Fano versus Kondo resonances in a multilevel "semiopen" quantum dot

Linear conductance across a large quantum dot via a single level epsilon(0) with large hybridization to the contacts is strongly sensitive to quasibound states localized in the dot and weakly coupled to epsilon(0). The conductance oscillates with the gate voltage due to interference of the Fano type. At low temperature and Coulomb blockade, Kondo correlations damp the oscillations on an extended range of gate voltage values, by freezing the occupancy of the epsilon(0) level itself. As a consequence, the antiresonances of Fano origin are washed out. The results are in good correspondence with experimental data for a large quantum dot in the semiopen regime.     

Enhanced Thermal Oxidation Stability of Reduced Graphene Oxide by Nitrogen Doping

Nitrogen‐doped reduced graphene oxide (N‐doped RGO) samples with a high level of doping, up to 13 wt. %, have been prepared by annealing graphene oxide under a flow of pure ammonia. The presence of nitrogen within the structure of RGO induces a remarkable increase in the thermal stability against oxidation by air. The thermal stability is closely related with the temperature of synthesis and the nitrogen content. The combustion reaction of nitrogen in different coordination environments (pyridinic, pyrrolic, and graphitic) is analyzed against a graphene fragment (undoped) from a thermodynamic point of view. In agreement with the experimental observations, the combustion of undoped graphene turns out to be more spontaneous than when nitrogen atoms are present.     

A Promising Thermodynamic Study of Hole Transport Materials to Develop Solar Cells: 1,3-Bis(N-carbazolyl)benzene and 1,4-Bis(diphenylamino)benzene

The thermochemical study of the 1,3-bis(N-carbazolyl)benzene (NCB) and 1,4-bis(diphenylamino)benzene (DAB) involved the combination of combustion calorimetric (CC) and thermogravimetric techniques. The molar heat capacities over the temperature range of (274.15 to 332.15) K, as well as the melting temperatures and enthalpies of fusion were measured for both compounds by differential scanning calorimetry (DSC). The standard molar enthalpies of formation in the crystalline phase were calculated from the values of combustion energy, which in turn were measured using a semi-micro combustion calorimeter. From the thermogravimetric analysis (TGA), the rate of mass loss as a function of the temperature was measured, which was then correlated with Langmuir’s equation to derive the vaporization enthalpies for both compounds. From the combination of experimental thermodynamic parameters, it was possible to derive the enthalpy of formation in the gaseous state of each of the title compounds. This parameter was also estimated from computational studies using the G3MP2B3 composite method. To prove the identity of the compounds, the ¹H and ¹³C spectra were determined by nuclear magnetic resonance (NMR), and the Raman spectra of the study compounds of this work were obtained.     

Chickpeas from a Chilean Region Affected by a Climate-Related Catastrophe: Effects of Water Stress on Grain Yield and Flavonoid Composition

The Valparaiso region in Chile was decreed a zone affected by catastrophe in 2019 as a consequence of one of the driest seasons of the last 50 years. In this study, three varieties (‘Alfa-INIA’, ‘California-INIA’, and one landrace, ‘Local Navidad’) of kabuli-type chickpea seeds produced in 2018 (control) and 2019 (climate-related catastrophe, hereafter named water stress) were evaluated for their grain yield. Furthermore, the flavonoid profile of both free and esterified phenolic extracts was determined using liquid chromatography-mass spectrometry, and the concentration of the main flavonoid, biochanin A, was determined using liquid chromatography with diode array detection. The grain yield was decreased by up to 25 times in 2019. The concentration of biochanin A was up to 3.2 times higher in samples from the second season (water stress). This study demonstrates that water stress induces biosynthesis of biochanin A. However, positive changes in the biochanin A concentration are overshadowed by negative changes in the grain yield. Therefore, water stress, which may be worsened by climate change in the upcoming years, may jeopardize both the production of chickpeas and the supply of biochanin A, a bioactive compound that can be used to produce dietary supplements and/or nutraceuticals.     

Synthesis of chiral β-3-amino-2-hydroxyalkanoates and 3-alkyl-3-hydroxy-β-lactams by double asymmetric induction

Reactions of chiral (2S)-enolates of dioxolan-4-ones, derived from lactic, mandelic, and phenyllactic acids, with aliphatic (S_S)- and (S_R)-tert-butylsulfinyl aldimines afforded conformationally restrained C2-disubstituted N,O-orthogonally protected 3-amino-2-hydroxyalkanoates in the form of N-sulfinyl protected 1′-aminodioxolan-4-ones. The product distribution showed that there is significant kinetic selectivity, due to the presence of ‘matched’ and ‘mismatched’ components, between the (S)- or (R)-tert-butylsulfinyl aldimines and the (2S)-enolates of the 1,3-dioxolan-4-ones. Selective methoxide-induced removal of the acetal group of the N-sulfinyl-1′-aminodioxolanones yielded the corresponding N-sulfinyl protected methyl alkanoates. In addition, the selective acid-induced removal of the sulfinyl group of the N-sulfinyl-1′-aminodioxolanones provided the corresponding N-unprotected 1′-aminodioxolanones, whose base-induced cyclization afforded the corresponding β-lactams.     

Solid state radiolysis of sulphur-containing amino acids: cysteine,cystine and methionine

The sulphur-containing proteinaceous amino acids l-cysteine, l-cystine and l-methionine were irradiated in the solid state to a dose of 3.2 MGy. This dose corresponds to that delivered by radionuclide decay in a timescale of 1.05 × 10⁹ years to the organic matter buried at a depth >20 m in comets and asteroids. The purity of the sulphur-containing amino acids was studied by differential scanning calorimetry (DSC) before and after the solid state radiolysis and the preservation of the chirality after the radiolysis was studied by chirooptical methods (optical rotatory dispersion, ORD) and by FT-IR spectroscopy. Although the high radiation dose of 3.2 MGy delivered, all the amino acids studied show a high radiation resistance. The best radiation resistance was offered by l-cysteine. The radiolysis of l-cysteine leads to the formation of l-cystine. The radiation resistance of l-methionine is not at the level of l-cysteine but also l-methionine is able to survive the dose of 3.2 MGy. Furthermore in all cases examined the preservation of chirality after radiolysis was clearly observed by the ORD spectroscopy although a certain level of radioracemization was measured in all cases. The radioracemization is minimal in the case of l-cysteine and is more pronounced in the case of l-methionine. In conclusion, the study shows that the sulphur-containing amino acids can survive for 1.05 × 10⁹ years and, after extrapolation of the data, even to the age of the Solar System i.e. to 4.6 × 10⁹ years.     

Mass spectrometry of substituted 1,3-dihydro-2H-imidazole-2-thiones

The electron impact mass spectra of the 4-formyl-1, 3-dihydro-2H-imidazole-2-thione, its six 1-methyl(n-propyl, n-hexyl)-3-methyl(phenyl)-disubstptuted derivatives, and the 1,3-dihydro-1-phenyl-2H-imidazole-2-thiome are discussed. The fragmentation pattern is strongly influenced by the alkyl or phenyl N-substituents, as well as by the length of the alkyl chain. The odd-electron ions containing an N-phenyl substituent, but not a propyl or hexyl group, eject a hydrogen atom from the phenyl ring, while the presence of a long alkyl chain greatly enhances the loss of the sulphyhydryl radical and facilitates the expulsion of several alkenes, and alkyl and alkenyl radicals.     

Suppressed ion chromatography for monitoring chemical impurities in steam for geothermal power plants

A suppressed ion chromatography (IC) technique has been evaluated as a chemical monitoring tool for detecting major anions (F-, Cl-, NO3- and SO4(2-)) of condensed steam in geothermal power plants. It is shown that the suppressed IC technique provides a suitable means for preventing possible damage to generating equipment in the geothermal industry. An electrical conductivity detector (0.1 microS sensitivity) with an anion-exchange column (IonPac AS4A-SC), a micro-membrane suppressor (AMMS II), and an isocratic high-pressure pump system were successfully used for detecting low concentrations of inorganic anions. Method detection limits for the anions of interest were <0.184 mg/L. Details of the IC methodology as well as some experimental results obtained during its application for the chemical monitoring of geothermal steam pipes are also described.