On the fly multi-modal observation of ligand synthesis and complexation of Cu complexes in flow with ‘benchtop’ NMR and mass spectrometry

Exploring complex chemical systems requires reproducible and controllable ways to access non-equilibrium conditions. Herein we present a programmable flow system that can do both ligand synthesis and complexation on the fly, and the conditions of the reaction can be monitored using two simultaneous techniques, namely NMR and mass spectrometry. By using this approach we monitored the formation of unknown complexes, followed by crystallization that resulted in the characterisation of their structures giving 5 new compounds (4 isolated and fully characterised) which can be formulated as: Cu2(L1)4(μ-CO3)](BF4)2 (2); [Cu3(L1)6(μ-CO3)](PF6)2(OH)2 (3) [Cu2(L2)2](BF4)2 (4) and [Cu(L2)2](BF4)2·CH3CN (5)

Age of second language acquisition affects nonverbal conflict processing in children : an fMRI study

Background: In their daily communication, bilinguals switch between two languages, a process that involves the selection of a target language and minimization of interference from a nontarget language. Previous studies have uncovered the neural structure in bilinguals and the activation patterns associated with performing verbal conflict tasks. One question that remains, however is whether this extra verbal switching affects brain function during nonverbal conflict tasks. Methods: In this study, we have used fMRI to investigate the impact of bilingualism in children performing two nonverbal tasks involving stimulus-stimulus and stimulus-response conflicts. Three groups of 8-11-year-old children - bilinguals from birth (2L1), second language learners (L2L), and a control group of monolinguals (1L1) - were scanned while performing a color Simon and a numerical Stroop task. Reaction times and accuracy were logged. Results: Compared to monolingual controls, bilingual children showed higher behavioral congruency effect of these tasks, which is matched by the recruitment of brain regions that are generally used in general cognitive control, language processing or to solve language conflict situations in bilinguals (caudate nucleus, posterior cingulate gyrus, STG, precuneus). Further, the activation of these areas was found to be higher in 2L1 compared to L2L. Conclusion: The coupling of longer reaction times to the recruitment of extra language-related brain areas supports the hypothesis that when dealing with language conflicts the specialization of bilinguals hampers the way they can process with nonverbal conflicts, at least at early stages in life

Spectral geometry as a probe of quantum spacetime

Employing standard results from spectral geometry, we provide strong evidence that in the classical limit the ground state of three-dimensional causal dynamical triangulations is de Sitter spacetime. This result is obtained by measuring the expectation value of the spectral dimension on the ensemble of geometries defined by these models, and comparing its large scale behaviour to that of a sphere (Euclidean de Sitter). From the same measurement we are also able to confirm the phenomenon of dynamical dimensional reduction observed in this and other approaches to quantum gravity -- the first time this has been done for three-dimensional causal dynamical triangulations. In this case, the value for the short-scale limit of the spectral dimension that we find is approximately 2. We comment on the relevance of these results for the comparison to asymptotic safety and Horava-Lifshitz gravity, among other approaches to quantum gravity.Comment: 25 pages, 6 figures. Version 2: references to figures added, acknowledgment added

Multilevel Aggregation Methods for Small-World Graphs with Application to Random-Walk Ranking

We describe multilevel aggregation in the specific context of using Markov chains to rank the nodes of graphs. More generally, aggregation is a graph coarsening technique that has a wide range of possible uses regarding information retrieval applications. Aggregation successfully generates efficient multilevel methods for solving nonsingular linear systems and various eigenproblems from discretized partial differential equations, which tend to involve mesh-like graphs. Our primary goal is to extend the applicability of aggregation to similar problems on small-world graphs, with a secondary goal of developing these methods for eventual applicability towards many other tasks such as using the information in the hierarchies for node clustering or pattern recognition. The nature of small-world graphs makes it difficult for many coarsening approaches to obtain useful hierarchies that have complexity on the order of the number of edges in the original graph while retaining the relevant properties of the original graph. Here, for a set of synthetic graphs with the small-world property, we show how multilevel hierarchies formed with non-overlapping strength-based aggregation have optimal or near optimal complexity. We also provide an example of how these hierarchies are employed to accelerate convergence of methods that calculate the stationary probability vector of large, sparse, irreducible, slowly-mixing Markov chains on such small-world graphs. The stationary probability vector of a Markov chain allows one to rank the nodes in a graph based on the likelihood that a long random walk visits each node. These ranking approaches have a wide range of applications including information retrieval and web ranking, performance modeling of computer and communication systems, analysis of social networks, dependability and security analysis, and analysis of biological systems

Spacelike distance from discrete causal order

Any discrete approach to quantum gravity must provide some prescription as to how to deduce continuum properties from the discrete substructure. In the causal set approach it is straightforward to deduce timelike distances, but surprisingly difficult to extract spacelike distances, because of the unique combination of discreteness with local Lorentz invariance in that approach. We propose a number of methods to overcome this difficulty, one of which reproduces the spatial distance between two points in a finite region of Minkowski space. We provide numerical evidence that this definition can be used to define a `spatial nearest neighbor' relation on a causal set, and conjecture that this can be exploited to define the length of `continuous curves' in causal sets which are approximated by curved spacetime. This provides evidence in support of the ``Hauptvermutung'' of causal sets.Comment: 32 pages, 16 figures, revtex4; journal versio

Quantum Dynamics without the Wave Function

When suitably generalized and interpreted, the path-integral offers an alternative to the more familiar quantal formalism based on state-vectors, selfadjoint operators, and external observers. Mathematically one generalizes the path-integral-as-propagator to a {\it quantal measure} $\mu$ on the space $\Omega$ of all ``conceivable worlds'', and this generalized measure expresses the dynamics or law of motion of the theory, much as Wiener measure expresses the dynamics of Brownian motion. Within such ``histories-based'' schemes new, and more ``realistic'' possibilities open up for resolving the philosophical problems of the state-vector formalism. In particular, one can dispense with the need for external agents by locating the predictive content of $\mu$ in its sets of measure zero: such sets are to be ``precluded''. But unrestricted application of this rule engenders contradictions. One possible response would remove the contradictions by circumscribing the application of the preclusion concept. Another response, more in the tradition of ``quantum logic'', would accommodate the contradictions by dualizing $\Omega$ to a space of ``co-events'' and effectively identifying reality with an element of this dual space.Comment: plainTeX, 24 pages, no figures. To appear in a special volume of {\it Journal of Physics A: Mathematical and General} entitled ``The Quantum Universe'' and dedicated to Giancarlo Ghirardi on the occasion of his 70th birthday. Most current version is available at http://www.physics.syr.edu/~sorkin/some.papers/ (or wherever my home-page may be

Age Differentiation within Gray Matter, White Matter, and between Memory and White Matter in an Adult Life Span Cohort.

It is well established that brain structures and cognitive functions change across the life span. A long-standing hypothesis called "age differentiation" additionally posits that the relations between cognitive functions also change with age. To date, however, evidence for age-related differentiation is mixed, and no study has examined differentiation of the relationship between brain and cognition. Here we use multigroup structural equation models (SEMs) and SEM trees to study differences within and between brain and cognition across the adult life span (18-88 years) in a large (N > 646, closely matched across sexes), population-derived sample of healthy human adults from the Cambridge Centre for Ageing and Neuroscience (www.cam-can.org). After factor analyses of gray matter volume (from T1- and T2-weighted MRI) and white matter organization (fractional anisotropy from diffusion-weighted MRI), we found evidence for the differentiation of gray and white matter, such that the covariance between brain factors decreased with age. However, we found no evidence for age differentiation among fluid intelligence, language, and memory, suggesting a relatively stable covariance pattern among cognitive factors. Finally, we observed a specific pattern of age differentiation between brain and cognitive factors, such that a white matter factor, which loaded most strongly on the hippocampal cingulum, became less correlated with memory performance in later life. These patterns are compatible with the reorganization of cognitive functions in the face of neural decline, and/or with the emergence of specific subpopulations in old age.SIGNIFICANCE STATEMENT The theory of age differentiation posits age-related changes in the relationships among cognitive domains, either weakening (differentiation) or strengthening (dedifferentiation), but evidence for this hypothesis is mixed. Using age-varying covariance models in a large cross-sectional adult life span sample, we found age-related reductions in the covariance among both brain measures (neural differentiation), but no covariance change among cognitive factors of fluid intelligence, language, and memory. We also observed evidence of uncoupling (differentiation) between a white matter factor and cognitive factors in older age, most strongly for memory. Together, our findings support age-related differentiation as a complex, multifaceted pattern that differs for brain and cognition, and discuss several mechanisms that might explain the changing relationship between brain and cognition

Classifying the precancers: A metadata approach

BACKGROUND: During carcinogenesis, precancers are the morphologically identifiable lesions that precede invasive cancers. In theory, the successful treatment of precancers would result in the eradication of most human cancers. Despite the importance of these lesions, there has been no effort to list and classify all of the precancers. The purpose of this study is to describe the first comprehensive taxonomy and classification of the precancers. As a novel approach to disease classification, terms and classes were annotated with metadata (data that describes the data) so that the classification could be used to link precancer terms to data elements in other biological databases. METHODS: Terms in the UMLS (Unified Medical Language System) related to precancers were extracted. Extracted terms were reviewed and additional terms added. Each precancer was assigned one of six general classes. The entire classification was assembled as an XML (eXtensible Mark-up Language) file. A Perl script converted the XML file into a browser-viewable HTML (HyperText Mark-up Language) file. RESULTS: The classification contained 4700 precancer terms, 568 distinct precancer concepts and six precancer classes: 1) Acquired microscopic precancers; 2) acquired large lesions with microscopic atypia; 3) Precursor lesions occurring with inherited hyperplastic syndromes that progress to cancer; 4) Acquired diffuse hyperplasias and diffuse metaplasias; 5) Currently unclassified entities; and 6) Superclass and modifiers. CONCLUSION: This work represents the first attempt to create a comprehensive listing of the precancers, the first attempt to classify precancers by their biological properties and the first attempt to create a pathologic classification of precancers using standard metadata (XML). The classification is placed in the public domain, and comment is invited by the authors, who are prepared to curate and modify the classification

Parallel Unsmoothed Aggregation Algebraic Multigrid Algorithms on GPUs

We design and implement a parallel algebraic multigrid method for isotropic graph Laplacian problems on multicore Graphical Processing Units (GPUs). The proposed AMG method is based on the aggregation framework. The setup phase of the algorithm uses a parallel maximal independent set algorithm in forming aggregates and the resulting coarse level hierarchy is then used in a K-cycle iteration solve phase with a $\ell^1$-Jacobi smoother. Numerical tests of a parallel implementation of the method for graphics processors are presented to demonstrate its effectiveness.Comment: 18 pages, 3 figure