Divergent pathways of β,γ-unsaturated α-diazocarbonyl compounds catalyzed by dirhodium and Lewis acids catalysts separately or in combination

β,γ-Unsaturated a-diazocarbonyl compounds possess two reactive sites for electrophilic addition-one at the diazo carbon and the other at the vinylogous γ-position.Controlled by catalyst,divergent transformations are achieved starting from the same starting materials,either by Lewis acid-catalyzed addition or by dirhodium-catalyzed metal carbene reactions.In select cases two catalysts working in combination or in sequence provide a relay for cascade transformations.In this review,we summarize advances in catalyst-dependent divergent transformations of β,γ-unsaturated α-diazocarbonyl compounds and highlight the potential of this exciting research area and the many challenges that remain.     

Programming With Models: Writing Statistical Algorithms for General Model Structures With NIMBLE

We describe NIMBLE, a system for programming statistical algorithms for general model structures within R. NIMBLE is designed to meet three challenges: flexible model specification, a language for programming algorithms that can use different models, and a balance between high-level programmability and execution efficiency. For model specification, NIMBLE extends the BUGS language and creates model objects, which can manipulate variables, calculate log probability values, generate simulations, and query the relationships among variables. For algorithm programming, NIMBLE provides functions that operate with model objects using two stages of evaluation. The first stage allows specialization of a function to a particular model and/or nodes, such as creating a Metropolis-Hastings sampler for a particular block of nodes. The second stage allows repeated execution of computations using the results of the first stage. To achieve efficient second-stage computation, NIMBLE compiles models and functions via C++, using the Eigen library for linear algebra, and provides the user with an interface to compiled objects. The NIMBLE language represents a compilable domain-specific language (DSL) embedded within R. This article provides an overview of the design and rationale for NIMBLE along with illustrative examples including importance sampling, Markov chain Monte Carlo (MCMC) and Monte Carlo expectation maximization (MCEM). Supplementary materials for this article are available online.     

Why is Rose Bengal More Phototoxic to Fibroblasts In Vitro Than In Vivo?

Photosensitized protein cross‐linking has been recently developed to seal wounds and strengthen tissue. Although the photosensitizing dye, Rose Bengal (RB), is phototoxic to cultured cells, cytotoxicity does not accompany RB‐photosensitized tissue repair in vivo. We investigated whether the environment surrounding cells in tissue or the high irradiances used for photo–cross‐linking inhibited RB phototoxicity. Fibroblasts (FB) grown within collagen gels to mimic a tissue environment and monolayer cultured FB were treated with RB (0.01–1 mm ) and the high 532 nm laser irradiances used in vivo for tissue repair (0.10–0.50 W cm^?2). Monolayer FB were substantially more sensitive to RB photosensitization: the LD₅₀ was >200‐fold lower than that in collagen gels. Collagen gel protection was associated with increased Akt phosphorylation, a prosurvival pathway. RB phototoxicity in collagen gels was 25‐fold greater at low (0.030 W cm^?2) that at high (0.50 W cm^?2) irradiances. Oxygen depletion at high irradiance only partially accounted for the irradiance dependence of phototoxicity as replacing air with nitrogen only increased the LD₅₀ by four‐fold in monolayers. These results indicate that the lack of RB phototoxicity during in vivo tissue repair results from upregulation of prosurvival pathways in tissue cells, oxygen depletion and irradiance‐dependent RB photochemistry.     

Asymmeric formal [3 + 3]-cycloaddition reactions of nitrones with electrophilic vinylcarbene intermediates

With metal carbene access to dipolar intermediates, 3,6-dihydro-1,2-oxazines are produced in high yields by dirhodium(II) carboxylate catalyzed reactions between nitrones and a β-TBSO-substituted vinyldiazoacetate. High enantiocontrol occurs with catalysis by N-phthaloyl-(S)-(amino acid)-ligated dirhodium carboxylates for [3 + 3]-cycloaddition reactions with both acyclic and cyclic nitrones.     

Thiocyanate and nitrite analysis using miniaturised isotachophoresis on a planar polymer chip

A new method has been developed to improve the determination of thiocyanate using isotachophoresis. This method uses complexation with copper(II) as a mechanism for improving the separation of thiocyanate from chlorate and perchlorate. By using a pH of 3.25 the method can also be used to analyse nitrite. Separations were carried out using a miniaturised poly(methyl methacrylate) (PMMA) separation device. Linearity was observed from 1.25 to 75 mg dm(-3) with a correlation coefficient of 0.998 for both thiocyanate and nitrite. Limits of detection for these two species were calculated to be 0.8 mg dm(-3) and 0.9 mg dm(-3) respectively. The method was successfully applied to the analysis of these anions in a range of samples including explosive residues.     

Synthesis, cytotoxicity and cellular uptake studies of N3 functionalized Re(CO)3 thymidine complexes

Nucleoside-derived drugs play an important role in the treatment of cancer. Here, we present the synthesis and characterization of an intriguing series of N3 conjugated Re(CO)(3) thymidine complexes. The complexes were characterized by NMR spectroscopy and mass spectrometry and their cytotoxicity was assessed against A549 cells. A similar dependence on the spacer length and the toxicity has been found for N3 functionalized complexes as recently reported for their C5' counterparts. A remarkable cytotoxic complex 22, carrying a dodecylene spacer at position N3 with a bis-quinoline metal chelate moiety, with an IC(50) value of 3.4 ± 1.6 μM, has been identified. Addition of a 100-fold excess of thymidine did not statistically reduce the observed cytotoxicity of all complexes. Cellular uptake studies of complex 22 have been performed by fluorescent microscopy, showing that compound 22 was clearly internalized into A549 cells. Temperature dependent uptake studies, blocking experiments with thymidine, and endosomal co-localization suggest that uptake of 22 occurs via passive diffusion and endocytosis.     

Redox switching and oxygen evolution at oxidized metal and metal oxide electrodes: iron in base

Outstanding issues regarding the film formation, redox switching characteristics and the oxygen evolution reaction (OER) electrocatalytic behaviour of multicycled iron oxyhydroxide films in aqueous alkaline solution have been revisited. The oxide is grown using a repetitive potential multicycling technique, and the mechanism of the latter hydrous oxide formation process has been discussed. A duplex layer model of the oxide/solution interphase region is proposed. The acid/base behaviour of the hydrous oxide and the microdispersed nature of the latter material has been emphasised. The hydrous oxide is considered as a porous assembly of interlinked octahedrally coordinated anionic metal oxyhydroxide surfaquo complexes which form an open network structure. The latter contains considerable quantities of water molecules which facilitate hydroxide ion discharge at the metal site during active oxygen evolution, and also charge compensating cations. The dynamics of redox switching has been quantified via analysis of the cyclic voltammetry response as a function of potential sweep rate using the Laviron-Aoki electron hopping diffusion model by analogy with redox polymer modified electrodes. Steady state Tafel plot analysis has been used to elucidate the kinetics and mechanism of oxygen evolution. Tafel slope values of ca. 60 mV dec(-1) and ca. 120 mV dec(-1) are found at low and high overpotentials respectively, whereas the reaction order with respect to hydroxide ion activity changes from ca. 3/2 to ca. 1 as the potential is increased. These observations are rationalised in terms of a kinetic scheme involving Temkin adsorption and the rate determining formation of a physisorbed hydrogen peroxide intermediate on the oxide surface. The dual Tafel slope behaviour is ascribed to the potential dependence of the surface coverage of adsorbed intermediates.     

Cold heteromolecular dipolar collisions

Cold molecules promise to reveal a rich set of novel collision dynamics in the low-energy regime. By combining for the first time the techniques of Stark deceleration, magnetic trapping, and cryogenic buffer gas cooling, we present the first experimental observation of cold collisions between two different species of state-selected neutral polar molecules. This has enabled an absolute measurement of the total trap loss cross sections between OH and ND(3) at a mean collision energy of 3.6 cm(-1) (5 K). Due to the dipolar interaction, the total cross section increases upon application of an external polarizing electric field. Cross sections computed from ab initio potential energy surfaces are in agreement with the measured value at zero external electric field. The theory presented here represents the first such analysis of collisions between a (2)Π radical and a closed-shell polyatomic molecule.