Parent,Unsubstituted Hemiporphycene: Synthesis and Properties

Among seven possible nitrogen‐in constitutional isomers of porphyrin only one, porphycene, has been obtained so far in the free, unsubstituted form. Herein, the synthesis of another isomer, parent hemiporphycene ( HPc ), and its thorough structural, spectral, photophysical, electrochemical, and theoretical characterization are reported. Most of the properties of HPc are intermediate between those of porphyrin and porphycene, as evidenced by the values of inner‐cavity dimensions, orbital‐energy splittings, absorption coefficients, magnetic circular dichroism parameters, NH‐stretching frequencies, fluorescence quantum yields, tautomerization rates, and redox potentials. The largest differences arise with respect to tautomerism, due to the low symmetry of HPc and inequivalence of the four nitrogen atoms that define the inner cavity. Two trans tautomers are observed, separated in energy by about 1 kcal mol^?1. Tautomerization from the higher‐ to the lower‐energy form is detected in the lowest‐excited singlet state and occurs at a rate that is about four orders of magnitude lower than that observed for porphycene. Hemiporphycene is a very good model for the investigation of inequivalent intramolecular H‐bonds present in one molecule; two such bonds in HPc reveal unusual characteristics, and the bond strength results from the interplay between the N ??? N distance and the N?H?N angle.     

Deuterium isotope effects on 13C chemical shifts of negatively charged NH…N systems

Deuterium isotope effects on ¹³C chemical shifts are investigated in anions of 1,8‐bis(4‐toluenesulphonamido)naphthalenes together with N,N‐(naphthalene‐1,8‐diyl)bis(2,2,2‐trifluoracetamide) all with bis(1,8‐dimethylamino)napthaleneH⁺ as counter ion. These compounds represent both “static” and equilibrium cases. NMR assignments of the former have been revised. The NH proton is deuteriated. The isotope effects on ¹³C chemical shifts are rather unusual in these strongly hydrogen bonded systems between a NH and a negatively charged nitrogen atom. The formal four‐bond effects are found to be negative indicating transmission via the hydrogen bond. In addition, unusual long range effects are seen. Structures, ¹H and ¹³C NMR chemical shifts and changes in nuclear shieldings upon deuteriation are calculated using density functional theory methods. Copyright © 2013 John Wiley & Sons, Ltd.     

Influence of inner transducer properties on EMF response and stability of solid-contact anion-selective membrane electrodes based on metalloporphyrin ionophores

The performance of solid-contact coated-wire-type electrodes with plasticized poly(vinyl chloride) membranes containing metalloporphyrins as anion-selective ionophores is reported. The membranes are deposited on transducers based on graphite pastes and graphite rods. The hydrophobicity of the underlying conductive transducer surface is found to be a key factor that influences the formation of an aqueous layer beneath the polymer film. Elimination of this ill-defined water layer greatly improves the electrochemical properties of the ion-sensors, such as electromotive force stability and lifetime. Only highly lipophilic electrode substrates, namely graphite paste with mineral oil, were shown to prevent the formation of aqueous layer underneath the ion-sensing membrane. The possibility of employing Co(III)-tetraphenylporphyrin both as NO₂ ⁻ selective ionophore and as electron- and ion-conducting species to ensure ion-to-electron translation was also discussed based on the results of preliminary experiments.     

MgO/CaO-loaded porous carbons for carbon dioxide capture

Nanoporous carbons loaded with both MgO and CaO were prepared by a simple heating of mixtures consisting of poly(ethylene terephthalate) and natural dolomite. Preparations were carried out at temperatures ranging from 850 to 1,000 °C that ensured complete thermal decomposition of the dolomite contained in the mixtures to the oxides. An influence of the PET/dolomite weight ratio and temperature of the preparation process on the porosity of the obtained composite products and on CaO and MgO crystallite sizes are discussed using the results of nitrogen adsorption/desorption at 77 K and X-ray diffraction analyses, respectively. Performances of the hybrid materials as sorbents for carbon dioxide were examined using thermogravimetric analyses. Finally, possibility of regeneration of the spent sorbent materials together with a side—effect accompanying this process are discussed on the basis of thermogravimetric measurements. As found, a part of CO₂ captured by the hybrid sorbents gets adsorbed weakly and another portion is fixed strongly. During thermal regeneration, the strongly fixed CO₂ reacts with carbon material. In this way small fraction of a sorbent is lost.     

Solid Contact Nitrate Ion‐selective Electrode Based on Cobalt(II) Complex with 4,7‐Diphenyl‐1,10‐phenanthroline

Nitrates are a group of compounds widely distributed in the natural environment with many applications in various industries. Due to their ambiguous impact on the human body and suspicions of their carcinogenic activity, they have been very popular for decades and are the subject of research by many scientists in the field of medicine, biology and chemistry. Due to the need to monitor their content in environmental and food samples, various methods for their determination are developed. This paper proposes the use of a nitrate ion‐sensitive ion selective electrode with a membrane containing as the active ingredient a new cobalt(II) complex with 4,7‐diphenyl‐1,10‐phenanthroline (Bphen) of the formula Co(Bphen)₂(NO₃)₂(H₂O)₂. The obtained sensor showed the theoretical slope of the characteristic curve, a wide measuring range, as well as short response time and very good potential stability. It was successfully used for the determination of nitrates in real samples: in mineral water, tap water and river water from eastern Poland.     

NO2 removal on adsorbents prepared from coffee industry waste materials

A technology for obtaining carbonaceous adsorbents by physical and chemical activation of waste materials from coffee industry is described. The effect of pyrolysis temperature and type of activation procedure on the textural parameters, acid–base character of the surface and sorption properties of activated carbons has been tested. The resulting carbons were characterized by low-temperature nitrogen sorption, determination of pH and the number of surface oxygen groups. The sorption properties of the activated carbons obtained were characterized by evaluation of nitrogen dioxide adsorption in dry and wet conditions. The final products were adsorbents of specific surface area ranging from 5 to 2,076 m²/g and pore volume from 0.03 to 1.25 cm³/g, showing very diverse acidic–basic character of the surface. The results obtained in our study have proved that a suitable choice of the pyrolysis and activation procedure for coffee industry wastes permits production of adsorbents with high sorption capacity of nitrogen dioxide, reaching to 44.5 and 84.1 mg NO₂/g in dry and wet conditions, respectively.     

Impact of Harvest Conditions and Host Tree Species on Chemical Composition and Antioxidant Activity of Extracts from Viscum album L.

The content of plant secondary metabolites is not stable, and factors such as the region/location effect and seasonal variations have an impact on their chemical composition, especially in parasitic plants. Research in this area is an important step in the development of quality parameter standards of medicinal plants and their finished products. The effects of the time and place of harvest and the host tree species on the chemical composition and antioxidant activity of mistletoe extracts were investigated. Statistical tools were used to evaluate the results of the spectrophotometric and LC-ESI-MS/MS studies of the phenolic composition and antioxidant activity. The investigations indicate that the qualitative and quantitative composition, influencing the biological activity of mistletoe extracts, largely depends on the origin of the plant. The mistletoe extracts exhibited a rich phenol profile and high antioxidant activity. The chemometric analysis indicated that mistletoe collected from conifers (Viscum abietis and Viscum austriacum) had the most advantageous chemical composition and antioxidant activity. Moreover, the chemical profile and biological activity of the plant material were closely related to the climatic conditions and location of the harvested plant. Higher levels of phenolic compounds and high antioxidant activity were found in extracts obtained from plant material collected in cold weather with the presence of snow and less sunshine (autumn–winter period).     

Dynamics of [n.3]paracyclophanes (n = 2 – 4) as studied by NMR. Obtaining separate Arrhenius parameters for two dynamic processes in [4.3]paracyclophane

Extending our earlier findings for [3.3]paracyclophane, NMR line shape studies of the conformational dynamics in [3.2] and [4.3]paracyclophanes are reported, of which the former is conformationally homogeneous and the latter occurs in two enantiomeric forms. For [3.2]paracyclophane, the Arrhenius activation energy E_a = 11.6 ± 0.1 kcal/mol and preexponential factor log (A/s^?1) = 12.92 ± 0.07 were found. In [4.3]paracyclophane, the conformational dynamics are quite complicated because, apart from interconversions of each enantiomer into itself proceeding via inversion of the propano bridge with rate constant k₁, the enantiomers mutually rearrange with rate constant k₂ due to inversion of the butano bridge. The determination of Arrhenius parameters from dynamic ¹H spectra of the aromatic protons for these two conformational processes (E_a = 11.2 ± 0.5 kcal/mol and log (A/s^?1) = 13.6 ± 0.5 for the former, and E_a = 9.7 ± 0.4 kcal/mol and log (A/s^?1) = 13.2 ± 0.4 for the latter) is the highlight of this work. In the investigated temperature range, in [4.3]paracyclophane, the occurrence of other conformational processes beyond those mentioned above can be excluded, because they would produce different line shape patterns than those actually observed. Copyright © 2013 John Wiley & Sons, Ltd.     

Reaching Milestones in the Oxygenation Chemistry of Magnesium Alkyls: towards Intimate States of O2 Activation and the First Monomeric Well-Defined Magnesium Alkylperoxide

Despite decades of extensive studies on the reactivity of magnesium alkyls towards O₂, the isolation and structural characterization of discrete products of these reactions still remains a challenge. Although the formation of the most frequently encountered magnesium alkoxides through unstable alkylperoxide intermediates has commonly been accepted, the latter species have been elusive for over 100 years. Probing the oxygenation of a seemingly simple well-defined neo-pentylmagnesium complex stabilized by a β-diketiminate ligand, (^dippBDI)MgCH₂CMe₃, we report on the isolation and structure characterization of both a dimeric magnesium alkoxide [(^dippBDI)Mg(μ-OCH₂CMe₃)]₂ and the first example of monomeric magnesium alkylperoxide [(^dippBDI)Mg(thf)OOCH₂CMe₃] (^dippBDI=[(ArNCMe)₂CH]⁻ and Ar=C₆H₃iPr₂-2,6). The formation of monomeric magnesium alkylperoxide demonstrates a crucial role of an additional Lewis base for stabilizing the most elusive oxygenation products likely due to increasing of the electron density on the metal centre. Moreover, the ¹H NMR studies at −80 °C revealed that the dissociation of a coordinated Lewis base from the solvated complex (^dippBDI)Mg(L)CH₂CMe₃ (where L=thf or 4-methylpyridine) is likely not required prior to the effective attack of an O₂ molecule on the metal centre and the four-coordinate alkylmagnesium complex reacts smoothly with O₂ under these conditions. The results can be expected to aid future engineering of various organomagnesium/O₂-based reaction systems.     

A comparison of the GWCE and mixed P − P1 formulations in finite‐element linearized shallow‐water models

The appearance of spurious pressure modes in early shallow‐water (SW) models has resulted in two common strategies in the finite element (FE) community: using mixed primitive variable and generalized wave continuity equation (GWCE) formulations of the SW equations. One FE scheme in particular, the P ? P₁ pair, combined with the primitive equations may be advantageously compared with the wave equation formulations and both schemes have similar data structures. Our focus here is on comparing these two approaches for a number of measures including stability, accuracy, efficiency, conservation properties, and consistency. The main part of the analysis centres on stability and accuracy results via Fourier‐based dispersion analyses in the context of the linear SW equations. The numerical solutions of test problems are found to be in good agreement with the analytical results. Copyright © 2011 John Wiley & Sons, Ltd.