Spectral Data for Generation of Molecular Complexity from Cyclooctatetraene: Preparation of Optically Active Protected Aminocycloheptitols and Bicyclo[4.4.1]undecatriene

Spectral data created in the course of the research project. Supports specific findings in Generation of Molecular Complexity from Cyclooctatetraene: Preparation of Optically Active Protected Aminocycloheptitols and Bicyclo[4.4.1]undecatriene . The racemic (6-cyclo-heptadienyl)Fe(CO)3+ cation ((±)-7), prepared from cyclooctatetraene, was treated with a variety of carbon and heteroatom nucleophiles. Attack took place at the less hindered C1 dienyl carbon and decomplexation of the (cycloheptadiene)Fe(CO)3 complexes gave products rich in functionality for further synthetic manipulation. In particular, a seven-step route was developed from racemic (6-styryl-2,4-cycloheptadien-1-yl)phthalimide ((±)-9 d) to afford the optically active aminocycloheptitols (−)-20 and (+)-20

Generation of Molecular Complexity from Cyclooctatetraene: Preparation of Optically Active Protected Aminocycloheptitols and Bicyclo[4.4.1]undecatriene

The racemic (6-cyclo-heptadienyl)Fe(CO)3+ cation ((±)-7), prepared from cyclooctatetraene, was treated with a variety of carbon and heteroatom nucleophiles. Attack took place at the less hindered C1 dienyl carbon and decomplexation of the (cycloheptadiene)Fe(CO)3 complexes gave products rich in functionality for further synthetic manipulation. In particular, a seven-step route was developed from racemic (6-styryl-2,4-cycloheptadien-1-yl)phthalimide ((±)-9 d) to afford the optically active aminocycloheptitols (−)-20 and (+)-20

Macroscopic 2D Wigner islands

In this paper we present new versatile "2D macroscopic Wigner islands" useful to investigate the various behaviors observed in mesoscopic confined systems. Our "Wigner islands" consist of electrostatically-interacting charged balls with millimetric size. We have experimentally determined the ground configurations for systems of N particles (N=1-30) confined in a parabolic potential and checked the influence of the confinement and interacting potentials. The results obtained are compared with the published numerical results.Comment: 8 pages, 4 figure

Synthesis of 12-Membered and 13-Membered Sulfur-Containing Lactones by Homolytic Macrocyclization of Mercaptoacetic Esters with Alkynes

Starting from mercaptoacetic acid esters of 1,2- or 1,3-diols and substituted acetylenes 12- and 13-membered sulfur-containing lactones as 1:1 adducts were synthesized in yields up to 48%. The mechanism of this homolytic reaction, which is initiated by the tripropylborane/oxygen system, includes generation of thiyl radicals and their addition to the triple bond of alkynes

Charge Delocalization in Self-Assembled Mixed-Valence Aromatic Cation Radicals

The spontaneous assembly of aromatic cation radicals (D+•) with their neutral counterpart (D) affords dimer cation radicals (D2+•). The intermolecular dimeric cation radicals are readily characterized by the appearance of an intervalence charge-resonance transition in the NIR region of their electronic spectra and by ESR spectroscopy. The X-ray crystal structure analysis and DFT calculations of a representative dimer cation radical (i.e., the octamethylbiphenylene dimer cation radical) have established that a hole (or single positive charge) is completely delocalized over both aromatic moieties. The energetics and the geometrical considerations for the formation of dimer cation radicals is deliberated with the aid of a series of cyclophane-like bichromophoric donors with drastically varied interplanar angles between the cofacially arranged aryl moieties. X-ray crystallography of a number of mixed-valence cation radicals derived from monochromophoric benzenoid donors established that they generally assemble in 1D stacks in the solid state. However, the use of polychromophoric intervalence cation radicals, where a single charge is effectively delocalized among all of the chromophores, can lead to higher-order assemblies with potential applications in long-range charge transport. As a proof of concept, we show that a single charge in the cation radical of a triptycene derivative is evenly distributed on all three benzenoid rings and this triptycene cation radical forms a 2D electronically coupled assembly, as established by X-ray crystallography

Supernatural belief is not modulated by intuitive thinking style or cognitive inhibition

According to the Intuitive Belief Hypothesis, supernatural belief relies heavily on intuitive thinking—and decreases when analytic thinking is engaged. After pointing out various limitations in prior attempts to support this Intuitive Belief Hypothesis, we test it across three new studies using a variety of paradigms, ranging from a pilgrimage field study to a neurostimulation experiment. In all three studies, we found no relationship between intuitive or analytical thinking and supernatural belief. We conclude that it is premature to explain belief in gods as ‘intuitive’, and that other factors, such as socio-cultural upbringing, are likely to play a greater role in the emergence and maintenance of supernatural belief than cognitive style

Direct measurement of warm Atlantic Intermediate Water close to the grounding line of Nioghalvfjerdsfjorden (79N) Glacier, North-east Greenland"

The Northeast Greenland Ice Stream has recently seen significant change to its floating margins and has been identified as vulnerable to future climate warming. Inflow of warm Atlantic Intermediate Water (AIW) from the continental shelf has been observed in the vicinity of the Nioghalvfjerdsfjorden (79gg€¯N) Glacier calving front, but AIW penetration deep into the ice shelf cavity has not been observed directly. Here, we report temperature and salinity measurements from profiles in an epishelf lake, which provide the first direct evidence of AIW proximal to the grounding line of 79gg€¯N Glacier, over 50g€¯km from the calving front. We also report evidence for partial un-grounding of the margin of 79gg€¯N Glacier taking place at the western end of the epishelf lake. Comparison of our measurements to those close to the calving front shows that AIW transits the cavity to reach the grounding line within a few months. The observations provide support for modelling studies that infer AIW-driven basal melt proximal to the grounding line and demonstrate that offshore oceanographic changes can be rapidly transmitted throughout the sub-ice-shelf cavity, with implications for near-future stability of the ice stream

Phenotypic Modulation of Smooth Muscle Cells in Atherosclerosis Is Associated With Downregulation of LMOD1, SYNPO2, PDLIM7, PLN, and SYNM

OBJECTIVE: Key augmented processes in atherosclerosis have been identified, whereas less is known about downregulated pathways. Here, we applied a systems biology approach to examine suppressed molecular signatures, with the hypothesis that they may provide insight into mechanisms contributing to plaque stability. APPROACH AND RESULTS: Muscle contraction, muscle development, and actin cytoskeleton were the most downregulated pathways (false discovery rate=6.99e-21, 1.66e-6, 2.54e-10, respectively) in microarrays from human carotid plaques (n=177) versus healthy arteries (n=15). In addition to typical smooth muscle cell (SMC) markers, these pathways also encompassed cytoskeleton-related genes previously not associated with atherosclerosis. SYNPO2, SYNM, LMOD1, PDLIM7, and PLN expression positively correlated to typical SMC markers in plaques (Pearson r>0.6, P0.8, P<0.0001). By immunohistochemistry, the proteins were expressed in SMCs in normal vessels, but largely absent in human plaques and intimal hyperplasia. Subcellularly, most proteins localized to the cytoskeleton in cultured SMCs and were regulated by active enhancer histone modification H3K27ac by chromatin immunoprecipitation-sequencing. Functionally, the genes were downregulated by PDGFB (platelet-derived growth factor beta) and IFNg (interferron gamma), exposure to shear flow stress, and oxLDL (oxidized low-density lipoprotein) loading. Genetic variants in PDLIM7, PLN, and SYNPO2 loci associated with progression of carotid intima-media thickness in high-risk subjects without symptoms of cardiovascular disease (n=3378). By eQTL (expression quantitative trait locus), rs11746443 also associated with PDLIM7 expression in plaques. Mechanistically, silencing of PDLIM7 in vitro led to downregulation of SMC markers and disruption of the actin cytoskeleton, decreased cell spreading, and increased proliferation. CONCLUSIONS: We identified a panel of genes that reflect the altered phenotype of SMCs in vascular disease and could be early sensitive markers of SMC dedifferentiation

Cerebellar purkinje cells can differentially modulate coherence between sensory and motor cortex depending on region and behavior

Activity of sensory and motor cortices is essential for sensorimotor integration. In particular, coherence between these areas may indicate binding of critical functions like perception, motor planning, action, or sleep. Evidence is accumulating that cerebellar output modulates cortical activity and coherence, but how, when, and where it does so is unclear. We studied activity in and coherence between S1 and M1 cortices during whisker stimulation in the absence and presence of optogenetic Purkinje cell stimulation in crus 1 and 2 of awake mice, eliciting strong simple spike rate modulation. Without Purkinje cell stimulation, whisker stimulation triggers fast responses in S1 and M1 involving transient coherence in a broad spectrum. Simultaneous stimulation of Purkinje cells and whiskers affects amplitude and kinetics of sensory responses in S1 and M1 and alters the estimated S1–M1 coherence in theta and gamma bands, allowing bidirectional control dependent on behavioral context. These effects are absent when Purkinje cell activation is delayed by 20 ms. Focal stimulation of Purkinje cells revealed site specificity, with cells in medial crus 2 showing the most prominent and selective impact on estimated coherence, i.e., a strong suppression in the gamma but not the theta band. Granger causality analyses and computational modeling of the involved networks suggest that Purkinje cells control S1–M1 phase consistency predominantly via ventrolateral thalamus and M1. Our results indicate that activity of sensorimotor cortices can be dynamically and functionally modulated by specific cerebellar inputs, highlighting a widespread role of the cerebellum in coordinating sensorimotor behavior

The dangers of using intention as a surrogate for Retention in brand positioning decision support systems

The purpose of this paper is to explore the dangers of using intention as a surrogate for retention in a decision support system (DSS) for brand positioning. An empirical study is conducted, using structural equations modeling and both data from the internal transactional database and a survey. The study is aimed at evaluating whether the DSS recommends different product benefits for brand positioning when intention is used as opposed to retention as a criterion variable. The results show that different product benefits are recommended contingent upon the criterion variable (intention vs. retention). The findings also indicate that the strength of the structural relationships is inflated when intention is used. This study is limited in that it investigates only one industry; the newspaper industry. This study provides guidance for brand managers in selecting the most appropriate benefit for brand positioning and advices against the use of intention as opposed to retention in DSS. To the best of our knowledge this study is the first to challenge and refute the commonly held belief that intention is a valid surrogate for retention in a DSS for brand positioning