Salicylic Acid-Catalyzed One-Pot Hydrodeamination of Aromatic Amines by tert-Butyl Nitrite in Tetrahydrofuran

A significant acceleration in the hydrodeamination of in situ formed diazonium salts (from aromatic amines) has been observed in the presence of 10-mol% salicylic acid, using tetrahydrofuran as the hydrogen donor. The reaction proceeds efficiently at 20 °C for a wide range of substituted anilines, even at 10-mmol scale, without any other additive. The same protocol has been adapted to the selective deuterodeamination of some aromatic amines. Control experiments clearly show that aryl radicals are involved in the reaction mechanism.We thank the Ministerio de Economia y Competitividad (CTQ2015-66624-P) and the University of Alicante (VIGROB-173) for financial support

Direct 2D spatial coherence determination using the Fourier analysis method Multi parameter characterization of the P04 beamline at PETRA III

We present a systematic 2D spatial-coherence analysis of the soft-X-ray beamline P04 at PETRA III for various beamline configurations. The influence of two different beam-defining apertures on the spatial coherence properties of the beam is discussed and optimal conditions for coherence-based experiments are found. A significant degradation of the spatial coherence in the vertical direction has been measured and sources of this degradation are identified and discussed. The Fourier-analysis method, which gives fast and simple access to the 2D spatial coherence function of the X-ray beam, is used for the experiment. Here, we exploit the charge scattering of a disordered nanodot sample allowing the use of arbitrary X-ray photon energies with this method

Structure-activity relationships of anthraquinone derivatives derived from bromaminic acid as inhibitors of ectonucleoside triphosphate diphosphohydrolases (E-NTPDases)

Reactive blue 2 (RB-2) had been characterized as a relatively potent ectonucleoside triphosphate diphosphohydrolase (E-NTPDase) inhibitor with some selectivity for NTPDase3. In search for the pharmacophore and to analyze structure-activity relationships we synthesized a series of truncated derivatives and analogs of RB-2, including 1-amino-2-sulfo-4-ar(alk)ylaminoanthraquinones, 1-amino-2-methyl-4-arylaminoanthraquinones, 1-amino-4-bromoanthraquinone 2-sulfonic acid esters and sulfonamides, and bis-(1-amino-4-bromoanthraquinone) sulfonamides, and investigated them in preparations of rat NTPDase1, 2, and 3 using a capillary electrophoresis assay. Several 1-amino-2-sulfo-4-ar(alk)ylaminoanthraquinone derivatives inhibited E-NTPDases in a concentration-dependent manner. The 2-sulfonate group was found to be required for inhibitory activity, since 2-methyl-substituted derivatives were inactive. 1-Amino-2-sulfo-4-p-chloroanilinoanthraquinone (18) was identified as a nonselective competitive blocker of NTPDases1, 2, and 3 (Ki 16–18 μM), while 1-amino-2-sulfo-4-(2-naphthylamino)anthraquinone (21) was a potent inhibitor with preference for NTPDase1 (Ki 0.328 μM) and NTPDase3 (Ki 2.22 μM). Its isomer, 1-amino-2-sulfo-4-(1-naphthylamino)anthraquinone (20), was a potent and selective inhibitor of rat NTPDase3 (Ki 1.5 μM)

Understanding the electrochemistry of "water-in-salt" electrolytes: basal plane highly ordered pyrolytic graphite as a model system.

From Europe PMC via Jisc Publications RouterHistory: ppub 2020-06-01, epub 2020-06-08Publication status: PublishedFunder: Engineering and Physical Sciences Research Council; Grant(s): EP/R023034/1, EP/K005014/1A new approach to expand the accessible voltage window of electrochemical energy storage systems, based on so-called "water-in-salt" electrolytes, has been expounded recently. Although studies of transport in concentrated electrolytes date back over several decades, the recent demonstration that concentrated aqueous electrolyte systems can be used in the lithium ion battery context has rekindled interest in the electrochemical properties of highly concentrated aqueous electrolytes. The original aqueous lithium ion battery conception was based on the use of concentrated solutions of lithium bis(trifluoromethanesulfonyl)imide, although these electrolytes still possess some drawbacks including cost, toxicity, and safety. In this work we describe the electrochemical behavior of a simple 1 : 1 electrolyte based on highly concentrated aqueous solutions of potassium fluoride (KF). Highly ordered pyrolytic graphite (HOPG) is used as well-defined model carbon to study the electrochemical properties of the electrolyte, as well as its basal plane capacitance, from a microscopic perspective: the KF electrolyte exhibits an unusually wide potential window (up to 2.6 V). The faradaic response on HOPG is also reported using K3Fe(CN)6 as a model redox probe: the highly concentrated electrolyte provides good electrochemical reversibility and protects the HOPG surface from adsorption of contaminants. Moreover, this electrolyte was applied to symmetrical supercapacitors (using graphene and activated carbon as active materials) in order to quantify its performance in energy storage applications. It is found that the activated carbon and graphene supercapacitors demonstrate high gravimetric capacitance (221 F g-1 for activated carbon, and 56 F g-1 for graphene), a stable working voltage window of 2.0 V, which is significantly higher than the usual range of water-based capacitors, and excellent stability over 10 000 cycles. These results provide fundamental insight into the wider applicability of highly concentrated electrolytes, which should enable their application in future of energy storage technologies

Soil seal development under simulated rainfall: structural, physical and hydrological dynamics

This study delivers new insights into rainfall-induced seal formation through a novel approach in the use of X-ray Computed Tomography (CT). Up to now seal and crust thickness have been directly quantified mainly through visual examination of sealed/crusted surfaces, and there has been no quantitative method to estimate this important property. X-ray CT images were quantitatively analysed to derive formal measures of seal and crust thickness. A factorial experiment was established in the laboratory using open-topped microcosms packed with soil. The factors investigated were soil type (three soils: silty clay loam - ZCL, sandy silt loam - SZL, sandy loam - SL) and rainfall duration (2-14 minutes). Surface seal formation was induced by applying artificial rainfall events, characterised by variable duration, but constant kinetic energy, intensity, and raindrop size distribution. Soil porosities derived from CT scans were used to quantify the thickness of the rainfall-induced surface seals and reveal temporal seal micro-morphological variations with increasing rainfall duration. In addition, the water repellency and infiltration dynamics of the developing seals were investigated by measuring water drop penetration time (WDPT) and unsaturated hydraulic conductivity (Kun). The range of seal thicknesses detected varied from 0.6 - 5.4 mm. Soil textural characteristics and OM content played a central role in the development of rainfall-induced seals, with coarser soil particles and lower OM content resulting in thicker seals. Two different trends in soil porosity vs. depth were identified: i) for SL soil porosity was lowest at the immediate soil surface, it then increased constantly with depth till the median porosity of undisturbed soil was equalled; ii) for ZCL and SL the highest reduction in porosity, as compared to the median porosity of undisturbed soil, was observed in a well-defined zone of maximum porosity reduction c. 0.24 - 0.48 mm below the soil surface. This contrasting behaviour was related to different dynamics and processes of seal formation which depended on the soil properties. The impact of rainfall-induced surface sealing on the hydrological behaviour of soil (as represented by WDTP and Kun) was rapid and substantial: an average 60% reduction in Kun occurred for all soils between 2 and 9 minutes rainfall, and water repellent surfaces were identified for SZL and ZCL. This highlights that the condition of the immediate surface of agricultural soils involving rainfall-induced structural seals has a strong impact in the overall ability of soil to function as water reservoir

Volatile emissions of scented Alstroemeria genotypes are dominated by terpenes, and a myrcene synthase gene is highly expressed in scented Alstroemeria flowers

Native to South America, Alstroemeria flowers are known for their colourful tepals, and Alstroemeria hybrids are an important cut flower. However, in common with many commercial cut flowers, virtually all the commercial Alstroemeria hybrids are not scented. The cultivar ‘Sweet Laura’ is one of very few scented commercial Alstroemeria hybrids. Characterization of the volatile emission profile of these cut flowers revealed three major terpene compounds: (E)-caryophyllene, humulene (also known as α-caryophyllene), an ocimene-like compound, and several minor peaks, one of which was identified as myrcene. The profile is completely different from that of the parental scented species A. caryophyllaea. Volatile emission peaked at anthesis in both scented genotypes, coincident in cv. ‘Sweet Laura’ with the maximal expression of a putative terpene synthase gene AlstroTPS. This gene was preferentially expressed in floral tissues of both cv. ‘Sweet Laura’ and A. caryophyllaea. Characterization of the AlstroTPS gene structure from cv. ‘Sweet Laura’ placed it as a member of the class III terpene synthases, and the predicted 567 amino acid sequence placed it into the subfamily TPS-b. The conserved sequences R28(R)X8W and D321DXXD are the putative Mg2+-binding sites, and in vitro assay of AlstroTPS expressed in Escherichia coli revealed that the encoded enzyme possesses myrcene synthase activity, consistent with a role for AlstroTPS in scent production in Alstroemeria cv. ‘Sweet Laura’ flowers

Elevated CO2 degassing rates prevented the return of Snowball Earth during the Phanerozoic

The Cryogenian period (~720–635 Ma) is marked by extensive Snowball Earth glaciations. These have previously been linked to CO₂ draw-down, but the severe cold climates of the Cryogenian have never been replicated during the Phanerozoic despite similar, and sometimes more dramatic changes to carbon sinks. Here we quantify the total CO₂ input rate, both by measuring the global length of subduction zones in plate tectonic reconstructions, and by sea-level inversion. Our results indicate that degassing rates were anomalously low during the Late Neoproterozoic, roughly doubled by the Early Phanerozoic, and remained comparatively high until the Cenozoic. Our carbon cycle modelling identifies the Cryogenian as a unique period during which low surface temperature was more easily achieved, and shows that the shift towards greater CO₂ input rates after the Cryogenian helped prevent severe glaciation during the Phanerozoic. Such a shift appears essential for the development of complex animal life

Extremely Long-Lived Stigmas Allow Extended Cross-Pollination Opportunities in a High Andean Plant

High-elevation ecosystems are traditionally viewed as environments in which predominantly autogamous breeding systems should be selected because of the limited pollinator availability. Chaetanthera renifolia (Asteraceae) is an endemic monocarpic triennial herb restricted to a narrow altitudinal range within the high Andes of central Chile (3300–3500 m a.s.l.), just below the vegetation limit. This species displays one of the larger capitulum within the genus. Under the reproductive assurance hypothesis, and considering its short longevity (monocarpic triennial), an autogamous breeding system and low levels of pollen limitation would be predicted for C. renifolia. In contrast, considering its large floral size, a xenogamous breeding system, and significant levels of pollen limitation could be expected. In addition, the increased pollination probability hypothesis predicts prolonged stigma longevity for high alpine plants. We tested these alternative predictions by performing experimental crossings in the field to establish the breeding system and to measure the magnitude of pollen limitation in two populations of C. renifolia. In addition, we measured the stigma longevity in unpollinated and open pollinated capitula, and pollinator visitation rates in the field. We found low levels of self-compatibility and significant levels of pollen limitation in C. renifolia. Pollinator visitation rates were moderate (0.047–0.079 visits per capitulum per 30 min). Although pollinator visitation rate significantly differed between populations, they were not translated into differences in achene output. Finally, C. renifolia stigma longevity of unpollinated plants was extremely long and significantly higher than that of open pollinated plants (26.3±2.8 days vs. 10.1±2.2, respectively), which gives support to the increased pollination probability hypothesis for high-elevation flowering plants. Our results add to a growing number of studies that show that xenogamous breeding systems and mechanisms to increase pollination opportunities can be selected in high-elevation ecosystems

Directed self-assembly, symmetry breaking, and electronic modulation of metal oxide clusters by pyramidal heteroanions

Mixed valence/metal polyoxometalate (POM) clusters are one of the most interesting host species showing the ability to incorporate a wide range of heteroatoms of various charges and geometries. We report herein, the incorporation of different pyramidal EO32- heteroanions (E = PH, S, Se, Te) which are responsible not only for directing the templated assembly of a family of mixed-metal POMs but also for the symmetry-breaking of the traditional Dawson architecture and modulation of the electronic characteristics of the cluster's shell. The isolated family of POMs consists of four members: (Me2NH2)5Na2[Mo11V7O52(HPO3)]·MeOH·5H2O (1), (NH4)7[Mo11V7O52(SO3)]·12H2O (2), K7[Mo11V7O52(SeO3)]·31H2O (3), (Me2NH2)6Na[Mo11V7O52(TeO3)]·15H2O (4), and were characterized by X-ray structural analysis, electrospray ionization mass spectrometry (ESI-MS), thermogravimetric analysis (TGA), UV-vis, IR, elemental and flame atomic absorption spectroscopy (FAAS) analysis, and inductively coupled plasma optical emission spectroscopy (ICP-OES). Cyclic voltammetry (CV) and electron paramagnetic resonance (EPR) spectroscopic studies in concert with density functional theoretical (DFT) calculations elucidate the effect of the heteroatom on the electronic properties of the cluster