5,11-Diazadibenzo[hi,qr]tetracene: Synthesis,Properties, and Reactivity toward Nucleophilic Reagents

5,11-Diazadibenzo[hi,qr]tetracene was synthesized as a new nitrogen-substituted polycyclic heteroaromatic compound by Pd-catalyzed cycloisomerization of an alkyne precursor followed by oxidative cyclization with bis(trifluoroacetoxy)iodobenzene. The substitution of imine-type nitrogen atoms significantly enhanced its electron-accepting character and facilitated the direct nucleophilic addition of arylamines under strongly basic conditions to afford the desired amino-substituted products. The introduction of amino groups induced a remarkable red-shift in their absorption spectra; the tetrasubstituted product exhibited intense near-infrared absorbing property. Furthermore, the π-electronic system, which includes a redox-active 1,4-diazabutadiene moiety, underwent reversible interconversion to its corresponding reduced form upon reduction with NaBH₄ and aerobic oxidation.     

Synthesis of Benzopyran-4-Amides Potassium Channel Openers Via Palladium-Catalyzed Amidation

The novel potassium channel openers benzopyran-4-amides have been synthesized via palladium-catalyzed amidation of 4-bromobenzopyrans under an atmoshere in the presence of an equivalent of potassium iodide.     

Adsorption of ammonia and water on functionalized edge-rich carbon nanofibers

The preparation, characterization and ammonia and water adsorption properties of edge-rich carbon nanofibers (CNFs) were studied, including platelet CNFs (PCNFs) and cup-stacked CNFs (CSCNFs). Since PCNFs and CSCNFs have many chemically active exposed edges, functionalization by oxidizing the edges was carried out by ozone stream and by nitric acid. Transmission electron microscopy, N₂ adsorption isotherms and temperature-programmed desorption analysis showed that the nitric acid treatment partly destroyed the graphite structure of the PCNFs and created acid functional groups and micropores, whereas the ozone treatment created functional groups without damaging the structure. Ammonia adsorption isotherms clarified that NH₃ adsorption on PCNFs and CSCNFs occurred mainly on oxygen-containing groups, whereas the adsorption on activated carbon fibers (ACFs) occurred on both oxygen-containing groups and the carbon surface without the functional groups, and the CSCNFs showed larger amounts of adsorbed ammonia compared to the PCNFs. Especially at a relatively low pressure range (<0.2 atm), the PCNFs/CSCNFs/ACFs showed the same ammonia adsorption mechanism; that is, the one-to-one interaction between oxygen atoms in the functional groups and hydrogen atoms in ammonia molecules. In addition, the adsorption on the ACFs appeared to occur mainly by interaction with the carbon surface at relatively high pressure (0.3–1.0 atm). Our experimental results and previous findings suggest that NH₃ adsorption on PCNFs is due mainly to NH…O hydrogen bonding between oxygen-containing groups and ammonia rather than to chemical bonding.     

Experimental and Computational Study of the Thermal Decomposition of 3‐Methyl‐3‐buten‐1‐ol in m‐Xylene Solution

An experimental study of the thermal decomposition of a β‐hydroxy alkene, 3‐methyl‐3‐buten‐1‐ol, in m‐xylene solution, has been carried out at five different temperatures in the range of 513.15–563.15 K. The temperature dependence of the rate constants for the decomposition of this compound in the corresponding Arrhenius equation is given by ln k (s^?1) = (25.65 ± 1.52) ? (17,944 ± 814) (kJ·mol^?1)·T^?1. A computational study has been carried out at the M05–2X/6–31+G(d,p) level of theory to calculate the rate constants and the activation parameters by the classical transition state theory. There is a good agreement between the experimental and calculated rate constants and activation Gibbs energies. The bonding characteristics of reactant, transition state, and products have been investigated by the natural bond orbital analysis, which provides the natural atomic charges and the Wiberg bond indices. Based on the results obtained, the mechanism proposed is a one‐step process proceeding through a six‐membered cyclic transition state, being a concerted and slightly asynchronous process. The results have been compared with those obtained previously by us (Struct Chem 2013, 24, 1811–1816) for the thermal decomposition of 3‐buten‐1‐ol, in m‐xylene solution. We can conclude that in the compound studied in this work, 3‐methyl‐3‐buten‐1‐ol, the effect of substitution at position 3 by a weakly activating CH₃ group is the stabilization of the transition state formed in the reaction and therefore a small increase in the rate of thermal decomposition.     

Power of isotopic fine structure for unambiguous determination of metabolite elemental compositions: In silico evaluation and metabolomic application

In mass spectrometry (MS)-based metabolomics studies, reference-free identification of metabolites is still a challenging issue. Previously, we demonstrated that the elemental composition (EC) of metabolites could be unambiguously determined using isotopic fine structure, observed by ultrahigh resolution MS, which provided the relative isotopic abundance (RIA) of ¹³C, ¹⁵N, ¹⁸O, and ³⁴S. Herein, we evaluated the efficacy of the RIA for determining ECs based on the MS peaks of 20,258 known metabolites. The metabolites were simulated with a ≤25% error in the isotopic peak area to investigate how the error size effect affected the rate of unambiguous determination of the ECs. The simulation indicated that, in combination with reported constraint rules, the RIA led to unambiguous determination of the ECs for more than 90% of the tested metabolites. It was noteworthy that, in positive ion mode, the process could distinguish alkali metal-adduct ions ([M + Na]⁺ and [M + K]⁺). However, a significant degradation of the EC determination performance was observed when the method was applied to real metabolomic data (mouse liver extracts analyzed by infusion ESI), because of the influence of noise and bias on the RIA. To achieve ideal performance, as indicated in the simulation, we developed an additional method to compensate for bias on the measured ion intensities. The method improved the performance of the calculation, permitting determination of ECs for 72% of the observed peaks. The proposed method is considered a useful starting point for high-throughput identification of metabolites in metabolomic research.     

1,2-Dihydro-1-hydroxy-2,3,1-benzodiazaborine Bearing an Acridine Moiety as a Circular Dichroism Probe for Determination of Absolute Configuration of Mono-Alcohols

A new chiral probe molecule for mono-alcohols is developed by using 1,2-dihydro-1-hydroxy-2,3,1-benzodiazaborine (DAB) bearing an acridine moiety 1 . In the presence of mono-alcohols, DAB 1 forms borate 2 by boronic ester formation, followed by coordination of the acridine moiety to the boron atom. Borate 2 has a chiral center on the boron atom and works as a stereodynamic circular dichroism (CD) probe molecule for chiral mono-alcohols based on the π–π interaction between the acridine moiety and the carbon–carbon unsaturated moiety on mono-alcohols.     

A quantitative model of preferential evaporation and retention for atom probe tomography

It is well known that the apparent concentration of a solute element in metal, detected by atom probe tomography analysis, depends on the measurement condition such as specimen temperature, pulse fraction, and pulse frequency. The dependence was qualitatively interpreted to be caused by preferential evaporation and retention in field evaporation. A quantitative physical model accounting for the preferential evaporation and retention was proposed herein for the first time. The proposed model was applied to a ferritic iron–copper (Fe–Cu) alloy for preferential evaporation and a ferritic iron–silicon (Fe–Si) alloy for preferential retention. The model explained the temperature dependence on the apparent concentration of the solute element and the unwindowed background noise in each alloy well, whereas the dependence of pulse fraction and pulse frequency was not completely explained. The cause of the difference between the experimental and calculated results based on the model was discussed. Copyright © 2014 John Wiley & Sons, Ltd.