Computational Study of the Mechanism and Selectivity of Palladium‐Catalyzed Propargylic Substitution with Phosphorus Nucleophiles

The mechanism and sources of selectivity in the palladium‐catalyzed propargylic substitution reaction that involves phosphorus nucleophiles, and which yields predominantly allenylphosphonates and related compounds, have been studied computationally by means of density functional theory. Full free‐energy profiles are computed for both H‐phosphonate and H‐phosphonothioate substrates. The calculations show that the special behavior of H‐phosphonates among other heteroatom nucleophiles is indeed reflected in higher energy barriers for the attack on the central carbon atom of the allenyl/propargyl ligand relative to the ligand‐exchange pathway, which leads to the experimentally observed products. It is argued that, to explain the preference of allenyl‐ versus propargyl‐phosphonate/phosphonothioate formation in reactions that involve H‐phosphonates and H‐phosphonothioates, analysis of the complete free‐energy surfaces is necessary, because the product ratio is determined by different transition states in the respective branches of the catalytic cycle. In addition, these transition states change in going from a H‐phosphonate to a H‐phosphonothioate nucleophile.     

Photopolymerized polypyrrole microvessels

We report on the preparation of water-filled polymer microvessels through the photopolymerization of pyrrole in a water/chloroform emulsion. The resulting structures were characterized by complementary spectroscopic and microscopic techniques, including Raman spectroscopy, XPS, SEM, and TEM. The encapsulation of fluorescent, magnetic, and ionic species within the microvessels has been demonstrated. Confocal microscopy and fluorescence anisotropy measurements revealed that the encapsulated chromophore (Rhodamine 6G) resides within voids in the capsules; however, strong interaction of the dye with polypyrrole results in a measurable decrease in its rotational dynamics. Microvessels loaded with ferrofluid exhibit magnetic properties, and their structures can be directed with an external magnetic field. TEM measurements allowed imaging of individual nanoparticles entrapped within the vessels. The application of Cu(2+)-loaded microvessels as a transducer layer in all-solid-state ion-selective electrodes was also demonstrated.     

Synthesis and optoelectronic properties of hexahydroxylated 10-O-R-substituted anthracenes via a new modification of the Friedel-Crafts reaction using O-protected ortho-acetal diarylmethanols

A new modification of the Friedel-Crafts type intramolecular cyclization involving O-protected ortho-acetal diarylmethanols as a new type of reactant, was carried out for the first time in a medium containing a large amount of water at room temperature and enabled synthesis of a series of electron-rich, hexahydroxylated 10-O-R-substituted anthracenes, where R is an alkyl (Me, nBu, n-C(16)H(33)) or arylalkyl group (CH(2)Ph, CH(2)-2-Napht, CH(2)C(6)H(4)CH(2)OAr) and also evaluation of their electronic and optoelectronic properties in solution, crystal, and solid thin film. In this transformation, a central 10-O-R-substituted benzene ring was formed, fused to rings originating from two independent aromatic aldehydes. The reaction proceeded via two identified mechanisms involving acetal and/or free aldehyde groups. The acid sensitive acetal and dibenzyl alkoxy functions have never been used together in the intramolecular Friedel-Crafts type cyclization. The new compounds revealed deep blue fluorescence and quantum yields in solution around 0.3. The electrical properties investigated for thin films obtained by vacuum deposition on glass were 10-O-R-substituent dependent and showed much faster transient current decay in the case of the 10-O-CH(2)Ph derivative than for the material with a 10-O-Me substituent (the lifetime of charge carriers was 25 times shorter in this case). The AFM images of thin films, Stokes shifts, and X-ray analysis of π-stacking interactions in crystals of the new materials have been also obtained.     

Computational study of the mechanism and selectivity of palladium-catalyzed propargylic substitution with phosphorus nucleophiles

The mechanism and sources of selectivity in the palladium-catalyzed propargylic substitution reaction that involves phosphorus nucleophiles, and which yields predominantly allenylphosphonates and related compounds, have been studied computationally by means of density functional theory. Full free-energy profiles are computed for both H-phosphonate and H-phosphonothioate substrates. The calculations show that the special behavior of H-phosphonates among other heteroatom nucleophiles is indeed reflected in higher energy barriers for the attack on the central carbon atom of the allenyl/propargyl ligand relative to the ligand-exchange pathway, which leads to the experimentally observed products. It is argued that, to explain the preference of allenyl- versus propargyl-phosphonate/phosphonothioate formation in reactions that involve H-phosphonates and H-phosphonothioates, analysis of the complete free-energy surfaces is necessary, because the product ratio is determined by different transition states in the respective branches of the catalytic cycle. In addition, these transition states change in going from a H-phosphonate to a H-phosphonothioate nucleophile.     

Application of click chemistry to the production of DNA microarrays

The copper-catalyzed alkyne-azide cycloaddition (CuAAC) reaction was applied as the novel method of DNA immobilization on a modified solid support. The CuAAC click reaction enables the covalent binding of DNA modified with pentynyl groups at its 5'-end to azide-loaded slides. Click microarrays were produced using this approach and successfully employed in biological/model experiments.     

Effect of Methyl Jasmonate on the Terpene Trilactones,Flavonoids, and Phenolic Acids in Ginkgo biloba L. Leaves: Relevance to Leaf Senescence

The present study compared the effects of natural senescence and methyl jasmonate (JA-Me) treatment on the levels of terpene trilactones (TTLs; ginkgolides and bilobalide), phenolic acids, and flavonoids in the primary organs of Ginkgo biloba leaves, leaf blades, and petioles. Levels of the major TTLs, ginkgolides B and C, were significantly higher in the leaf blades of naturally senesced yellow leaves harvested on 20 October compared with green leaves harvested on 9 September. In petioles, a similar effect was found, although the levels of these compounds were almost half as high. These facts indicate the importance of the senescence process on TTL accumulation. Some flavonoids and phenolic acids also showed changes in content related to maturation or senescence. Generally, the application of JA-Me slightly but substantially increased the levels of TTLs in leaf blades irrespective of the difference in its application side on the leaves. Of the flavonoids analyzed, levels of quercetin, rutin, quercetin-4-glucoside, apigenin, and luteolin were dependent on the JA-Me application site, whereas levels of (+) catechin and (−) epicatechin were not. Application of JA-Me increased ferulic acid and p-coumaric acid esters in the petiole but decreased the levels of these compounds in the leaf blade. The content of p-coumaric acid glycosides and caffeic acid esters was only slightly modified by JA-Me. In general, JA-Me application affected leaf senescence by modifying the accumulation of ginkogolides, flavonoids, and phenolic acids. These effects were also found to be different in leaf blades and petioles. Based on JA-Me- and aging-related metabolic changes in endogenous levels of the secondary metabolites in G. biloba leaves, we discussed the results of study in the context of basic research and possible practical application.     

Representations of analytic functions as infinite products and their application to numerical computations

Let D be an open disk of radius ≤1 in $\mathbb{C}$ , and let (? _n ) be a sequence of ±1. We prove that for every analytic function $f: D \to \mathbb{C}$ without zeros in D, there exists a unique sequence (α _n ) of complex numbers such that $f(z) = f(0)\prod_{n=1}^{\infty} (1+\epsilon_{n}z^{n})^{\alpha_{n}}$ for every z∈D. From this representation we obtain a numerical method for calculating products of the form ∏ _p prime f(1/p) provided f(0)=1 and f′(0)=0; our method generalizes a well-known method of Pieter Moree. We illustrate this method on a constant of Ramanujan $\pi^{-1/2}\prod _{p~\text{prime}} \sqrt{p^{2}-p}\ln(p/(p-1))$ . From the properties of the exponents α _n , we obtain a proof of the following congruences, which have been the subject of several recent publications motivated by some questions of Arnold: for every n×n integral matrix A, every prime number p, and every positive integer k we have $\operatorname{tr} A^{p^{k}} \equiv\operatorname{tr} A^{p^{k-1}} { \hbox {\rm { (mod\ $p^{k}$) }}}$ .     

Lower and upper Ginchev derivatives of vector functions and their applications to multiobjective optimization

Based on the definitions of lower and upper limits of vector functions introduced in Rahmo and Studniarski (J Math Anal Appl 393:212–221, 2012), we extend the lower and upper Ginchev directional derivatives to functions with values in finite-dimensional spaces where partial order is introduced by a polyhedral cone. This allows us to obtain some modifications of the optimality conditions from Luu (Higher-order optimality conditions in nonsmooth cone-constrained multiobjective programming. Institute of Mathematics, Hanoi, Vietnam 2008) with weakened assumptions on the minimized function.     

On ideal equal convergence

We consider ideal equal convergence of a sequence of functions. This is a generalization of equal convergence introduced by Császár and Laczkovich [Császár Á., Laczkovich M., Discrete and equal convergence, Studia Sci. Math. Hungar., 1975, 10(3–4), 463–472]. Our definition of ideal equal convergence encompasses two different kinds of ideal equal convergence introduced in [Das P., Dutta S., Pal S.K., On and *-equal convergence and an Egoroff-type theorem, Mat. Vesnik, 2014, 66(2), 165–177]_and [Filipów R., Szuca P., Three kinds of convergence and the associated I-Baire classes, J. Math. Anal. Appl., 2012, 391(1), 1–9]. We also solve a few problems posed in the paper by Das, Dutta and Pal.