Cyclizing Radical Carboiodination,Carbotelluration, and Carboaminoxylation of Aryl Amines

Radical carboiodination of various aryl amines is reported. Aryl diazonium salts, generated in situ from the corresponding aryl amines, are reacted with Bu₄NI to provide the corresponding aryl radicals which undergo 5‐exo or 6‐exo cyclization. Iodine abstraction eventually affords the carboiodinated products in good to excellent yields. If TEMPO is added, the cascade provides the cyclized carboaminoxylation products. Running the reaction in the presence of PhTeTePh affords the phenyltellurated cyclized products.     

Back cover: Mn2+ or Mn3+? Investigating transition metal dissolution of manganese species in lithium ion battery electrolytes by capillary electrophoresis

A new CE method with ultraviolet–visible detection was developed in this study to investigate manganese dissolution in lithium ion battery electrolytes. The aqueous running buffer based on diphosphate showed excellent stabilization of labile Mn³⁺, even under electrophoretic conditions. The method was optimized regarding the concentration of diphosphate and modifier to obtain suitable signals for quantification. Additionally, the finally obtained method was applied on carbonate-based electrolytes samples. Dissolution experiments of the cathode material LiNi_0.5Mn_1.5O₄ (lithium nickel manganese oxide [LNMO]) in aqueous diphosphate buffer at defined pH were performed to investigate the effect of a transition metal-ion-scavenger on the oxidation state of dissolved manganese. Quantification of both Mn species revealed the formation of mainly Mn³⁺, which can be attributed to a comproportionation reaction of dissolved and complexed Mn²⁺ with Mn⁴⁺ at the surface of the LNMO structure. It was also shown that the formation of Mn³⁺ increased with lower pH. In contrast, dissolution experiments of LNMO in carbonate-based electrolytes containing LIPF₆ showed only dissolution of Mn²⁺.     

Self-Assembly of DNA and RNA Building Blocks Explored by Nitrogen-14 NMR Crystallography: Structure and Dynamics

The isotopic enrichment of nucleic acids with nitrogen-15 is often carried out by solid-phase synthesis of oligonucleotides using phosphoramidite precursors that are synthetically demanding and expensive. These synthetic challenges, combined with the overlap of chemical shifts, explain the lag of nitrogen-15 NMR studies of nucleic acids behind those of proteins. For the structural characterization of DNA and RNA-related systems, new NMR methods that exploit the naturally occurring 99.9 % abundant nitrogen-14 isotope are therefore highly desirable. In this study, we have investigated nitrogen-14 spectra of self-assembled quartets based on the nucleobase guanine in the solid state by means of magic-angle spinning NMR spectroscopy. The network of dipolar proton–nitrogen couplings between neighboring stacked purine units is probed by 2D spectra based on ¹H→¹⁴N→¹H double cross-polarization. Interplane dipolar contacts are identified between the stacked G quartets. The assignment is supported by density functional theory (DFT) calculations of the anisotropic chemical shifts and quadrupolar parameters. The experimental spectra are fully consistent with internuclear distances obtained in silico. Averaging of chemical shifts due to internal motions can be interpreted by semiempirical calculations. This method can easily be extended to synthetic G quartets based on nucleobase or nucleoside analogs and potentially to oligonucleotides.     

Isoshamixanthone: a new pyrano xanthone from endophytic Aspergillus sp. ASCLA and absolute configuration of epiisoshamixanthone

Abstract

Isoshamixanthone (1), a new stereoisomeric pyrano xanthone together with the previously known fungal metabolites, epiisoshamixanthone (2), sterigmatocystin (3), arugosin C (4), norlichexanthone (5), diorcinol (6), ergosterol and methyllinoleate, were obtained from the endophytic fungal strain Aspergillus sp. ASCLA isolated from leaf tissues of the medicinal plant Callistemon subulatus. The chemical structure of the new xanthone (1) was elucidated by extensive 1D, 2D NMR, and ESI HR mass measurements, and by comparison with literature data. The constitutions and absolute configurations of 1 and epiisoshamixanthone (2) were additionally confirmed by X-ray crystallography. Compounds 1,2 were evaluated for their potential anticancer activity using the human cervix carcinoma cell line (KB-3-1). The antimicrobial activities of the fungal extract and compounds 1,2 were studied using a panel of pathogenic microorganisms as well.     

Nonlinear optical polymers. Second harmonic generation in corona-poled thin films

The synthesis and second harmonic coefficients, d_3,1 and d_3,3 as well as the related susceptibilities χ⁽²⁾_zzz of five series of (NLO-dye methacrylate)-(methyl methacrylate) copolymers were investigated. The NLO-chromophores bound covalently to the polymer backbone were 5-(2,2-dicyanovinyl)-or 4-(2-cyano-2-methoxycarbonyl)vinyl-1-piperidino-2-thiophene (P₁ and P₂), 4-nitro-4′-alkoxy-stilbene (P₃), 4-nitro-3′-methoxy-4′-alkoxystilbene (P₄) and 4-nitro-4′-alkoxy-α-cyano stilbene (P₅). The second order nonlinear optical properties of corona-poled aligned thin polymer films, using a needle electrode in order to induce noncentrosymmetry, were evaluated. Nonlinear susceptibilities, χ⁽²⁾_zzz, of the films were derived from the analysis of full-angle Maker fringe patterns at 1064 nm, χ⁽²⁾_zzz values as high as 1.98×10⁻⁷ esu for P₂ copolymers and of 1.19×10⁻⁷ esu for P₃ copolymers could be achieved.     

Damage induced in garnets by heavy ion irradiations: a study by optical spectroscopies

The damage induced by heavy-ion irradiation has been studied in yttrium iron garnet (Y₃Fe₅O₁₂ or YIG) films, doped with Ca, Tb and Tm, grown by liquid-phase epitaxy on gadolinium gallium garnet (Gd₃Ga₅O₁₂ or GGG) substrates. Irradiations of doped-YIG epitaxial films and GGG substrates with 36-MeV ¹⁸³W and 12-MeV ¹⁹⁷Au ions were applied for fluences between 1 × 10¹³ and 3 × 10¹⁵ cm^–2 near room temperature. The radiation damage was monitored by micro-Raman spectroscopy and UV–visible optical absorption spectroscopy. Raman spectra revealed that amorphisation was achieved in YIG for both ions, whereas a high lattice disorder was induced in GGG without reaching amorphisation for the Au ion irradiation. Raman spectra also showed that a major damage of the tetrahedral sites was induced in GGG, as previously found for YIG. It is concluded that with such ions reaching the stopping power threshold of track formation in YIG and GGG the observed rate of amorphisation may result from a combination of electronic and nuclear energy losses as calculated using the unified thermal spike model.     

Permutation groups generated by cycles of fixed length

Combinatorial conditions on a set of cycles of fixed degree inS _n are studied, so that they generateA _n orS _n . It is shown thatA _n orS _n is so generated if and only if a graph associated with the set of cycles is connected, provided two of the cycles satisfy certain, not too restrictive, criteria. As a corollary, the minimum number of cycles of degreem ≧ 2 that generateA _n or S_n is determined.     

Passively mode-locked Yb:KLu(WO4)2 thin-disk oscillator operated in the positive and negative dispersion regime

We demonstrate a passively mode-locked femtosecond Yb:KLu(WO(4))(2) thin-disk laser oscillator. Chirped-pulse operation in the positive dispersion regime as well as solitary operation have been realized, and the laser performance of both configurations are compared. In the solitary mode-locking regime the output power exceeds 25 W in a diffraction-limited beam, and pulse durations as short as 440 fs at a 34.7 MHz repetition rate have been generated. For the first time we present a chirped-pulse operation of a thin-disk oscillator that yields a maximum average output power of 9.5 W with a Fourier limit of 450 fs.     

Correlation measure to detect time series distances, whence economy globalization

An instantaneous time series distance is defined through the equal time correlation coefficient. The idea is applied to the Gross Domestic Product (GDP) yearly increments of 21 rich countries between 1950 and 2005 in order to test the process of economic globalisation. Some data discussion is first presented to decide what (EKS, GK, or derived) GDP series should be studied. Distances are then calculated from the correlation coefficient values between pairs of series. The role of time averaging of the distances over finite size windows is discussed. Three network structures are next constructed based on the hierarchy of distances. It is shown that the mean distance between the most developed countries on several networks actually decreases in time, —which we consider as a proof of globalization. An empirical law is found for the evolution after 1990, similar to that found in flux creep. The optimal observation time window size is found ?15 years.