Novel cyclization cascades to functionalized indanes and tetrahydronaphthalenes

Cyclization cascades involving C-C bond formations followed by lactonization reactions provide fast access to structurally complex tricyclic indane and tetrahydronaphthalene derivatives.     

Asymptotic Behavior of the Value Functions of Discrete-Time Discounted Optimal Control

We study deterministic discounted optimal control problems associated with discrete-time systems. It is shown that, for small discount rates, the controllability properties of the underlying system can guarantee the convergence of the discounted value function to the value function of the average yield. An application in the theory of exponential growth rates of discrete inclusions is presented. This application motivates the analysis of infinite-horizon optimal control problems with running yields that are unbounded from below.     

Electromagnetic and nuclear fission of238U in the reaction of 100, 500, and 1000 A·MeV208Pb with238U

The folding- and azimuthal-angle and velocity distributions for the²³⁸U fission fragments have been measured in reactions with 100, 500, and 1000 A·MeV²⁰⁸Pb. These distributions were used to decompose the fission cross section into its electromagnetic and nuclear components. The fraction of electromagnetic fission was found to be 0.16±0.07, 0.48±0.08, and 0.60±0.04, respectively. The electromagnetic fission cross section as a function of the²⁰⁸Pb nucleus energy is compared with theoretical predictions. The measured fission cross section from nuclear reactions (≈1.5 b) is approximately constant between 100 and 1000 A·MeV.     

Adlayers of dimannoside thiols on gold: surface chemical analysis

Carbohydrate films on gold based on dimannoside thiols (DMT) were prepared, and a complementary surface chemical analysis was performed in detail by X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), near-edge X-ray absorption fine structure (NEXAFS), FT-IR, and contact angle measurements in order to verify formation of ω-carbohydrate-functionalized alkylthiol films. XPS (C 1s, O 1s, and S 2p) reveals information on carbohydrate specific alkoxy (C-O) and acetal moieties (O-C-O) as well as thiolate species attached to gold. Angle-resolved synchrotron XPS was used for chemical speciation at ultimate surface sensitivity. Angle-resolved XPS analysis suggests the presence of an excess top layer composed of unbound sulfur components combined with alkyl moieties. Further support for DMT attachment on Au is given by ToF-SIMS and FT-IR analysis. Carbon and oxygen K-edge NEXAFS spectra were interpreted by applying the building block model supported by comparison to data of 1-undecanethiol, poly(vinyl alcohol), and polyoxymethylene. No linear dichroism effect was observed in the angle-resolved C K-edge NEXAFS.     

Activity-based chemical proteomics accelerates inhibitor development for deubiquitylating enzymes

Converting lead compounds into drug candidates is a crucial step in drug development, requiring early assessment of potency, selectivity, and off-target effects. We have utilized activity-based chemical proteomics to determine the potency and selectivity of deubiquitylating enzyme (DUB) inhibitors in cell culture models. Importantly, we characterized the small molecule PR-619 as a broad-range DUB inhibitor, and P22077 as a USP7 inhibitor with potential for further development as a chemotherapeutic agent in cancer therapy. A striking accumulation of polyubiquitylated proteins was observed after both selective and general inhibition of cellular DUB activity without direct impairment of proteasomal proteolysis. The repertoire of ubiquitylated substrates was analyzed by tandem mass spectrometry, identifying distinct subsets for general or specific inhibition of DUBs. This enabled identification of previously unknown functional links between USP7 and enzymes involved in DNA repair.     

The imaging ammeter

A method for measuring local current density, not requiring segmentation of the electrode or spatial scanning, is presented. The motion of colloidal particles in response to local current density, characterized by the intensity of the light they scatter, is the fundamental phenomenon of the technique. The scattering was produced and measured with the electrochemical total internal reflection microscope, a tool that places an electrochemical cell within a total internal reflection apparatus. The electrolysis of water and the oxidation of ferrocene monocarboxylic acid were used as test reactions. Light scattered by a probe particle produced an "image" of current density; scattered light was converted to local current density by a function derived herein. Numerical simulations supplemented experimental evidence that local current density controlled the probe particle's vertical motion. The spatial resolution of the method was approximately the length scale of the probe particle, in this case 5.7 μm. The resolution of current density was better than 100 nA cm(-2). The method might find use in high throughput screening of electrocatalysts.     

Tuning the light absorption of a molecular vanadium oxide system for enhanced photooxidation performance

A new mechanism for enhancing the visible light absorption of a homogeneous polyoxovanadate system is described. The photoactive pentanuclear {V(5)} isopolyoxovanadate cluster is formed in situ by a thermally-induced condensation reaction starting from a tetranuclear {V(4)} precursor. Upon irradiation with visible light, {V(5)} undergoes a light induced reduction reaction resulting in the formation of a 2-electron reduced {V(10)} cluster. Simultaneously, the oxidant methanol is selectively oxidized to formaldehyde. The {V(10)} cluster can subsequently be re-oxidized using H(2)O(2) or O(2).