Refoldable Foldamers: Global Conformational Switching by Deletion or Insertion of a Single Hydrogen Bond

Small changes in the structure of a foldamer may lead to gross changes in conformational preference. We show that the simple insertion or deletion of a single hydrogen bond by changes in pH or by photochemical deprotection is sufficient to refold a helical oligomer, interconverting M and P screw‐sense preference. As a consequence of the switch, information may be transmitted to a remote catalytic site, selectively directing the formation of either of two enantiomeric products by a reaction involving 1,22‐remote intermolecular asymmetric induction.     

Diagnosing laser-driven,shock-heated foam target with Al absorption spectroscopy on OMEGA EP

Results on diagnoses of laser-driven, shock-heated foam plasma with time-resolved Al 1s-2p absorption spectroscopy are reported. Experiments were carried out to produce a platform for the study of relativistic electron transport. In cone-guided Fast Ignition (FI), relativistic electrons generated by a high-intensity, short-pulse igniter beam must be transported through a cone tip to an imploded core. Transport of the energetic electrons could be significantly affected by the temperature-dependent resistivity of background plasmas. The experiment was conducted using four UV beams of the OMEGA EP laser at the Laboratory For Laser Energetics. One UV beam (1.2 kJ, 3.5 ns square) was used to launch a shock wave into a foam package target, consisting of 200 mg/cm³ CH foam with aluminum dopant and a solid plastic container surrounding the foam layer. The other three UV beams with the total energy of 3.2 kJ in 2.5 ns pulse duration were tightly focused onto a Sm dot target to produce a point X-ray source in the energy range of 1.4–1.6 keV. The quasi-continuous X ray signal was transmitted through the shock-heated Al-doped, foam layer and recorded with an X-ray streak camera. The measured 1s-2p Al absorption features were analyzed using an atomic physics code FLYCHK. Electron temperature of 40 eV inferred from the spectral analysis is consistent with 2-D DRACO Radiation-hydrodynamic simulations.     

Potential of CE for the determination of inorganic and acidic anions in cyanoacrylate adhesives

In this work, a CZE method with indirect UV detection was developed for the simultaneous determination of the inorganic and acidic anions, chloride, sulfate, nitrate, fluoride, formate, phosphate, diethylphosphate, methyl sulfonate, cyanoacetate, and methacrylate present in cyanoacrylate adhesives. Chromate was employed as the probe ion, and the EOF was reversed by incorporating CTAB into BGE. Detection limits of 0.7-4.6 microg/mL were obtained for all the anions studied. The CE method developed is a significant improvement on traditionally used chromatographic methods such as ion chromatography, as it resulted in shorter analysis times with enhanced separation efficiencies. This method was successfully employed for the analysis of inorganic and acidic anions in cyanoacrylate adhesive samples.     

Microscale features and surface chemical functionality patterned by electron beam lithography: a novel route to poly(dimethylsiloxane) (PDMS) stamp fabrication

Poly(dimethylsiloxane) (PDMS) has become a ubiquitous material for microcontact printing, yet there are few methods available to pattern a completed PDMS stamp in a single step. It is shown here that electron beam lithography (EBL) is effective in writing patterns directly onto cured PDMS stamps, thus overcoming the need for multiple patterning steps. Not only does this method allow the modification of an existing lithographic pattern, but new 3D features such as cones, pits, and channels can also be fabricated. EBL can also be used to fabricate PDMS masks for photolithography whereby 1:1 pattern transfer into a photoresist is achieved. Additionally, direct EBL writing of surface chemical features has been achieved using a PDMS stamp coated with a self-assembled monolayer. An electrostatic mechanism appears to be operative in the EBL patterning process, as supported by calculations, thermogravimetric analysis, time-of-flight secondary ion mass spectroscopy, optical and atomic force microscopy, and chemical functionalization assays.     

A second generation mesoscopic lipid bilayer model: connections to field-theory descriptions of membranes and nonlocal hydrodynamics

A new mesoscopic membrane model is developed in order to examine long-wavelength structural and dynamical membrane phenomena. Two different explicit mesoscopic solvent models are employed. The first mesoscopic solvent is denoted the big liquid oscillating blob system, which is parametrized to model water at a coarse-grained level and is motivated by a Langevin-like approach; the resulting membrane dynamics predict a solvent viscosity dependence consistent with the known viscosity of water. The second mesoscopic solvent is a Weeks-Chandler-Anderson model. Here, it is found that the correct mesoscopic hydrodynamic scaling of the membrane undulation dynamics is still preserved, although accelerated. When the behavior of the two membranes in close proximity to one another is examined, very little correlated motion is observed. However, the theoretically predicted scaling of the entropic undulation energy is confirmed, demonstrating that the entropic interaction between two membranes becomes increasingly repulsive with decreasing separation.     

Stereoselective synthesis of 2-dienyl-substituted pyrrolidines using an eta4-dienetricarbonyliron complex as the stereodirecting element: Elaboration to the pyrrolizidine skeleton

Primary amines react with keto-aldehyde functionality located in the side-chain of an eta4-dienetricarbonyliron complex to provide the corresponding pyrrolidines in excellent diastereoselectivity. Two of the pyrrolidine products, 1i and 1k, have been elaborated into pyrrolizidines using a 1,5-C-H insertion and radical cyclization strategy, respectively.     

Concise synthesis of 22-hydroxyacuminatine, cytotoxic camptothecinoid from Camptotheca acuminata, by pyridone benzannulation

A short, efficient synthesis of 22-hydroxyacuminatine, starting from a readily accessible hydroxy pyridone, is presented; key steps include a Heck coupling with methyl pentadienoate, a flash vacuum pyrolytic cyclization, and a Friedl?nder condensation.     

Impulsive differential equations with Gamma distributed moments of impulses and p-moment exponential stability

Differential equations with impulses at random moments are set up and investigated. We study the case of Gamma distributed random moments of impulses. Several properties of solutions are studied based on properties of Gammma distributions. Some sufficient conditions for p-moment exponential stability of the solutions are given.     

In search of goals: increasing ice hockey’s attractiveness by a sides swap

The popularity and business impact of major sports have been growing globally over time. This paper focuses on ice hockey, specifically the National Hockey League in North America. It reports a striking irregularity in ice hockey’s scoring dynamics relative to comparable sports such as soccer and rugby, namely a scoring surge in the middle section of the game. We explore an explanation for this irregularity related to the convention on the spatial location of the teams’ benches (which are fixed throughout the game) and on-ice sides (which are switched every period). Because a large number of the players’ substitutions occur while the play is in progress, this convention determines the distance forwards and defenders need to travel to make a substitution, and thus indirectly substitution strategies and scoring. We consider two simple operational changes that could increase the number of goals in the NHL by approximately 5 and 10%, respectively, corresponding to roughly 350 and 700 additional goals each season. This would partly offset the current downward scoring trend and thus enhance the game’s attractiveness. The estimated impact of the proposed reforms, one of which is largely costless, is robust across several specifications—using per-minute and per-second scoring data and controlling for various factors, such as bookmakers’ odds.