Novel Synthetic Approach to Heteroatom Doped Polycyclic Aromatic Hydrocarbons: Optimizing the Bottom-Up Approach to Atomically Precise Doped Nanographenes

The success of the rational bottom-up approach to nanostructured carbon materials and the discovery of the importance of their doping with heteroatoms puts under the spotlight all synthetic organic approaches to polycyclic aromatic hydrocarbons. The construction of atomically precise heteroatom doped nanographenes has evidenced the importance of controlling its geometry and the position of the doping heteroatoms, since these parameters influence their chemical–physical properties and their applications. The growing interest towards this research topic is testified by the large number of works published in this area, which have transformed a once “fundamental research” into applied research at the cutting edge of technology. This review analyzes the most recent synthetic approaches to this class of compounds.     

Antioxidant and Antisteatotic Activities of Fucoidan Fractions from Marine and Terrestrial Sources

Fucoidan is a fucose-rich sulfated polysaccharide typically found in the cell wall of marine algae but also recently isolated from terrestrial sources. Due to a variety of biological activities, including antioxidant properties, fucoidan exhibits an attractive therapeutic potential against a wide array of metabolic diseases associated with oxidative stress. We used FTIR, ¹H NMR and ¹³C NMR spectroscopy to investigate the structural features of a fucoidan fraction extracted from the brown alga Cystoseira compressa (CYS). The antioxidant potential of CYS was measured by DPPH, ABTS and FRAP assays, which revealed a radical scavenging capacity that was confirmed in in vitro cellular models of hepatic and endothelial cells. The same antioxidant effects were observed for another fucoidan fraction previously identified in the terrestrial tree Eucalyptus globulus (EUC). Moreover, in hepatic cells, CYS and EUC exhibited a significant antisteatotic action, being able to reduce intracellular triglyceride content through the regulation of key genes of hepatic lipid metabolism. EUC exerted stronger antioxidant and antisteatotic effects as compared to CYS, suggesting that both marine and terrestrial sources should be considered for fucoidan extraction and therapeutic applications.     

The development of a gas chromatographic–mass spectrometric analytical procedure for the determination of lipids,proteins and resins in the same paint micro-sample avoiding interferences from inorganic media

This paper presents a GC–MS analytical procedure for determining proteinaceous materials, glycerolipids, natural waxes and terpenoid resins in the same paint micro-sample. The procedure is also reliable when high amounts of interfering inorganic pigments, dryers and charges are present. The characterisation of proteinaceous binders in a paint sample can be subject to analytical interferences by inorganic materials. Such materials may form complexes with functional groups of proteins, thus preventing their efficient derivatisation, which is necessary prior to GC analysis. For this reason an analytical procedure has been developed based on two extractions and a clean-up step, in order to obtain two fractions: a lipid-resinous fraction and a proteinaceous fraction. The lipid-resinous fraction is subjected to salification/saponification assisted by microwaves, followed by acidification, extraction, derivatisation and GC–MS analysis. The proteinaceous fraction is analysed by GC–MS after hydrolysis and derivatisation of the freed amino acids. The desalting step is applied before the hydrolysis, and is based on the use of the monolithic sorbent tip technology with a C4 stationary phase. Reference paint replicas of egg, casein and animal glue were prepared with and without several metals containing pigments, and used to develop and validate the analytical procedure. The procedure proved to be efficient in desalting the proteinaceous materials both from cations and anions. Although non quantitative, it is reliable in the analysis of samples whose content of extractable proteins is <1 μg, thus showing it to be suitable for the characterisation of paint samples. An example of how the analytical procedure was used to characterise a sample from a 15th century panel painting is also discussed.     

Conformationally gated photoinduced processes within photosensitizer-acceptor dyads based on osmium(II) complexes with triarylpyridinio-functionalized terpyridyl ligands: insights from theoretical analysis

A theoretical analysis, based on density functional theory, has been carried out to study photoinduced processes within a recently experimentally characterized (Lainé, P. P.; Bedioui, F.; Loiseau, F.; Chiorboli, C.; Campagna, S. J. Am. Chem. Soc. 2006, http://dx.doi.org/10.1021/ja058357w.) series of Os(II) bis-tpy complexes (tpy = 2,2':6'2' '-terpyridine) functionalized by 2,4,6-triarylpyridinium groups, TP+. These dyad systems, designed to produce a charge-separated state (CSS) upon light excitation, are made up of a photosensitizer unit (P, the metal complex) and a tunable acceptor unit (A, the TP+). A full ab initio characterization of the electronic and structural properties of the lowest-lying triplet excited states, as well as of the CSS, allowed for a complete rationalization of the photoinduced processes taking place within the dyads. Among salient insights, theory allowed (i) substantiation of the inner P structural planarization as the relaxation mode of the MLCT states, (ii) confirmation of the existence of a ligand-centered triplet excited state (3LC) shown to essentially involve the nitro substituent of A (TP+-NO2) and lying very close in energy to the P-centered 3MLCT state, and (iii) a demonstration that the energy of the 3LC level is independent of intercomponent tilt angle (theta1). On this basis, the occurrence of a reversible electronic energy transfer between the 3MLCT and the 3LC states could be substantiated and shown to depend on the intramolecular conformation represented by theta1, which actually governs their electronic coupling (essentially via the degree of intercomponent conjugation). These computational issues were checked against experimental data already available and the results of a specifically undertaken photophysical study. Finally, CSS formation has been confirmed by studying the spin density patterns of reduced nitro-derivatized dyads. Taken together, these findings accurately account for the different excited-state behaviors of the dyads as a function of the level of structural restriction of their intercomponent conformation (and related amplitude for torsional fluctuations), thus providing theoretical evidence of conformationally gated photoinduced electron- and energy-transfer processes.     

Microwave-assisted extraction of coumarin and related compounds from Melilotus officinalis (L.) Pallas as an alternative to Soxhlet and ultrasound-assisted extraction

Soxhlet extraction, ultrasound-assisted extraction (USAE) and microwaves-assisted extraction (MAE) in closed system have been investigated to determine the content of coumarin, o-coumaric and melilotic acids in flowering tops of Melilotus officinalis. The extracts were analyzed with an appropriate HPLC procedure. The reproducibility of extraction and of chromatographic analysis was proved. Taking into account the extraction yield, the cost and the time, we studied the effects of extraction variables on the yield of the above-mentioned compounds. Better results were obtained with MAE (50% v/v aqueous ethanol, two heating cycles of 5 min, 50 degrees C). On the basis of the ratio extraction yield/extraction time, we therefore propose MAE as the most efficient method.     

Synthesis and characterization of new difunctional alkynylated (η-arene)(η-cycloocta-1,5-diene)ruthenium(0) complexes as molecular models for organometallic polymers

The new dialkynylated complexes Ru(η⁶-DEB-Si)(η⁴-COD), 4a, Ru(η⁶-DEBP-Si)(η⁴-COD), 4b1, Ru₂(η⁶,η⁶-DEBP)(η⁴-COD)₂, 4b2 [COD = 1,5-cyclooctadiene; DEB-Si = 1,4-bis(trimethylsilylethynyl)benzene; DEBP-Si = 4,4′-bis(trimethylsilylethynyl)biphenyl] have been synthesized by the arene exchange reaction with the complex Ru(η⁶-naphthalene)(η⁴-COD). The complexes Ru(η⁶-DEB)(η⁴-COD), 5a, and Ru(η⁶-DEBP)(η⁴-COD), 5b1, have been prepared by desilylation of the corresponding compounds 4a and 4b1. All the complexes have been fully characterized by means of spectroscopic techniques.     

Sampling soil-derived CO2 for analysis of isotopic composition: a comparison of different techniques

A new system for soil respiration measurement [P. Rochette, L.B. Flanagan, E.G. Gregorich. Separating soil respiration into plant and soil components using analyses of the natural abundance of carbon-13. Soil Sci. Soc. Am. J., 63, 1207-1213 (1999).] was modified in order to collect soil-derived CO2 for stable isotope analysis. The aim of this study was to assess the suitability of this modified soil respiration system to determine the isotopic composition (delta13C) of soil CO2 efflux and to measure, at the same time, the soil CO2 efflux rate, with the further advantage of collecting only one air sample. A comparison between different methods of air collection from the soil was carried out in a laboratory experiment. Our system, as well as the other dynamic chamber approach tested, appeared to sample the soil CO2, which is enriched with respect to the soil CO2 efflux, probably because of a mass dependent fractionation during diffusion and because of the atmospheric contribution in the upper soil layer. On the contrary, the static accumulation of CO2 into the chamber headspace allows sampling of delta13C-CO2 of soil CO2 efflux.     

The rotational spectrum of methyl trifluoroacetate

ABSTRACT

The pulsed supersonic jet expansion microwave spectra of the parent and all three ¹³C mono-substituted isotopologues of methyl trifluoroacetate have been measured in the 6.5–18 GHz range. All observed transitions are split into two component lines, due to the internal rotation of the methyl group. The corresponding barrier has been determined to be V ₃ = 4.379(3) kJ/mol. Structural information has been obtained from the 12 available rotational constants.     

Single-step versus stepwise two-electron reduction of polyarylpyridiniums: insights from the steric switching of redox potential compression

Contrary to 4,4'-dipyridinium (i.e., archetypal methyl viologen), which is reduced by two single-electron transfers (stepwise reduction), the 4,1'-dipyridinium isomer (so-called "head-to-tail" isomer) undergoes two electron transfers at apparently the same potential (single-step reduction). A combined theoretical and experimental study has been undertaken to establish that the latter electrochemical behavior, also observed for other polyarylpyridinium electrophores, is due to potential compression originating in a large structural rearrangement. Three series of branched expanded pyridiniums (EPs) were prepared: N-aryl-2,4,6-triphenylpyridiniums (Ar-TP), N-aryl-2,3,4,5,6-pentaphenylpyridiniums (Ar-XP), and N-aryl-3,5-dimethyl-2,4,6-triphenylpyridinium (Ar-DMTP). The intramolecular steric strain was tuned via N-pyridinio aryl group (Ar) phenyl (Ph), 4-pyridyl (Py), and 4-pyridylium (qPy) and their bulky 3,5-dimethyl counterparts, xylyl (Xy), lutidyl (Lu), and lutidylium (qLu), respectively. Ferrocenyl subunits as internal redox references were covalently appended to representative electrophores in order to count the electrons involved in EP-centered reduction processes. Depending on the steric constraint around the N-pyridinio site, the two-electron reduction is single-step (Ar = Ph, Py, qPy) or stepwise (Ar = Xy, Lu, qLu). This steric switching of the potential compression is accurately accounted for by ab initio modeling (Density Functional Theory, DFT) that proposes a mechanism for pyramidalization of the N(pyridinio) atom coupled with reduction. When the hybridization change of this atom is hindered (Ar = Xy, Lu, qLu), the first reduction is a one-electron process. Theory also reveals that the single-step two-electron reduction involves couples of redox isomers (electromers) displaying both the axial geometry of native EPs and the pyramidalized geometry of doubly reduced EPs. This picture is confirmed by a combined UV-vis-NIR spectroelectrochemical and time-dependent DFT study: comparison of in situ spectroelectrochemical data with the calculated electronic transitions makes it possible to both evidence the distortion and identify the predicted electromers, which play decisive roles in the electron-transfer mechanism. Last, this mechanism is further supported by in-depth analysis of the electronic structures of electrophores in their various reduction states (including electromeric forms).