Asymmetric synthesis of antimicrotubule biaryl hybrids of allocolchicine and steganacin

The asymmetric synthesis of novel axially chiral biaryl compounds 5 a-f containing a seven- or eight-membered heterocyclic medium ring is described. These molecules can be considered to be structural hybrids of allocolchicine- and steganacin-type natural products. The synthesis featured an atropo-diastereoselective biaryl Suzuki coupling in which a benzylic stereocenter efficiently transferred its stereochemical information to the biaryl axis. The coupling conditions were optimized, and two biphenylphosphane ligands (DavePhos and S-Phos) were found to give the highest yields and diastereoselectivities. A three-element stereochemical model was proposed to explain the observed diastereoselectivities. In a second key step, the medium ring of the target molecules was formed by a stereoselective S(N)1-type cyclodehydration that probably involved a configurationally stable carbocationic intermediate, as supported by calculations. Alternatively, S(N)2-type cyclizations were employed on the same Suzuki coupling products to give the target molecules in a stereodivergent or stereoconvergent manner. These cyclization methods furnished the target hybrid analogues 5 a-f with ee values above 94 %. All analogues were evaluated as antimicrotubule agents and against a panel of cancer-cell lines using colchicine (1) and N-acetylcolchinol (3) as references. Promising activities were found for R,aR-configured compounds 5 a, b and 5 f; in particular, ethyl analogue 5 b showed a twofold antimicrotubule activity relative to colchicine.     

Femtosecond time resolved coherent anti-Stokes Raman spectroscopy: experiment and modelization of speed memory effects on H2-N2 mixtures in the collision regime

With the aim of temperature diagnostic, femtosecond time-resolved CARS (coherent anti-Stokes Raman spectroscopy) is applied to probe H2 in H2-N2 mixtures. In a first part, a Lorentzian profile is used to model the femtosecond CARS response. A difference between the experimental broadening and the expected one is observed in the collision regime. The observed broadening increases strongly in an inhomogeneous way with respect to the perturber concentration. This is of considerable importance for temperature measurements. In a second part, we show that in the collision regime, this inhomogeneous broadening is due to the speed dependence of the collisional parameters and the memory effects of the radiator speed. A new modelization of the time-resolved CARS response taking into account the speed memory effects is presented and applied to the temperature diagnostic in H2-N2 mixtures. The numerical results are in good agreement with experiments.     

A new anti-inflammatory β-carboline alkaloid from the hairy-root cultures of Eurycoma longifolia

One new β-carboline alkaloid 7-methoxy-(9H-β-carbolin-1-il)-(E)-1-propenoic acid (1) together with 9-methoxycanthin-6-one (2) and 9-hydroxycanthin-6-one (3) were isolated from the hairy-root cultures of Eurycoma longifolia. The effects of these compounds on lipopolysaccharide (LPS)-induced nitric oxide (NO) production in RAW264.7 cells were investigated. Compound 1 strongly inhibited the production of NO while 2 and 3 having weak or inactive effect. Consistently, compound 1 decreased the expression of cyclooxygenase-2 and inducible nitric oxide synthase.     

Fast determination of the tin content in cassiterite ores by photon activation method

Photon activation analysis has been success-fully applied to the fast and non-destructive analysis of tin in cassiterite ores based on the 159.7 keV gamma line of^123mSn produced in the¹²⁴Sn/γ, n/^123mSn reaction. In order to improve the accuracy of analytical results, corrections for self-absorption and pile-up effects were performed. Under typical conditions /15 μA electron beam current, 15 MeV bremsstrahlung energy, 5 min irradiation time and 10 min measurement/ the sensitivity of the analysis is 10 ppm. The proposed method can be used for routine analysis of tin in geological samples.     

Chemical Constituents of the Leaves of Artocarpus integer

Chemistry of Natural Compounds -     

Copper ferrite superparamagnetic nanoparticles as a heterogeneous catalyst for directed phenol/formamide coupling

The copper ferrite-catalyzed, directed coupling of ortho-arylated phenols and dialkylformamides in the presence of a peroxide oxidant is described. Acyclic and cyclic amides were compatible with the reaction conditions. The copper ferrite catalyst is heterogeneous since substantial leaching was not detected and re-use of the catalyst for 9 consecutive reactions proceeded without a significant decrease in yield. To the best of our knowledge, this transformation has not been previously performed under heterogeneous catalysis conditions.     

Orbits in a stochastic Goodwin–Lotka–Volterra model

This paper examines the cycling behavior of a deterministic and a stochastic version of the economic interpretation of the Lotka–Volterra model, the Goodwin model. We provide a characterization of orbits in the deterministic highly non-linear model. We then study a stochastic version, with Brownian noise introduced via a heterogeneous productivity factor. Existence conditions for a solution to the system are provided. We prove that the system produces cycles around a unique equilibrium point in finite time for general volatility levels, using stochastic Lyapunov techniques for recurrent domains. Numerical insights are provided.     

Improved bounds for separating hash families

An ${(N;n,m,\{w_1,\ldots, w_t\})}$ -separating hash family is a set ${\mathcal{H}}$ of N functions ${h: \; X \longrightarrow Y}$ with ${|X|=n, |Y|=m, t \geq 2}$ having the following property. For any pairwise disjoint subsets ${C_1, \ldots, C_t \subseteq X}$ with ${|C_i|=w_i, i=1, \ldots, t}$ , there exists at least one function ${h \in \mathcal{H}}$ such that ${h(C_1), h(C_2), \ldots, h(C_t)}$ are pairwise disjoint. Separating hash families generalize many known combinatorial structures such as perfect hash families, frameproof codes, secure frameproof codes, identifiable parent property codes. In this paper we present new upper bounds on n which improve many previously known bounds. Further we include constructions showing that some of these bounds are tight.     

Generalized Random Spectral Measures

In an attempt to examine the random version of the spectral theorem, the notion of random spectral measures and generalized random spectral measures are introduced and investigated. It is shown that each generalized random spectral measure on $(\mathbb C ,\mathcal{B}(\mathbb C ))$ admits a modification which is a random spectral measure.