Carbon Dioxide.

General routes for the synthesis of silica-immobilized symmetrical and unsymmetrical salophen and salen ligands and metal complexes have been developed starting from the natural product 4-allylanisole (methyl-chavicol and estragole). The key step of the syntheses is a microwave-assisted, platinum oxide catalyzed hydrosilylation of the terminal alkene of 5-allyl-2-hydroxybenzaldehyde to afford a sol-gel precursor which can be immobilized into silica before or after conversion to salen and salophen ligands to afford unsymmetrical and symmetrical silica-supported ligands, respectively. Both the symmetrical and unsymmetrical silica-supported salophens were found to catalyze the formation of cyclic carbonates from epoxides and carbon dioxide with catalytic activities at least comparable to those previously reported for non-immobilized homogeneous salophens. This reaction could also be carried out in a multi-phase flow reactor using ethyl acetate solutions of 3-phenoxypropylene oxide. Metal complexes of the silica-immobilized ligands could be prepared, and the aluminum complexes were also found to catalyze cyclic carbonate formation.

Neural reactivation and judgements of vividness reveal separable contributions to mnemonic representation.

Mnemonic representations vary in fidelity, sharpness, and strength-qualities that can be examined using both introspective judgements of mental states and objective measures of brain activity. Subjective and objective measures are both valid ways of "reading out" the content of someone's internal mnemonic states, each with different strengths and weaknesses. St-Laurent and colleagues (2015) compared the neural correlates of memory vividness ratings with patterns of neural reactivation evoked during memory recall and found considerable overlap between the two, suggesting a common neural basis underlying these different markers of representational quality. Here we extended this work with meta-analytic methods by pooling together four neuroimaging datasets in order to contrast the neural substrates of neural reactivation and those of vividness judgements. While reactivation and vividness judgements correlated positively with one another and were associated with common univariate activity in the dorsal attention network and anterior hippocampus, some notable differences were also observed. Vividness judgments were tied to stronger activation in the striatum and dorsal attention network, together with activity suppression in default mode network nodes. We also observed a trend for reactivation to be more closely associated with early visual cortex activity. A mediation analysis found support for the hypothesis that neural reactivation is necessary for memory vividness, with activity in the anterior hippocampus associated with greater reactivation. Our results suggest that neural reactivation and vividness judgements reflect common mnemonic processes but differ in the extent to which they engage effortful, attentional processes. Additionally, the similarity between reactivation and vividness appears to arise, partly, through hippocampal engagement during memory retrieval.

Processing differences between monolingual and bilingual young adults on an emotion n-back task.

Bilingualism is associated with enhancement of executive control (EC) across the lifespan. Working memory and non-verbal emotion regulation both draw upon EC mechanisms so may also be affected by bilingualism, but these relationships are not fully understood. These relationships were explored using an n-back task with distracting emotional stimuli administered to young adults while continuous EEG was recorded. Monolinguals were faster but less accurate on the 2-back than bilinguals, and monolingual accuracy was more impeded by the presence of emotional stimuli than was that of bilinguals. The P300 event-related potential, a neural signature of working memory processing in the n-back, had smaller amplitudes in both groups on the 2-back than the 1-back, but attenuation in response to distracting emotional stimuli was greater for bilinguals than monolinguals. P300 latencies were also differentially affected by emotional stimuli in each group: Bilingual latencies were constant across emotions but monolingual latencies increased from neutral to angry conditions. In general, bilingual performance was less impacted by the emotional distraction than was that of the monolinguals. Additionally, bilinguals adjusted to the changing demands of the 1-back and 2-back conditions by recruiting neural networks to support different behavioral outcomes than monolinguals.

The relation between brain signal complexity and task difficulty on an executive function task.

On a daily basis, we constantly deal with changing environmental cues and perceptual conflicts and as such, our brains must flexibly adapt to current demands in order to act appropriately. Brains become more efficient and are able to switch states more readily by increasing the complexity of their neural networks. However, it is unclear how brain signal complexity relates to behavior in young adults performing cognitively demanding executive function tasks. Here we used multiscale entropy analysis and multivariate statistics on EEG data while participants performed a bivalency effect task-switching paradigm to show that brain signal complexity in young adults increases as task demands increase, that increases in brain signal complexity are associated with both speed gains and losses depending on scalp location, and that more difficult tasks are associated with more circumscribed complexity across the scalp. Overall, these findings highlight a critical role for brain signal complexity in predicting behavior on an executive function task among young adults.

Effects of bilingualism on white matter integrity in older adults.

Bilingualism can delay the onset of dementia symptoms and has thus been characterized as a mechanism for cognitive or brain reserve, although the origin of this reserve is unknown. Studies with young adults generally show that bilingualism is associated with a strengthening of white matter, but there is conflicting evidence for how bilingualism affects white matter in older age. Given that bilingualism has been shown to help stave off the symptoms of dementia by up to four years, it is crucial that we clarify the mechanism underlying this reserve. The current study uses diffusion tensor imaging (DTI) to compare monolinguals and bilinguals while carefully controlling for potential confounds (e.g., I.Q., MMSE, and demographic variables). We show that group differences in Fractional Anisotropy (FA) and Radial Diffusivity (RD) arise from multivariable interactions not adequately controlled for by sequential bivariate testing. After matching and statistically controlling for confounds, bilinguals still had greater axial diffusivity (AD) in the left superior longitudinal fasciculus than monolingual peers, supporting a neural reserve account for healthy older bilinguals.

Discovery of Selective Phosphodiesterase 1 Inhibitors with Memory Enhancing Properties.

A series of potent thienotriazolopyrimidinone-based PDE1 inhibitors was discovered. X-ray crystal structures of example compounds from this series in complex with the catalytic domain of PDE1B and PDE10A were determined, allowing optimization of PDE1B potency and PDE selectivity. Reduction of hERG affinity led to greater than a 3000-fold selectivity for PDE1B over hERG. 6-(4-Methoxybenzyl)-9-((tetrahydro-2H-pyran-4-yl)methyl)-8,9,10,11-tetrahydropyrido[4',3':4,5]thieno[3,2-e][1,2,4]triazolo[1,5-c]pyrimidin-5(6H)-one was identified as an orally bioavailable and brain penetrating PDE1B enzyme inhibitor with potent memory-enhancing effects in a rat model of object recognition memory.

Molecular characterization of a homolog of the ferric-uptake regulator, Fur, from the marine bacterium Marinobacter algicola DG893.

Full length recombinant iron regulatory protein, Fur, has been isolated and characterized from the algal-associated marine bacterium Marinobacter algicola DG893. Under nondenaturing conditions the Fur protein behaves on size exclusion chromatography as a dimer while it is monomeric under SDS PAGE conditions. ICP-MS and fluorescence quenching experiments show that Mb-Fur binds a single metal ion (Zn, Mn, or Co) per monomer. Electrophoretic mobility shift assays were used to probe the interaction of Mb-Fur with the purported Fur box in the promoter region upstream of the vibrioferrin biosynthetic operon. Interaction of Mb-Fur with a 100 bp DNA fragment containing the Fur box in the presence of 10 µM Mn, Co or Zn(II) resulted in decreased migration of DNA on a 7.5% polyacrylamide gel. In the absence of the Fur protein or the metal, no interaction is seen. The presence of EDTA in the binding, loading or running buffers also abolished all activity demonstrating the importance of the metal in formation of the promoter-repressor complex. Based on a high degree of similarity between Mb-Fur and its homolog from Pseudomonas aeruginosa (PA) whose X-ray structure is known we developed a structural model for the former which suggested that only one of the several metal binding sites found in other Fur's would be functional. This is consistent with the single metal binding stoichiometry we observed. Since the purported metal binding site was one that has been described as "structural" rather than "functional" in PA and yet the monometallic Mb-Fur retains DNA Fur box binding ability it reopens the question of which site is which, or if different species have adapted the sites for different purposes.

Borate as a synergistic anion for Marinobacter algicola ferric binding protein, FbpA: a role for boron in iron transport in marine life.

Boron in the ocean is generally considered a nonbiological element due to its relatively high concentration (0.4 mM) and depth independent concentration profile. Here we report an unexpected role for boron in the iron transport system of the marine bacterium Marinobacter algicola. Proteome analysis under varying boron concentrations revealed that the periplasmic ferric binding protein (Mb-FbpA) was among the proteins whose expression was most affected, strongly implicating the involvement of boron in iron utilization. Here we show that boron facilitates Fe(3+) sequestration by Mb-FbpA at pH 8 (oceanic pH) by acting as a synergistic anion (B(OH)4(1-)). Fe(3+) sequestration does not occur at pH 6.5 where boric acid (B(OH)3; pK(a) = 8.55) is the predominant species. Borate anion is also shown to bind to apo-Mb-FbpA with mM affinity at pH 8, consistent with the biological relevance implied from boron's oceanic concentration (0.4 mM). Borate is among those synergistic anions tested which support the strongest Fe(3+) binding to Mb-FbpA, where the range of anion dependent affinity constants is log K'(eff) = 21-22. Since the pKa of boric acid (8.55) lies near the pH of ocean water, changes in oceanic pH, as a consequence of fluctuations in atmospheric CO2, may perturb iron uptake in many marine heterotrophic bacteria due to a decrease in oceanic borate anion concentration.

Regulation of iron transport related genes by boron in the marine bacterium Marinobacter algicola DG893.

While there has been extensive interest in the use of boron isotope ratios as a surrogate of pH in paleoclimate studies in the context of climate change-related questions, the high (0.4 mM) concentration and the depth-independent (conservative or non-nutrient-like) concentration profile of this element have led to boron being neglected as a potentially biologically relevant element in the modern ocean. Here we report that boron affects the expression of a number of protein and genes in the "algal-associated" Gram-negative marine bacterium Marinobacter algicola DG893. Most intriguingly, a number of these proteins and genes are related to iron uptake. In a recent separate publication we have shown that boron regulates one such iron transport related protein, i.e. the periplasmic iron binding protein FbpA via a direct interaction of the metalloid with this protein. Here we show that a number of other iron uptake related genes are also affected by boron but in the opposite way i.e. they are up-regulated. We propose that the differential effect of boron on FbpA expression relative to other iron transport related genes is a result of an interaction between boron and the global iron regulatory protein Fur.