7-(Dialkylamino)coumarin-4-yl]methyl-Caged Compounds as Ultrafast and Effective Long-Wavelength Phototriggers of 8-Bromo-Substituted Cyclic Nucleotides

[7-(Dimethylamino)coumarin-4-yl]methyl (DMACM) and [7-(diethylamino)coumarin-4-yl]methyl (DEACM) esters of 8-bromoadenosine 3',5'-cyclic monophosphate (8-Br-cAMP) and 8-bromoguanosine 3',5'-cyclic monophosphate (8-Br-cGMP) are described as novel caged compounds for 8-bromo-substituted cyclic nucleotides. Synthesis is accomplished by treatment of the free acids of the cyclic nucleotides with the corresponding 7(dialkylamino)-substituted 4(diazomethyl)coumarins. Irradiation of the DMACM- and DEACM-caged cyclic nucleotides with UV light stimulates the release of the cyclic nucleotides within roughly a nanosecond. The new caged compounds are resistant to hydrolysis in aqueous buffers and exhibit long-wavelength absorption properties with maxima at 400 nm, high extinction coefficients, and high quantum yields (0.15-0.31). Their favorable properties render these compounds the most efficient and rapid phototriggers of 8-bromo-substituted cyclic nucleotides known. The usefulness of the compounds for physiological studies under nondamaging light conditions was examined in HEK293 cells expressing the alpha subunit of the cyclic-nucleotide-gated (CNG) channel of cone photoreceptors (CNGA3) and of olfactory neurons (CNGA2) by using confocal laser scanning microscopy and the patch clamp technique.     

The chemical feeding ecology ofNeodiprion dubiosus schedl,N. rugifrons midd., andN. lecontei (Fitch) on jack pine (Pinus banksiana lamb.)

Two monophagous sawflies,Neodiprion dubiosus andN. rugifrons, actively avoid feeding on the current season's needles of jack pine,Pinus banksiana, while the polyphagousN. lecontei feeds indiscriminately on foliage of all age classes. Bioassay studies with needle extracts indicate thatN. dubiosus andN. rugifrons larval feeding preference is governed by a group of tricyclic diterpene resin acids. Resin acids commonly occur in needles of all ages; however, levopimaric, palustric, dehydroabietic, and neoabietic acids were at higher concentrations in the new needles.N. dubiosus was significantly deterred from feeding on 1-year-old foliage when treated with the pure resin acids, palustric and levopimaric, at 0.5 and 1.0 mg/ml MeOH.N. rugifrons larvae were deterred from feeding by pure dehydroabietic, neoabietic, and palustric acids at 1.0 mg/ml MeOH.     

An embedding approach for the design of state‐feedback tracking controllers for references with jumps

We study the problem of designing state‐feedback controllers to track time‐varying state trajectories that may exhibit jumps. Both plants and controllers considered are modeled as hybrid dynamical systems, which are systems with both continuous and discrete dynamics, given in terms of a flow set, a flow map, a jump set, and a jump map. Using recently developed tools for the study of stability in hybrid systems, we recast the tracking problem as the task of asymptotically stabilizing a set, the tracking set, and derive conditions for the design of state‐feedback tracking controllers with the property that the jump times of the plant coincide with those of the given reference trajectories. The resulting tracking controllers guarantee that solutions of the plant starting close to the reference trajectory stay close to it and that the difference between each solution of the controlled plant and the reference trajectory converges to zero asymptotically. Constructive conditions for tracking control design in terms of LMIs are proposed for a class of hybrid systems with linear maps and input‐triggered jumps. The results are illustrated by various examples. Copyright © 2013 John Wiley & Sons, Ltd.     

Manipulating the microstructure and rheology in polymer‐organoclay composites

A series of nanocomposites prepared by melt‐blending of cloisite‐based organoclays with poly(ethylene‐vinylacetate) (EVA) and neutralized poly (ethylene‐methacrylic acid) (EMA) copolymers were investigated via DSC, small‐angle X‐ray scattering (SAXS), and rheological techniques. SAXS results indicated partial clay exfoliation in all samples. In both EMA and EVA systems, the nominal melting temperature T_m and bulk crystallinity are not significantly affected by the presence of organoclays, suggesting that clay particles are predominantly confined in the amorphous phase. In rheological measurements (above T_m), the EVA‐clay system demonstrated a solid‐like rheological behavior under the small‐strain oscillatory shear, yet it was able to yield and flow under a steady shear, which is the characteristic of physical crosslinking. In contrast, the EMA‐clay system exhibited a melt‐like rheological behavior, where the influence of organoclay on the thermorheological behavior of the EMA composite was quite minimal. We propose that the carbonyl groups of vinylacetate in EVA interact with the clay surface, resulting in a strong physically crosslinking like interaction in the melt. On the other hand, the interaction between EMA and clay is weak because of repulsion between carboxyl anions and negatively charged clay surface.     

Relationship between structure and dynamic mechanical properties of a carbon nanofiber reinforced elastomeric nanocomposite

The tensile and dynamic mechanical properties of a nanocomposite, containing modified carbon nanofibers (MCNFs) homogenously dispersed in an elastomeric ethylene/propylene (EP) copolymer semicrystalline matrix (84.3 wt% P), have been correlated with the structure development. These properties were characterized by in situ synchrotron X-ray diffraction during stretching, dynamic mechanical analysis and X-ray analysis techniques over a wide temperature range. Upon sequential drawing, the tensile strength of the nanocomposite film was notably higher than that of the unfilled polymer even though both samples exhibited a similar amount of crystal fraction and the same degree of crystal orientation, revealing the effect of nanofiller reinforcement in the semicrystalline matrix. The mechanical spectra of the 10 wt% MCNF filled samples in both stretched and non-stretched states showed broadening of the elastic modulus at high temperatures, where the corresponding crystallinity index also decreased. It is conceivable that a significant fraction of chain orientation is induced in the vicinity of the nanofillers during stretching, and these stretched chains with reduced mobility significantly enhance the thermal mechanical properties.     

Dissolution of perfluoroalkyl oligomers in lubricating oil for enhancing wear resistance and fuel economy

Perfluorobutyl-1,1,2-tri-H-1-hexene and perfluoroalkyl methacrylate have been solubilized in lubricating oil by single-step free radically grafting onto poly(ethylene-co-propylene). Perfluoroalkyl-1,1,2,2-tetra-H-ethanol and perfluoropolyether carboxylic acid were solubilized by condensing with poly[(ethylene-co-propylene)-g-glycidyl methacrylate], generating the corresponding perfluoroalkyl ether or ester, respectively. Solubilization of 1,1,2,2-tetra-H-ethanol was also achieved by condensing with poly[(ethylene-co-propylene)-g-2-isocyanoethyl methacrylate] to the corresponding perfluoroalkyl urethane. Scar diameter reductions ranged from 9.4 to 58% using perfluoro-modified graft copolymers as determined using the Four Ball Wear Test, although optimum reductions were obtained using perfluoroalkyl urethane-modified graft copolymers. Moreover, a semiquantitative correlation of scar reductions and thermal instability was determined. Sequence VI engine testing of perfluoroalkyl urethane graft copolymers containing pendant perfluoroalkyl chain lengths of 8.2 and 7.2 had an Equivalent Fuel Economy Index of 4.33 and 4.27, respectively. © 1994 John Wiley & Sons, Inc.     

Influence of air oxidation on the pressure exerted by coking coals during carbonization

The effects of air oxidation of three Spanish coals on the pressure exerted during carbonization have been studied. Coals were oxidized by air in an oven at 120 and 140 °C. The extent of oxidation was assessed by the Audibert-Arnu dilatometer test. Coal samples oxidized at different levels were subjected to the Koppers-lncar laboratory coking pressure test. The results obtained indicated that for coals classified as ‘dangerous’ the ‘danger’ increased and reached a maximum at a certain level of oxidation, after which it decreased sharply. This behaviour did not occur with coals classified as safe.     

Breaking Bad in Cyberspace: Understanding why and how Black Hat Hackers Manage their Nerves to Commit their Virtual Crimes

Information Systems Frontiers - What is happening in hacker’s minds when they are committing criminal activities? How black hat hackers manage nerves, which is about managing fear and...     

Popular News Are Relevant News! How Investor Attention Affects Algorithmic Decision-Making and Decision Support in Financial Markets

Algorithmic decision-making plays an important role in financial markets. Current tools in trading focus on popular companies which are discussed in thousands of news items. However, it remains unclear whether methodologies from the field of data analytics relying on large samples can also be applied to small datasets of less popular companies or whether these methodologies lead to the discovery of meaningless patterns resulting in economic losses. We analyze whether the impact of media sentiment on financial markets is influenced by two levels of investor attention and whether this impacts algorithmic decision-making. We find that the influence differs substantially between news and companies with high and low investor attention. We apply a trading simulation to outline the practical consequences of these interrelations for decision support systems. Our results are of high importance for financial market participants, especially for algorithmic traders that consider sentiment for investment decision support.

     

Effects of Al:Si and (Al + Na):Si ratios on the properties of the international simple glass,part II: Structure

High-alumina containing high-level waste (HLW) will be vitrified at the Waste Treatment Plant at the Hanford Site. The resulting glasses, high in alumina, will have distinct composition-structure-property (C-S-P) relationships compared to previously studied HLW glasses. These C-S-P relationships determine the processability and product durability of glasses and therefore must be understood. The main purpose of this study is to understand the detailed structural changes caused by Al:Si and (Al + Na):Si substitutions in a simplified nuclear waste model glass (ISG, international simple glass) by combining experimental structural characterizations and molecular dynamics (MD) simulations. The structures of these two series of glasses were characterized by neutron total scattering and ²⁷Al, ²³Na, ²⁹Si, and ¹¹B solid-state nuclear magnetic resonance (NMR) spectroscopy. Additionally, MD simulations were used to generate atomistic structural models of the borosilicate glasses and simulation results were validated by the experimental structural data. Short-range (eg, bond distance, coordination number, etc) and medium-range (eg, oxygen speciation, network connectivity, polyhedral linkages) structural features of the borosilicate glasses were systematically investigated as a function of the degree of substitution. The results show that bond distance and coordination number of the cation-oxygen pairs are relatively insensitive to Al:Si and (Al + Na):Si substitutions with the exception of the B-O pair. Additionally, the Al:Si substitution results in an increase in tri-bridging oxygen species, whereas (Al + Na):Si substitution creates nonbridging oxygen species. Charge compensator preferences were found for Si-[NBO] (Na⁺), ^[3]B-[NBO] (Na⁺), ^[4]B (mostly Ca²⁺), ^[4]Al (nearly equally split Na⁺ and Ca²⁺), and ^[6]Zr (mostly Ca²⁺). The network former-BO-network former linkages preferences were also tabulated; Si-O-Al and Al-O-Al were preferred at the expense of lower Si-O-^[3]B and ^[3]B-O-^[3]B linkages. These results provide insights on the structural origins of property changes such as glass-transition temperature caused by the substitutions, providing a basis for future improvements of theoretical and computer simulation models.