Large Deviation Techniques Applied to Systems with Long-Range Interactions

We discuss a method to solve models with long-range interactions in the microcanonical and canonical ensemble. The method closely follows the one introduced by R.S. Ellis, Physica D 133:106 (1999), which uses large deviation techniques. We show how it can be adapted to obtain the solution of a large class of simple models, which can show ensemble inequivalence. The model Hamiltonian can have both discrete (Ising, Potts) and continuous (HMF, Free Electron Laser) state variables. This latter extension gives access to the comparison with dynamics and to the study of non-equilibrium effects. We treat both infinite range and slowly decreasing interactions and, in particular, we present the solution of the α-Ising model in one-dimension with 0 ⩽ α < 1.     

Three-stage auto-ignition of n-heptane and methyl-cyclohexane mixtures at lean conditions in a flat piston rapid compression machine

One approach to enhancing the thermal efficiency of combustion systems is to burn fuels at ultra-lean conditions (equivalence ratio below 0.5). It has been recently reported that the auto-ignition of some hydrocarbon fuels, under specific temperature, pressure, and mixture conditions, releases heat in three distinctive stages. The three auto-ignition stages can be divided as a first low-temperature auto-ignition stage with conventional low temperature, and a high-temperature stage separated into two sub-stages. This study presents ignition delay time measurements of n-heptane and methyl-cyclohexane (MCH) mixtures in a flat piston rapid compression machine (RCM) under ultra-lean conditions. It provides experimental evidence of three-stage auto-ignition. This phenomenon of delayed high-temperature heat release is seldom reported in the literature and this is the first time to be reported for these types of fuels. The experiments cover two binary n-heptane/MCH mixtures of 15/85 and 70/30 by volume, pressures of 11 bar and 16 bar, temperature range of 700 to 900 K, and equivalence ratio of 0.4. The RCM optical access was utilized for high-speed chemiluminescence imaging. Detailed chemical kinetic simulations in a homogenous batch reactor with variable volume were conducted to further interrogate the three-stage auto-ignition phenomenon. Chemiluminescence shows that three-stage auto-ignition occurs in the adiabatically compressed end-gas, which indicates that this phenomenon is chemically-driven and is not induced by a thermal stratification in the RCM experiments. The model predicts the features of three-stage auto-ignition, which were experimentally observed at temperatures approximately below 750 K. As expected, significant discrepancies are observed in the ignition delays of experiment and simulation in the negative temperature coefficient (NTC) region. The simulation of the n-heptane/MCH 70/30 mixture shows better agreement with experiments in the Positive Temperature Coefficient (PTC) region compared to the 15/85 mixture.     

Functionalization of Organic Molecules by Transition‐Metal‐Catalyzed C(sp3)?H Activation

Transition‐metal‐catalyzed C? H activation has recently emerged as a powerful tool for the functionalization of organic molecules. While many efforts have focused on the functionalization of arenes and heteroarenes by this strategy in the past two decades, much less research has been devoted to the activation of non‐acidic C? H bonds of alkyl groups. This Minireview highlights recent work in this area, with a particular emphasis on synthetically useful methods.     

In‐ and Out‐of‐Cavity Interactions by Modulating the Size of Ruthenium Metallarectangles

Cationic (arene)ruthenium‐based tetranuclear complexes of the general formula [Ru₄(η⁶‐p‐cymene)₄(μ‐N∩N)₂(μ‐OO∩OO)₂]⁴⁺ were obtained from the dinuclear (arene)ruthenium complexes [Ru₂(η⁶‐p‐cymene)₂(μ‐OO∩OO)₂Cl₂] (p‐cymene=1‐methyl‐4‐(1‐methylethyl)benzene, OO∩OO=5,8‐dihydroxy‐1,4‐naphthoquinonato(2?), 9,10‐dihydroxy‐1,4‐anthraquinonato(2?), or 6,11‐dihydroxynaphthacene‐5,12‐dionato(2?)) by reaction with pyrazine or bipyridine linkers (N∩N=pyrazine, 4,4′‐bipyridine, 4,4′‐[(1E)‐ethene‐1,2‐diyl]bis[pyridine]) in the presence of silver trifluoromethanesulfonate (CF₃SO₃Ag) (Scheme). All complexes 4 – 12 were isolated in good yield as CF₃SO salts, and characterized by NMR and IR spectroscopy. The host–guest properties of the metallarectangles incorporating 4,4′‐bipyridine and (4,4′‐[(1E)‐ethene‐1,2‐diyl]bis[pyridine] linkers were studied in solution by means of multiple NMR experiments (1D, ROESY, and DOSY). The largest metallarectangles 10 – 12 incorporating (4,4′‐[(1E)‐ethene‐1,2‐diyl]bis[pyridine] linkers are able to host an anthracene, pyrene, perylene, or coronene molecule in their cavity, while the medium‐size metallarectangles 7 – 9 incorporating 4,4′‐bipyridine linkers are only able to encapsulate anthracene. However, out‐of‐cavity interactions are observed between these 4,4′‐bipyridine‐containing rectangles and pyrene, perylene, or coronene. In contrast, the small pyrazine‐containing metallarectangles 4 – 6 show no interaction in solution with this series of planar aromatic molecules.     

Photoinduced electron transfer in Zn(II)porphyrin-bridge-Pt(II)acetylide complexes: variation in rate with anchoring group and position of the bridge

The synthesis and photophysical characterization of two sets of zinc porphyrin platinum acetylide complexes are reported. The two sets of molecules differ in the way the bridging phenyl-ethynyl unit is attached to the porphyrin ring. One set is attached via an ethynyl unit on the β position, while the other set is attached via a phenyl unit on the meso position of the porphyrin. These were compared with previously studied complexes where attachment was made via an ethynyl unit on the meso position. Femtosecond transient absorption measurements showed in all systems a rapid quenching of the porphyrin singlet state. Electron transfer is suggested as the quenching mechanism, followed by an even faster recombination to form both the porphyrin ground and triplet excited states. This is supported by the variation in quenching rate and porphyrin triplet yield with solvent polarity, and the observation of an intermediate state in the meso-phenyl linked systems. The different linking motifs between the dyads resulted in significant variations in electron transfer rates.     

Synthesis and evaluation of an Iejimalide-archazolid chimera

Even though the macrolides of the iejimalide family are of marine origin, whereas those of the archazolid series derive from terrestrial myxobacteria, a comparison of their constitution, stereochemistry, and biological activity suggests that these natural products are close structural and functional relatives. Guided by this perception, compound 5 was prepared, which hybridizes the macrolactone core of iejimalide B (2) with the tail of archazolid A (3). The cytotoxicity profile of this chimera, as determined with a panel of 12 human cancer cell lines, corresponds to that of the parent compound 2, although its potency is lower. This outcome may be interpreted on the basis of molecular dynamics calculations, which suggest that the low energy conformations of 2 and 5 are similar but the energetic barriers between the relevant conformers are distinctly higher for the hybrid structure. The synthesis of 5 hinged on a regioselective functionalization of 2,4-dibromothiazole 6, a highly selective CBS-reduction of ketone 8, a Suzuki cross coupling of vinyl boronate 17 with the elaborate alkenyl iodide 16, and a productive closure of the macrocycle by RCM, which requires the selective activation of two out of eight double bonds present in the cyclization precursor 20 by the second-generation Grubbs catalyst 21.     

Memory of chirality in cascade rearrangements of enediynes

The cascade rearrangement of chiral enediynes 1c-e, involving successively 1,3-proton shift, Saito-Myers cyclization, 1,5-hydrogen atom transfer, and intramolecular coupling of the resulting biradical, proceeded at 80 °C to form tri- and tetracyclic heterocycles possessing a quaternary stereogenic center with a very high level of memory of chirality.     

IEF pattern classification‐derived criteria for the identification of epoetin‐δ in urine

Epoetin‐δ (Dynepo? Shire Pharmaceuticals, Basing stoke, UK) is a synthetic form of erythropoietin (EPO) whose resemblance with endogenous EPO makes it hard to identify using the classical identification criteria. Urine samples collected from six healthy volunteers treated with epoetin‐δ injections and from a control population were immuno‐purified and analyzed with the usual IEF method. On the basis of the EPO profiles integration, a linear multivariate model was computed for discriminant analysis. For each sample, a pattern classification algorithm returned a bands distribution and intensity score (bands intensity score) saying how representative this sample is of one of the two classes, positive or negative. Effort profiles were also integrated in the model. The method yielded a good sensitivity versus specificity relation and was used to determine the detection window of the molecule following multiple injections. The bands intensity score, which can be generalized to epoetin‐α and epoetin‐β, is proposed as an alternative criterion and a supplementary evidence for the identification of EPO abuse.     

Bimetallic ruthenium-tin chemistry: Synthesis and molecular structure of arene ruthenium complexes containing trichlorostannyl ligands

A series of neutral, anionic and cationic arene ruthenium complexes containing the trichlorostannyl ligand have been synthesised from SnCl₂ and the corresponding arene ruthenium dichloride dimers [(η⁶-arene)Ru(μ₂-Cl)Cl]₂ (arene = C₆H₆, PrⁱC₆H₄Me). While the reaction with triphenylphosphine and stannous chloride only gives the neutral mono(trichlorostannyl) complexes [(η⁶-C₆H₆)Ru(PPh₃)(SnCl₃)Cl] (1) and [(η⁶-PrⁱC₆H₄Me)Ru(PPh₃)(SnCl₃)Cl] (2), the neutral di(trichlorostannyl) complex [(η⁶-PrⁱC₆H₄Me)Ru(NCPh)(SnCl₃)₂] (3) could be obtained for the para-cymene derivative with benzonitrile as additional ligand. By contrast, the analogous reaction with the benzene derivative leads to a salt composed of the cationic mono(trichlorostannyl) complex [(η⁶-C₆H₆)Ru(NCPh)₂(SnCl₃)]⁺ (5) and of the anionic tris(trichlorostannyl) complex [(η⁶-C₆H₆)Ru(SnCl₃)₃]⁻ (6). On the other hand, [(η⁶-PrⁱC₆H₄Me)Ru(μ₂-Cl)Cl]₂ reacts with SnCl₂ and hexamethylenetetramine hydrochloride or 18-crown-6 to give the anionic di(trichlorostannyl) complex [(η⁶-PrⁱC₆H₄Me)Ru(SnCl₃)₂Cl]⁻ (4), isolated as the hexamethylenetetrammonium salt or the chloro-tin 18-crown-6 salt. The single-crystal X-ray structure analyses of 1, 2, [(CH₂)₆N₄H][4], [(18-crown-6)SnCl][4] and [5][6] reveal for all complexes a pseudo-tetrahedral piano-stool geometry with ruthenium-tin bonds ranging from 2.56 (anionic complexes) to 2.60 Å (cationic complex).