Active media based on SiO2 matrices with incorporated molecules of rhodamine dyes

SiO₂ matrices with incorporated molecules of Rhodamine 6G and Rhodamine 800 laser dyes were synthesized by the sol?Cgel method. The spectral properties of the matrices were studied. It was found that the incorporation of Rhodamine 6G molecules into the xerogel network decreased their association. The influence of the molar ratio of water and formamide on the transparency of the samples was studied. Laser emission of SiO₂ matrices activated with Rhodamine 800 was obtained in the near infrared spectral range. The values of laser spectrum halfwidth of SiO₂ matrices with Rhodamine 6G and Rhodamine 800 are 2?C6?nm. A well-defined structure of the laser emission spectra of the matrices at microsecond pumping duration testifies to their relatively high optical quality.     

Snapshot of the palladium(II)-catalyzed oxidative biaryl bond formation by X-ray analysis of the intermediate diaryl palladium(II) complex

Pd(II) caught in the act: The diaryl Pd(II) intermediate of a Pd(II)-catalyzed oxidative biaryl bond formation proceeding via a double C-H bond activation has been isolated and fully characterized, including an X-ray crystal structure analysis. Stabilization due to chelation by adjacent pivaloyloxy and acetyl groups has allowed the isolation of this long-sought crucial intermediate. On gentle warming, the complex is transformed into a carbazole product, and the catalytically active Pd(II) species is regenerated by oxidation with Cu(II).     

Stereoselective synthesis and hormonal activity of novel dafachronic acids and naturally occurring steroids isolated from corals

A stereoselective synthesis of (25S)-Δ(1)-, (25S)-Δ(1,4)-, (25S)-Δ(1,7)-, (25S)-Δ(8(14))-, (25S)-Δ(4,6,8(14))-dafachronic acid, methyl (25S)-Δ(1,4)-dafachronate and (25S)-5α-hydroxy-3,6-dioxocholest-7-en-26-oic acid is described. (25S)-Δ(1,4)-Dafachronic acid and its methyl ester are natural products isolated from corals and have been obtained by synthesis for the first time. (25S)-5α-Hydroxy-3,6-dioxocholest-7-en-26-oic acid represents a promising synthetic precursor for cytotoxic marine steroids.     

From pico to nano: biofunctionalization of cube-octameric silsesquioxanes by peptides and miniproteins

Polyhedral silsesquioxanes are considered valuable conjugation scaffolds. Nevertheless, only a few examples of silsesquioxane-assembled peptide oligomers have been reported to date. We developed a new bioorthogonal cube-octameric silsesquioxane (COSS) scaffold bearing eight aminooxy coupling sites allowing for the conjugation of diverse peptides via oxime ligation. We found that the coupling efficacy depends on the ligand in view of steric hindrance and electrostatic repulsion. For the first time scaffold-based conjugation of cystine-knot miniproteins having a backbone of about thirty amino acids was successfully accomplished without loss of bioactivity. Atomic force microscopy (AFM) provided further knowledge on the size of COSS verifying them as picoscaffolds growing upon bioconjugation to nano-dimension.     

Reactions of 1-alkyl-1,2-diphospholes with 1,3-dipoles: diphenyldiazomethane and nitrones

The reaction of 1-alkyl-1,2-diphosphacyclopenta-2,4-dienes (1-alkyl-1,2-diphospholes) (1) with diphenyldiazomethane proceeds at room temperature via unstable [3+2] cycloadducts to form bicyclic phosphiranes (2). However, 1-alkyl-1,2-diphospholes (1) react with N,alpha-diphenylnitrone or N-tert-butyl-alpha-phenylnitrone depending on the temperature to give either dimers of 1-alkyl-1-oxo-1,2-diphospholes (5) or 1-alkyl-1,7-dioxo-6-azo-1,7-diphospha-bicyclo[3.2.0]hept-2-enes (7) - phosphorus analogues of β-lactams.     

On definability in some lattices of semigroup varieties

An identity of the form x ₁?x _n ??x _1?? x _2?? ?x _n?? where ?? is a non-trivial permutation on the set {1,??,n} is called a permutation identity. If u??v is a permutation identity, then ?(u??v) [respectively r(u??v)] is the maximal length of the common prefix [suffix] of the words u and v. A variety that satisfies a permutation identity is called permutative. If $\mathcal{V}$ is a permutative variety, then $\ell=\ell(\mathcal{V})$ [respectively $r=r(\mathcal{V})$ ] is the least ? [respectively r] such that $\mathcal{V}$ satisfies a permutation identity ?? with ?(??)=? [respectively r(??)=r]. A?variety that consists of nil-semigroups is called a nil-variety. If ?? is a set of identities, then $\operatorname {var}\varSigma$ denotes the variety of semigroups defined by ??. If $\mathcal{V}$ is a variety, then $L (\mathcal{V})$ denotes the lattice of all subvarieties of $\mathcal{V}$ . For ?,r??0 and n>1 let $\mathfrak{B}_{\ell,r,n}$ denote the set that consists of n! identities of the form $$t_1\cdots t_\ell x_1x_2 \cdots x_n z_{1}\cdots z_{r}\approx t_1\cdots t_\ell x_{1\pi}x_{2\pi} \cdots x_{n\pi}z_{1}\cdots z_{r}, $$ where ?? is a permutation on the set {1,??,n}. We prove that for each permutative nil-variety $\mathcal{V}$ and each $\ell\ge\ell(\mathcal{V})$ and $r\ge r(\mathcal{V})$ there exists n>1 such that $\mathcal{V}$ is definable by a first-order formula in $L(\operatorname{var}{\mathfrak{B}}_{l,r,n})$ if ???r or $\mathcal{V}$ is definable up to duality in $L(\operatorname{var}{\mathfrak{B}}_{\ell,r,n})$ if ?=r.     

Exceedance probability of the integral of a stochastic process

Let X={X(s)}_s∈S be an almost sure continuous stochastic process (S compact subset of R^d) in the domain of attraction of some max-stable process, with index function constant over S. We study the tail distribution of ∫_SX(s)ds, which turns out to be of Generalized Pareto type with an extra ‘spatial’ parameter (the areal coefficient from Coles and Tawn (1996) [3]). Moreover, we discuss how to estimate the tail probability P(∫_SX(s)ds>x) for some high value x, based on independent and identically distributed copies of X. In the course we also give an estimator for the areal coefficient. We prove consistency of the proposed estimators. Our methods are applied to the total rainfall in the North Holland area; i.e. X represents in this case the rainfall over the region for which we have observations, and its integral amounts to total rainfall.The paper has two main purposes: first to formalize and justify the results of Coles and Tawn (1996) [3]; further we treat the problem in a non-parametric way as opposed to their fully parametric methods.     

New properties and representations for members of the power-variance family. I

We derive new Wright-function representations for the densities of the generating measures of most representatives of the power-variance family of distributions. For all members of this family, we construct new saddlepoint-type approximations having an arbitrary fixed number of refining terms. To this end, we derive new, ??exponentially small,?? Poincaré series for a subclass of the Wright functions whose coefficients are expressed in terms of the Zolotarev polynomials.     

Optimal and equilibrium balking strategies in the single server Markovian queue with catastrophes

We consider a Markovian queue subject to Poisson generated catastrophes. Whenever a catastrophe occurs, all customers are forced to abandon the system, the server is rendered inoperative and an exponential repair time is set on. We assume that the arriving customers decide whether to join the system or balk, based on a natural reward-cost structure. We study the balking behavior of the customers and derive the corresponding Nash equilibrium and social optimal strategies.     

Fluorene: An extended experimental thermodynamic study

This work reports new experimental thermodynamic results on fluorene. Vapor pressures of both crystalline and liquid phases were measured using a pressure gauge (capacitance diaphragm manometer) and Knudsen effusion methods over a wide temperature range (292.20 to 412.16) K yielding accurate determination of enthalpy and entropy of sublimation and of vaporization. The enthalpy of sublimation was also determined using Calvet microcalorimetry. The enthalpy of fusion was derived from vapor pressure results and from d.s.c. experiments. Static bomb calorimetry was used to determine the enthalpy of combustion of fluorene from which the standard enthalpy of formation in the crystalline phase was calculated. The enthalpy of formation in the gaseous phase was calculated combining the result derived for the crystalline phase with the enthalpy of sublimation.