Meissner Anisotropy in Deuterated (TMTSF)2Clo4

Both the Meissner-signal (flux expulsion on cooling through T_c) and the shielding signal (obtained by turning on a field in the superconducting state) have been observed in deuterated single crystals for fields oriented both along and normal to the chain axis. A possible isotope effect on T_c is discussed. We find complete diamagnetism in normal fields and incomplete (～ 40 %) diamagnetism in parallel fields. A dramatic drop of the Meissner-effect in parallel fields well below H_c1 is observed and not yet well explained.     

Reductive Ring Opening of Ephedrine and Pseudo-Ephedrine-Derived Oxazolidinium Methiodides by Sodium Borohydride. A Direct Access to New Chiral Amine-Borane Adducts

Sodiun borohydride reacts with oxazolidinium methiodides derived from ephedrine and pseudoephedrine, in ethereal solvents, cleaving regioselectively the C-N bond of the ring and leading, in good yields, to chiral amine-borane adducts of know absolute configuration. The ¹HNMR data allow to predict the most stable conformation.     

Identification of markers of thermal processing (“roasting”) in aqueous extracts of Coffea arabica L. seeds through NMR fingerprinting and chemometrics

Roasting of Coffea arabica L. seeds gives rise to chemical reactions that produce more than 800 compounds, some being responsible for the desired organoleptic properties for which the beverage called “coffee” is known. In the industry, the “roasting profile,” that is, the times and temperatures applied, is key to influence the composition of roasted coffee beans and the flavour of the beverage made from them. The impact of roasting on the chemical composition of coffee has been the subject of numerous studies, including by nuclear magnetic resonance (NMR) spectroscopy. However, the roasting equipment and profiles applied in these studies are often far from real industrial conditions. In this work, the effects of two critical technological parameters of the roasting process, namely, the “development time” (the period of time after the “first crack,” a characteristic noise due to seed disruption) and the final roasting temperature on coffee extracts, were investigated. Seeds were roasted at pilot scale according to 13 industrial roasting profiles and extracted in D₂O. The extracts were analysed by ¹H NMR experiments. The NMR spectra were compared using (a) quantitative analysis of main signals by successive orders of magnitude and (b) chemometric tools (principal component analysis, partial least squares and sparse-orthogonal partial least squares analysis). This allowed to identify compounds, which may serve as markers of roasting and showed that changes in chemical composition can be detected even for slight change in final temperature (~1°C) or in total roasting time (~25 s).     

Encagement of Gold Nanoclusters in Crosslinked Resorcinarene Shells

Monolayers of resorcinarene tetraene 1 on gold nanoclusters could be crosslinked by olefin metathesis into a nondesorptive shell. Crosslinking conditions were optimized by monitoring olefin metathesis of 1 by 1 H NMR spectroscopy and obtaining empirical rate constants. Gel permeation chromatography (GPC) was found to be a useful tool for evaluating the enhanced stability of the encaged nanoparticles; resorcinarene-encapsulated nanoparticles which were not subjected to olefin metathesis did not survive GPC analysis, whereas nanoparticles in crosslinked shells were found to be stable.     

Influence of some lime-containing additives on the thermal behavior of urea

Urea is one of the main nitrogen fertilizers used in agriculture. But being well soluble in water, hardly 50% of its nitrogen is assimilated by plants. One possibility to eliminate this disadvantage is to use coating agents for modification of urea to obtain a controlled-realized fertilizer. The aim of this research was to study the influence of different lime-containing additives on the thermal behavior and decomposition kinetics of urea in oxidizing atmosphere. Commercial fertilizer-grade urea (46.4% N) and analytical-grade CaO, MgO, CaCO₃, MgCO₃ were used in the experiments. In addition, one Estonian limestone and one dolomite sample were used as additive or coating material. The experiments with a Setaram Setsys 1750 thermoanalyzer coupled to a Nicolet 380 FTIR Spectrometer by a heated transfer line were carried out under non-isothermal conditions up to 900 °C at the heating rate of 5 °C min^?1 and to calculate kinetic parameters, additionally, at 1, 2, and 10 °C min^?1 in the atmosphere containing 80% of Ar and 20% of O₂. The differential isoconversional method of Friedman was used to calculate the kinetic parameters. The results obtained indicate that thermooxidative decomposition of urea as well as the blends of urea with lime-containing materials and urea prills coated with limestone or dolomite powder follows a complex reaction mechanism.     

TG-FTIR/MS analysis of thermal and kinetic characteristics of some coal samples

Thermooxidative decomposition (TOD) of seven coal samples from different deposits (Bulgaria, Russia, Ukraine) was studied with the aim to determine characteristics of the process and the differences related to the origin of the coal samples studied. The experiments with a Setaram Setsys 1750 or Labsys Evo 1600 thermoanalyzers coupled to a Nicolet 380 FTIR spectrometer or Pfeiffer mass spectrometer, respectively, were carried out under non-isothermal heating conditions up to 1,000 °C at the heating rates of 1, 2, 5, 10, and 20 °C min^?1 in an oxidizing atmosphere. A model-free kinetic analysis approach based on the differential isoconversional method of Friedman was used to calculate the kinetic parameters. The combined TG-FTIR and TG-MS study of TOD of the coal samples made it possible to identify a number of gaseous species formed and evolved at that as well as to determine the differences in the thermal behavior of the coal samples and in the emission profiles of these species depending on their origin. The value of activation energy E along the reaction progress α varied more for the samples with higher content of organic matter and, especially, for the samples having at that also quite high content of mineral matter, indicating to the close association of mineral matter with organic matter and fixed carbon.     

A simple method for methylmercury,inorganic mercury and ethylmercury determination in plasma samples by high performance liquid chromatography–cold-vapor-inductively coupled plasma mass spectrometry

A simple and sensitive method with a fast sample preparation procedure is proposed for the determination of mercury species in plasma/serum. The method combines online high-performance liquid chromatography separation, Hg cold-vapor formation and inductively coupled plasma mass spectrometry detection. Prior to analysis, plasma (250 μL) was accurately pipetted into 15 mL conical tubes. Then, an extractant solution containing mercaptoethanol, L-cysteine and HCl was added to the samples following sonication for 10 min. Quantitative mercury extraction was achieved with the proposed procedure. Separation of mercury species was accomplished in less than 8 min on a C8 reverse phase column with a mobile phase containing 3% v/v methanol + 97% v/v (0.5% v/v 2-mercaptoethanol + 0.05% v/v formic acid). The method detection limits were found to be 12 ng L⁻¹, 5 ng L⁻¹ and 4 ng L⁻¹ for inorganic mercury, ethylmercury and methylmercury, respectively. Method accuracy is traceable to Standard Reference Material (SRM) 966 Toxic Metals in Bovine Blood from NIST. Additional validation was provided by the analysis of a secondary reference serum sample from the INSQ-Canada. Finally, the method was successfully applied for the speciation of mercury in plasma samples collected from volunteers exposed to methylmercury through fish consumption. For the first time to our knowledge, levels of different species of Hg in plasma samples from riverside populations exposed to MeHg were determined.     

Phosphine-Free Suzuki Cross-Coupling Reaction Using an Efficient and Reusable Pd Catalyst in an Aqueous Medium Under Microwave Irradiation

Abstract

We report here an improved, highly efficient, and general method for the ligand-free Suzuki cross-coupling reaction to the synthesis of biaryls, bipyridyls, thienylpyridine, and allylphenols. Microwave irradiation of (het)aryl halides and (hetaryl, allyl)arylboronic acid N-methyl-iminodiacetic acid (MIDA) ester, using polyurea microencapsulated palladium catalyst (Pd EnCat 30), gave the coupling adducts 1a–x in excellent yields in just 10–18 min.     

Nonlinear transmission coefficient of ytterbium-holmium fiber at the wavelength 978 nm

An experimental and theoretical investigation of the nonlinear transmission coefficient of ytterbium-holmium codoped silica fiber (YHF) at continuous-wave 978-nm pumping is reported. An analysis of the fiber absorption and luminescence spectra under 978-nm pumping reveals a variety of processes participating in the mixed (Yb³⁺, Ho³⁺) system: the energy transfer Yb³⁺ → Ho³⁺, the up-conversion and excited-state absorption in Ho³⁺, and the luminescence quenching due to the presence of Yb³⁺-Yb³⁺ ion pairs. These processes are shown to notably affect the transmission coefficient of YHF, which is reflected in a pronounced modification of its dependences on pump power, fiber length, and dopant concentrations, in comparison with the case of purely ytterbium-doped fiber (YF). A modeling of the experimentally measured dependences of the YHF transmission coefficient on pump power and fiber length allows us to obtain the coefficients addressing the energy transfer process Yb³⁺ → Ho³⁺ in YHF. A comparison of YHF and YF at the same pumping conditions reveals that, in YHF, a considerable part of the pump power absorbed in the Yb³⁺ subsystem is transferred into the Ho³⁺ subsystem; this results in an effective population of its ⁵ I ₇ state and makes YHF promising for 2-μm lasing and amplifying.