Synthesis of 15N-enriched pseudouridine derivatives

[reaction: see text]. A procedure for the chemical synthesis of [3-15N]-labeled pseudouridine and a methylated derivative was developed. A suitably protected pseudouridine precursor was nitrated at N3 followed by treatment with 15NH4Cl to afford the 15N-labeled product in six steps with a 20% yield. This methodology will allow for the production of RNAs with [3-15N]pseudouridine and [3-15N-methyl]pseudouridine at specific locations.     

Novel Sesquiterpenes from the Fungus Lactarius piperatus

Four novel sesquiterpenes, namely 7α,8β,13‐trihydroxy‐5,13‐marasmanolide ( 2 ), isoplorantinone ( 5 ), 4,8,14‐trihydroxyilludala‐2,6,8‐triene ( 6 ), and 8‐hydroxy‐8,9‐secolactara‐1,6‐dien‐5,13‐olide ( 10 ), together with six known ones, 7α,8β‐dihydroxy‐5,13‐marasmanolide ( 1) , 7α,8α‐dihydroxy‐5,13‐marasmanolide ( 3 ), isolactarorufin ( 4 ), blennin A ( 7 ), blennin D ( 8 ), and lactarorufin ( 9 ), were isolated from the ethanolic extract of Lactarius piperatus. The structures of these sesquiterpenes, representing diversified structural types, were determined mainly by spectroscopic methods, especially 2D‐NMR techniques. The structure of 6 was further confirmed by a single‐crystal X‐ray‐diffraction determination.     

Extraction of aromatic organic compounds by polyurethane foam

The mechanism of extraction of organic compounds by open-cell polyurethane foam has been investigated through a detailed study with simple aromatic compounds. Comparison with identical extractions into diethyl ether suggests that the basic extraction mechanism is an ether-like solvent extraction process. The addition of salt increases the extraction and changing the dielectric constant of the aqueous solution also affects the extraction. For organic compounds which have a group capable of hydrogen bonding, some additional factor appears to influence the extraction. This appears to be hydrogen bonding with the polyurethane foam; it is stronger with polyether foam and reduced by the presence of a strong intramolecular hydrogen-bonding group placed ortho to the hydrogen-bonding group. Thermodynamic studies support these conclusions.     

Electrophotographic and microwave photodielectric studies on titanium dioxide pigments in the solid state

In this paper, we report some novel preliminary findings on the photoactivity of titanium dioxide pigments using photoconductive and microwave dielectric techniques. A variety of pigment types were investigated by both methods, including the two crystalline forms of titanium dioxide, anatase and rutile, and a variety of coated pigments. Analysis of the data obtained indicates that there are possible relationships between the photoconductive and photodielectric results, and that these may be used to characterize the pigment types rapidly. Photoconductive measurements were carried out on pigmented films of poly(N-vinylcarbazole) (PVK). Uncoated pigments were found to be more photoconductive than coated pigments with the anatase modification being the more active. It is believed that the pigments act as “trapping” sites to the holes produced by PVK, and that the more photoactive the pigment, the easier it is to regenerate the holes. Various factors influence the band gap of the pigment and these have a significant effect on the photoactivity and photoconductivity of the pigment samples. These include the presence of traps and recombination centres (present as coatings on the surface of the pigment particle) and impurities which can act as acceptors or donors.

Microwave dielectric measurements were carried out on the different anatase and rutile pigments, each exhibiting a different microwave resonant frequency loss depending on the nature of the crystalline modification and the coating. However, on illumination on the pigments with polychromatic light in the microwave cavity, the resonant frequency losses exhibit shifts, the nature of which depend on the pigment type and the coating. Thus the anatase pigments exhibit greater responses than the rutile pigments, particularly with regard to the shift in the resonant frequency values and the change in the Q factor of the resonant peak. The resonant frequency values of the anatase samples are also higher than those obtained for the rutile samples. Furthermore, the frequency shifts are in opposite directions, with the anatase modification exhibiting a more rapid shift to lower frequencies and rutile a slower shift to higher frequencies. It appears that, when the anatase samples are irradiated, their dielectric properties change from those characteristic of a conductor-like material to those of an insulator-like material. However, these changes are reversible once the illumination is terminated. With the rutile samples, irradiation increases the resonant frequency values and hence their dielectric constants. Thus the pigments appear to become more like conductors.     

Room temperature suzuki cross‐coupling polymerizations of aryl dihalides and aryldiboronic acid/acid esters with t‐Bu3P‐coordinated 2‐phenylaniline‐based palladacycle complex as the precatalyst

Room temperature Suzuki cross‐coupling polymerization of aryl dibromides/diiodides with aryldiboronic acids/acid esters with t‐Bu₃P‐coordinated 2‐phenylaniline‐based palladacycle complex, [2′‐(amino‐kN)[1,1′‐biphenyl]‐2‐yl‐kC]chloro(tri‐t‐butylphosphine)palladium, as a general precatalyst is described. Such room temperature Suzuki cross‐coupling polymerization is achieved by employing six equivalents or more of the base and affords polymers within an hour, with the yields and the molecular weights in general comparable to or higher than reported results that required higher reaction temperature and/or longer polymerization time. Our study provides a general catalyst system for the room temperature Suzuki cross‐coupling polymerization of aryl dibromides/diiodides with aryldiboronic acids/acid esters and paves the road for the investigation of employing other monodentate ligand‐coordinated palladacycle complexes including other electron‐rich monophosphine‐coordinated ones for room temperature cross‐coupling polymerizations. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1606–1611     

The cation-chelation mechanism of metal-ion sorption by polyurethanes

The mechanism of sorption of ions by polyurethanes has been investigated through detailed studies of the extraction of cobalt(II) thiocyanate and the salts of several organic acids. Polyether-based polyurethanes. particularly those containing poly(ethylene oxide), were found to be distinctly superior to polyesters in the sorption of salts and performed much better than might be expected by analogy with monomeric liquid solvents. The results were judged to be inconsistent with several possible mechanisms, including adsorption, solvent extraction, weak or strong base anion-exchange, and complexation of metal anions by the polymer. A new proposal, termed the cation chelation mechanism (CCM), was advanced to account for the observations. In this view, a number of cations (including those of the alkali metals, alkaline earth metals, some transition metals, NH(+)(4), RNH(+)(3) and perhaps H(3)O(+)) may be multiply complexed (chelated) by portions of the polymer, thus facilitating the sorption of accompanying anions. As predicted by the mechanism, moderately strong and selective complexation of several cations was observed to occur with the following order of selectivity: Li(+) < Na(+) < Cs(+) < Rb(+) < K(+) approximately NH(+)(4) < Ag(+) approximately Tl(+) < Ba(2+) < Hg(2+) < Pb(2+). Such behaviour parallels that known for many crown and non-cyclic polyethers and is therefore identified with the polyether portions of the polymer, which are thought to adopt helical conformations surrounding the complexed cations. The cation-chelation mechanism may be widely applicable to the sorption of ions of several types by polyether-based polyurethanes, particularly when large, hydrophobic anions (such as anionic metal complexes) are accompanied by an excess of chelatable cations.     

Finite element error estimates for non-linear elliptic equations of monotone type

Summary In this paper we shall consider the application of the finite element method to a class of second order elliptic boundary value problems of divergence form and with gradient nonlinearity in the principal coefficient, and the derivation of error estimates for the finite element approximations. Such problems arise in many practical situations — for example, in shock-free airfoil design, seepage through coarse grained porous media, and in some glaciological problems. By making use of certain properties of the nonlinear coefficients, we shall demonstrate that the variational formulations associated with these boundary value problems are well-posed. We shall also prove that the abstract operators accompanying such problems satisfy certain continuity and monotonicity inequalities. With the aid of these inequalities and some standard results from approximation theory, we show how one may derive error estimates for the finite element approximations in the energy norm.     

A numerical method for reconstructing the coefficient in a wave equation

We present a numerical method for reconstructing the coefficient in a wave equation from a single measurement of partial Dirichlet boundary data. The original inverse problem is converted to a nonlinear integral differential equation, which is solved by an iterative method. At each iteration, one linear second‐order elliptic problem is solved to update the reconstruction of the coefficient, then the reconstructed coefficient is used to solve the forward problem to obtain the new data for the next iteration. The initial guess of the iterative method is provided by an approximate model. This model extends the approximate globally convergent method proposed by Beilina and Klibanov, which has been well developed for the determination of the coefficient in a special wave equation. Numerical experiments are presented to demonstrate the stability and robustness of the proposed method with noisy data.© 2014 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq 31: 289–307, 2015     

Counting derangements, involutions and unimodal elements in the wreath product Cr ? Sn

We count derangements, involutions and unimodal elements in the wreath product C _r ≀ S _n by the numbers of excedances, fixed points and 2-cycles. Properties of the generating functions, including combinatorial formulas, recurrence relations and real-rootedness are studied. The results obtained specialize to those on the symmetric group S _n and on the hyperoctahedral group B _n when r = 1, 2, respectively.     

Asymptotic behavior of eigenvalues and random updating schemes

For a stochastic matrix (Q _ij ^T ) _i,j=1 ^M withQ _ij ^T exp(–U(ij)/T) at the off-diagonal positions, we develop an algorithm to evaluate the asymptotic convergence rate of all eigenvalues ofQ _ij ^T asT 0 using Ventcel's optimal graphs. As an application we can compare the convergence rates of some random updating schemes used in image processing.This research was partially supported by the National Science Council, Taiwan and Air Force Office of Scientific Research Contract No. F49620 S5C 0144, and was completed while Tzuu-Shuh Chiang was visiting the Center for Stochastic Processes, Department of Statistics, University of North Carolina, Chapel Hill, NC 27599-3260, USA.