An Interwoven Metal‐Organic Framework Combining Mechanically Interlocked Linkers and Interpenetrated Networks

New dibenzo[24]crown‐8 ether derivatives were prepared that contain appendages with thioether donors that can coordinate to a metal ion. These macrocycles were then combined with 1,2‐bis(pyridinium) ethane axles to create two types of [2]rotaxane ligands; those with the four thioether donors on the crown ether and those with six donor groups, four from the crown ether and two more attached to the stoppering groups of the dumbbell. The crown ethers and both types of [2]rotaxane ligands were allowed to react with Ag^I ions to form metal‐organic rotaxane framework (MORF) style coordination polymers. The interlocked hexadentate ligand forms the first example of a new type of lattice containing interwoven frameworks resulting from both interpenetration of frameworks due to the presence of an interlocked ligand and more classical interpenetration of independent frameworks.     

Using a cognitive architecture with a physiological substrate to represent effects of a psychological stressor on cognition

Adding a physiological representation to a cognitive architecture offers an attractive approach to modeling the effects of stress on cognition. We introduce ACT-R/Φ, an extended version of the ACT-R cognitive architecture that includes an integrative model of physiology. The extension allows the representation of how physiology and cognition interact. This substrate was used to represent potential effects of a startle response and task-based stress during a mental arithmetic (subtraction) task. We compare predictions from two models loaded into the new hybrid architecture to models previously developed within ACT-R. General behavior differed between models in that the ACT-R/Φ models had dynamic declarative memory noise over the course of the task based on varying epinephrine levels. They attempted more subtractions but were less accurate; this more closely matched human performance than the previous ACT-R models. Using ACT-R/Φ allows a more tractable integration of current physiological and cognitive perspectives on stress. ACT-R/Φ also permits further exploration of the interaction between cognition and physiology, and the emergent effects on behavior caused by the interaction among physiological subsystems. This extension is useful for anyone exploring how the human mind can occur in and be influenced by the physical universe.     

Nucleoside and oligonucleotide pyrene conjugates with 1,2,3-triazolyl or ethynyl linkers: synthesis,duplex stability,and fluorescence changes generated by the DNA-dye connector

Fluorescent nucleosides and oligonucleotides functionalized with pyrene were synthesized using ‘click’ chemistry or the Sonogashira cross-coupling reaction. The dye was connected to position-7 of 7-deaza-2′-deoxyguanosine or to the 2′-deoxyribofuranose moiety. Four different DNA-dye connectors with 1,2,3-triazolyl residues or triple bonds were constructed. Phosphoramidites of the pyrene conjugates (9, 14, 25) were prepared and used in solid-phase synthesis. Short linkers (2, 4) destabilize DNA, while long linkers (1) increased duplex stability. Nucleosides and oligonucleotides with single dye incorporations show linker dependent fluorescence. Linker dependent excimer emission with pyrenes in proximal positions was also observed. A ‘superchromophore’ formed by the 7-deaza-2′-deoxyguanosine ethynylpyrene conjugate shows strong red shifted fluorescence emission at 495 nm.     

Total synthesis of lansiumamides A and B and alatamide

The total syntheses of lansiumamide A, lansiumamide B and alatamide have been completed taking advantage of the dihalo-olefination of N-formylimides. The syntheses are convergent, flexible and allow for the generation of analogues not accessible through other routes.     

Two-loop virtual top-quark effect on Higgs-boson decay to bottom quarks

In most of the mass range encompassed by the limits from the direct search and the electroweak precision tests, the Higgs boson of the standard model preferably decays to bottom quarks. We present, in analytic form, the dominant two-loop electroweak correction, of O(GF2mt4), to the partial width of this decay. It amplifies the familiar enhancement due to the O(GFmt2) one-loop correction by about +16% and thus more than compensates the screening by about -8% through strong-interaction effects of order O(alphasGFmt2).     

Ultrabroadband continuum amplification in the near infrared using BiB3O6 nonlinear crystals pumped at 800 nm

Ultrabroadband parametric amplification of a white-light continuum in the near IR (approximately 100 THz, 1.2-2.4 microm) is demonstrated in BiB3O6 pumped by 45 fs long pulses at 800 nm at a repetition rate of 1 kHz. The energy obtained with a 5 mm thick crystal reached 50 microJ, corresponding to external conversion efficiency of 20%.