Pd nanoparticles as efficient catalysts for Suzuki and Stille coupling reactions of aryl halides in ionic liquids

Pd-catalyzed Suzuki and Stille cross-couplings of aryl bromides and chlorides were carried out in quaternary ammonium salts as solvents under mild conditions and with the recycling of the catalyst.     

Temperature-induced isomerization of violaxanthin in organic solvents and in light-harvesting complex II

Three main xanthophyll pigments are bound to the major photosynthetic pigment-protein complex of Photosystem II (LHCII): lutein, neoxanthin and violaxanthin. Chromatographic analysis of the xanthophyll fraction of LHCII reveals that lutein appears mainly in the all-trans conformation, neoxanthin in the 9'-cis conformation and major fraction of violaxanthin in the all-trans conformation. Nevertheless, a small fraction of violaxanthin appears always in a cis conformation: 9-cis and 13-cis (approximately 4% and 2% in the darkness, respectively). Illumination of the isolated complex (5 min, 445 nm, 250 micromolm-2s-1) results in the substantial increase in the concentration of the cis steric conformers of violaxanthin: up to 6% of 9-cis and 4% of 13-cis. Similar effect can be obtained by dark incubation of the same preparation for 30 min at 60 degrees C. Heating-induced isomerization of the all-trans violaxanthin can also be obtained in the organic solvent system but the formation of the 9-cis stereoisomer has not been observed under such conditions. The fact that the appearance of the 9-cis form of violaxanthin is specific for the protein environment suggests that violaxanthin may replace neoxanthin in LHCII in the N1 xanthophyll binding pocket and that the protein stabilizes this particular conformation. The analysis of the electronic absorption spectra of LHCII and the FTIR spectra of the protein in the Amid I band spectral region indicates that violaxanthin isomerization is associated with the disaggregation of the complex. It is postulated that this reorganization of LHCII provides conditions for desorption of violaxanthin from the pigment protein complexes, its diffusion within the thylakoid membrane and therefore, availability to the enzymatic deepoxidation within the xanthophyll cycle. It is also possible that violaxanthin isomerization plays the role of a security valve, by consuming an energy of excessive excitations in the antenna pigment network (in particular, exchanged at the triplet state levels).     

Model-based clustering of probability density functions

Complex data such as those where each statistical unit under study is described not by a single observation (or vector variable), but by a unit-specific sample of several or even many observations, are becoming more and more popular. Reducing these sample data by summary statistics, like the average or the median, implies that most inherent information (about variability, skewness or multi-modality) gets lost. Full information is preserved only if each unit is described by a whole distribution. This new kind of data, a.k.a. “distribution-valued data”, require the development of adequate statistical methods. This paper presents a method to group a set of probability density functions (pdfs) into homogeneous clusters, provided that the pdfs have to be estimated nonparametrically from the unit-specific data. Since elements belonging to the same cluster are naturally thought of as samples from the same probability model, the idea is to tackle the clustering problem by defining and estimating a proper mixture model on the space of pdfs. The issue of model building is challenging here because of the infinite-dimensionality and the non-Euclidean geometry of the domain space. By adopting a wavelet-based representation for the elements in the space, the task is accomplished by using mixture models for hyper-spherical data. The proposed solution is illustrated through a simulation experiment and on two real data sets.     

Microwave-Assisted Method for Synthesis of 1,3-Disubstituted Pyrroles

1,3-Disubstituted pyrroles were prepared by a microwave-assisted reaction of pyrrolidine and aldehydes in toluene as well as in solvent-free conditions. Reactions were completed in a few minutes in the solvent-free condition but a long time (up to 30 min) was necessary to complete reactions in toluene. Yields of products depended considerably on the aldehyde used.     

One Way Traffic: Base-to-Backbone Hole Transfer in Nucleoside Phosphorodithioate

The directionality of the hole-transfer processes between DNA backbone and base was investigated by using phosphorodithioate [P(S⁻)=S] components. ESR spectroscopy in homogeneous frozen aqueous solutions and pulse radiolysis in aqueous solution at ambient temperature confirmed initial formation of G^.+-P(S⁻)=S. The ionization potential of G-P(S⁻)=S was calculated to be slightly lower than that of guanine in 5′-dGMP. Subsequent thermally activated hole transfer from G^.+ to P(S⁻)=S led to dithiyl radical (P-2S^.) formation on the μs timescale. In parallel, ESR spectroscopy, pulse radiolysis, and density functional theory (DFT) calculations confirmed P-2S^. formation in an abasic phosphorodithioate model compound. ESR investigations at low temperatures and higher G-P(S⁻)=S concentrations showed a bimolecular conversion of P-2S^. to the σ²-σ*¹-bonded dimer anion radical [-P-2S 2S-P-]⁻ [ΔG (150 K, DFT)=−7.2 kcal mol⁻¹]. However, [-P-2S 2S-P-]⁻ formation was not observed by pulse radiolysis [ΔG° (298 K, DFT)=−1.4 kcal mol⁻¹]. Neither P-2S^. nor [-P-2S 2S-P-]⁻ oxidized guanine base; only base-to-backbone hole transfer occurs in phosphorodithioate.     

On the Strong Convergence of Subgradients of Convex Functions

In this paper, results on the strong convergence of subgradients of convex functions along a given direction are presented; that is, the relative compactness (with respect to the norm) of the union of subdifferentials of a convex function along a given direction is investigated.     

A Porous Sulfonated 2D Zirconium Metal–Organic Framework as a Robust Platform for Proton Conduction

By using the strategy of pre-assembly chlorosulfonation applied to a linker precursor, the first sulfonated zirconium metal–organic framework ( JUK-14 ) with two-dimensional (2D) structure, was synthesized. Single-crystal X-ray diffraction reveals that the material is built of Zr₆O₄(OH)₄(COO)₈ oxoclusters, doubly 4-connected by angular dicarboxylates, and stacked in layers spaced 1.5 nm apart by the presence of sulfonic groups. JUK-14 exhibits excellent hydrothermal stability, permanent porosity confirmed by gas adsorption studies, and shows high (>10⁻⁴ S/cm) and low (<10⁻⁸ S/cm) proton conductivity under humidified and anhydrous conditions, respectively. Post-synthesis inclusion of imidazole improves the overall conductivity increasing it to 1.7×10⁻³ S/cm at 60 °C and 90 % relative humidity, and by 3 orders of magnitude at 160 °C. The combination of 2D porous nature with robustness of zirconium MOFs offers new opportunities for exploration of the material towards energy and environmental applications.