Structural Effects of Gas Hydrate Antiagglomerant Molecules on Interfacial Interparticle Force Interactions.

Gas hydrate interparticle cohesive forces are important to determine the hydrate crystal particle agglomeration behavior and subsequent hydrate slurry transport that is critical to preventing potentially catastrophic consequences of subsea oil/gas pipeline blockages. A unique high-pressure micromechanical force apparatus has been employed to investigate the effect of the molecular structure of industrially relevant hydrate antiagglomerant (AA) inhibitors on gas hydrate crystal interparticle interactions. Four AA molecules with known detailed structures [quaternary ammonium salts with two long tails (R1) and one short tail (R2)] in which the R1 has 12 carbon (C12) and 8 carbon (C8) and saturated (C-C) versus unsaturated (C═C) bonding are used in this work to investigate their interfacial activity to suppress hydrate crystal interparticle interactions in the presence of two liquid hydrocarbons (n-dodecane and n-heptane). All AAs were able to reduce the interparticle cohesive force from the baseline (23.5 ± 2.5 mN m-1), but AA-C12 shows superior performance in both liquid hydrocarbons compared to the other AAs. The interfacial measurements indicate that the AA with an R1 longer alkyl chain length can provide a denser barrier, and the AA molecules may have higher packing density when the AA R1 alkyl tail length is comparable to that of the liquid hydrocarbon chain on the gas hydrate crystal surface. Increasing the salinity can promote the effectiveness of an AA molecule and can also eliminate the effect of longer particle contact times, which typically increases the interparticle cohesive force. This work reports the first experimental investigation of high-performance known molecular structure AAs under industrially relevant conditions, showing that these molecules can reduce the interfacial tension and increase the gas hydrate-water contact angle, thereby minimizing the gas hydrate interparticle interactions. The structure-performance relation reported in this work can be used to help in the design of improved AA inhibitor molecules that will be critical to industrial hydrate crystal slurry transport.

Polysaccharides and phenolics of miscanthus belowground cell walls and their influence on polyethylene composites.

Belowground materials from two miscanthus species were ground into fragments for preparing polyethylene composites. Both species show a lot of similarities in terms of polysaccharides, lignin and cell wall-linked p-coumaric and ferulic acids contents. The structures of polysaccharides and of lignins are markedly different in the miscanthus belowground and aboveground biomass. The non-cellulosic fraction of the samples comprises a high level of xylose, with the arabinose to xylose ratio about twice as high as that observed for analogous stem samples, suggesting that belowground arabinoxylans are more substituted than stem ones. The mechanical properties of the belowground miscanthus-polyethylene composites correlate with several of their compositional traits, with similar trends as for plant stem-polyethylene composites with positive correlations for lignin and p-coumaric acid contents and negative correlations for most non-cellulosic sugars.

Synergistic and Antagonistic Effects of Aromatics on the Agglomeration of Gas Hydrates.

Surfactants are often used to stabilize aqueous dispersions. For example, surfactants can be used to prevent hydrate particles from forming large plugs that can clog, and sometimes rupture pipelines. Changes in oil composition, however dramatically affect the performance of said surfactants. In this work we demonstrate that aromatic compounds, dissolved in the hydrocarbon phase, can have both synergistic and antagonistic effects, depending on their molecular structure, with respect to surfactants developed to prevent hydrate agglomerations. While monocyclic aromatics such as benzene were found to disrupt the structure of surfactant films at low surfactant density, they are expelled from the interfacial film at high surfactant density. On the other hand, polycyclic aromatics, in particular pyrene, are found to induce order and stabilize the surfactant films both at low and high surfactant density. Based on our simulation results, polycyclic aromatics could behave as natural anti-agglomerants and enhance the performance of the specific surfactants considered here, while monocyclic aromatics could, in some cases, negatively affect performance. Although limited to the conditions chosen for the present simulations, the results, explained in terms of molecular features, could be valuable for better understanding synergistic and antagonistic effects relevant for stabilizing aqueous dispersions used in diverse applications, ranging from foodstuff to processing of nanomaterials and advanced manufacturing.

Chemical constituents of Geum urbanum L. roots.

A new dehydrodigallic acid derivative (1), along with 19 known compounds, including 6 phenolic derivatives, 2 steroids and 11 triterpenoids were isolated from the ethanol extract of the root of Geum urbanum. Herein, there is the first report of steroid and triterpene in Geum urbanum. The purified metabolites were characterised by NMR spectroscopic and mass spectrometric analyses. The identification of the known compounds (2-20) was based on the comparison of their NMR spectroscopic features with previously published data. The structural characteristics of compound 1 were elucidated by comprehensive 1D and 2D NMR spectroscopic methods and acid hydrolysis.

Isotope effects and the nature of stereo- and regioselectivity in hydroaminations of vinylarenes catalyzed by palladium(ii)-diphosphine complexes.

[reaction: see text] The hydroamination of styrene with aniline catalyzed by phosphine-ligated palladium triflates exhibits a substantial (13)C isotope effect at the benzylic carbon. This supports rate-determining nucleophilic attack of amine on a eta(3)-phenethyl palladium complex. Deuterium exchange observations and predicted isotope effects based on DFT calculations support this mechanism. Selectivity in these reactions is determined by the facility of palladium displacement after reversible hydropalladation of the alkene.

A few molecules can control the enantiomeric outcome. Evidence supporting absolute asymmetric synthesis using the Soai asymmetric autocatalysis.

[reaction: see text] Experiments were carried out to investigate whether the Soai asymmetric autocatalysis can accomplish true absolute asymmetric synthesis. In 54 reactions, R and S enantiomeric products were obtained 27 times each. Of 25 pairs of side-by-side identical reactions, 12 afforded opposite enantiomers. In a test of the mechanistic viability of a random-chance process, it was found that a very few molecules (approximately 60 000) were sufficient to control the enantiomeric outcome of these reactions. These observations appear most consistent with asymmetric synthesis originating from the chance enantiomeric excess in a racemate.

Parietal plasticity after training with a complex video game is associated with individual differences in improvements in an untrained working memory task.

Researchers have devoted considerable attention and resources to cognitive training, yet there have been few examinations of the relationship between individual differences in patterns of brain activity during the training task and training benefits on untrained tasks (i.e., transfer). While a predominant hypothesis suggests that training will transfer if there is training-induced plasticity in brain regions important for the untrained task, this theory lacks sufficient empirical support. To address this issue we investigated the relationship between individual differences in training-induced changes in brain activity during a cognitive training videogame, and whether those changes explained individual differences in the resulting changes in performance in untrained tasks. Forty-five young adults trained with a videogame that challenges working memory, attention, and motor control for 15 2-h sessions. Before and after training, all subjects received neuropsychological assessments targeting working memory, attention, and procedural learning to assess transfer. Subjects also underwent pre- and post-functional magnetic resonance imaging (fMRI) scans while they played the training videogame to assess how these patterns of brain activity change in response to training. For regions implicated in working memory, such as the superior parietal lobe (SPL), individual differences in the post-minus-pre changes in activation predicted performance changes in an untrained working memory task. These findings suggest that training-induced plasticity in the functional representation of a training task may play a role in individual differences in transfer. Our data support and extend previous literature that has examined the association between training related cognitive changes and associated changes in underlying neural networks. We discuss the role of individual differences in brain function in training generalizability and make suggestions for future cognitive training research.

Ion-interactions as driving force in polysaccharide assembly.

The structure of cellulose is characterised by extensive non-covalent interactions. Recent discussions suggest that hydrophobic interactions between polymer chains also play a significant role in governing cellulose solubility. Surprisingly in almost all cellulose shaping processes, chemical systems or solvents are applied, which base on melts or solutions of charged molecules. Ionic interactions play a significant role in the shaping and modification of cellulose based materials. Dependent on the systems used different principles govern the processes and define the results, e.g. formation of associates with alkali hydroxides, ion-exchange reactions to selectively bind multivalent ions at carboxylic groups, adsorption of dissolved polymers through surface charge neutralisation or metal complex formation, where cellulose takes the role of a polymer ligand system. Presence of charged compounds takes a significant role in cellulose swelling and dissolution, but also directs reassembly of polysaccharide material to solid three-dimensional structures.

Videogame training strategy-induced change in brain function during a complex visuomotor task.

Although changes in brain function induced by cognitive training have been examined, functional plasticity associated with specific training strategies is still relatively unexplored. In this study, we examined changes in brain function during a complex visuomotor task following training using the Space Fortress video game. To assess brain function, participants completed functional magnetic resonance imaging (fMRI) before and after 30 h of training with one of two training regimens: Hybrid Variable-Priority Training (HVT), with a focus on improving specific skills and managing task priority, or Full Emphasis Training (FET), in which participants simply practiced the game to obtain the highest overall score. Control participants received only 6 h of FET. Compared to FET, HVT learners reached higher performance on the game and showed less brain activation in areas related to visuo-spatial attention and goal-directed movement after training. Compared to the control group, HVT exhibited less brain activation in right dorsolateral prefrontal cortex (DLPFC), coupled with greater performance improvement. Region-of-interest analysis revealed that the reduction in brain activation was correlated with improved performance on the task. This study sheds light on the neurobiological mechanisms of improved learning from directed training (HVT) over non-directed training (FET), which is related to visuo-spatial attention and goal-directed motor planning, while separating the practice-based benefit, which is related to executive control and rule management.

Predicting individuals' learning success from patterns of pre-learning MRI activity.

Performance in most complex cognitive and psychomotor tasks improves with training, yet the extent of improvement varies among individuals. Is it possible to forecast the benefit that a person might reap from training? Several behavioral measures have been used to predict individual differences in task improvement, but their predictive power is limited. Here we show that individual differences in patterns of time-averaged T2*-weighted MRI images in the dorsal striatum recorded at the initial stage of training predict subsequent learning success in a complex video game with high accuracy. These predictions explained more than half of the variance in learning success among individuals, suggesting that individual differences in neuroanatomy or persistent physiology predict whether and to what extent people will benefit from training in a complex task. Surprisingly, predictions from white matter were highly accurate, while voxels in the gray matter of the dorsal striatum did not contain any information about future training success. Prediction accuracy was higher in the anterior than the posterior half of the dorsal striatum. The link between trainability and the time-averaged T2*-weighted signal in the dorsal striatum reaffirms the role of this part of the basal ganglia in learning and executive functions, such as task-switching and task coordination processes. The ability to predict who will benefit from training by using neuroimaging data collected in the early training phase may have far-reaching implications for the assessment of candidates for specific training programs as well as the study of populations that show deficiencies in learning new skills.

Enantioselective synthesis without discrete optically active additives.

By an adaptation of the asymmetric autocatalysis reactions of Soai, it was found that small enantiomeric excesses may be amplified to an arbitrary extent. When this process was applied 48 times to reactions in the absence of discrete optically active additives, all ultimately afforded substantial optical activity in the product. However, observations strongly suggest that most (and likely all) of these reactions are not true examples of absolute asymmetric synthesis. Rather, the ultimate optical activity arises from optically active impurities. Trace amounts of optically active materials may dominate the outcome of reactions involving asymmetric autocatalysis, and in the presence of opposite chiral influences a single enantiomer tends to take over a reaction. The possible implications of these observations to the origin of biological homochirality are noted.