On-Line Coupling of Separation Techniques to NMR

The hyphenation of chromatographic separation techniques with NMR spectroscopy is one of the most powerful and time-saving methods for the separation and structural elucidation of unknown compounds and molecular compositions of mixtures. Most of the routinely used NMR flow-cells have detection volumes between 40–180 μL for conventional separations with analytical columns, and the newest designs employ detection volumes in the order of 200 nL for capillary separations. The low flow rates used in capillary chromatography permit the use of deuterated solvents. Unequivocal structural assignment of unknown chromatographic peaks is possible by two-dimensional stopped-flow capillary HPLC-NMR experiments.     

A shock tube study of the reactions of CH with CO2 and O2

The formation and consumption of CH radicals during shock-induced pyrolysis of a few ppm ethane diluted in argon was measured by a ring-dye laser spectrometer. Absorption-over-time profiles, measured at a resonance line in the Q-branch of the A²Δ − X²Π band of CH at λ = 431.1311 nm, were recorded and transformed into CH concentrations by known absorption coefficients. By adding some hundred ppm of CO₂ or O₂ to the initial mixtures, the CH concentration profiles were significantly perturbed. Both the perturbed and unperturbed CH concentration profiles have been compared with calculations based on a reaction kinetic model. A sensitivity analysis revealed that the perturbation process was dominated by direct reactions of CH with the added molecules. By fitting calculated to observed CH profiles the following rate coefficients were obtained The experiments were performed in the temperature range between 2500 K and 3500 K. © 1996 John Wiley & Sons, Inc.     

A coupled-channel lattice study of the resonance-like structure Zc(3900)

In this exploratory study, near-threshold scattering of D and \begin{document}$\bar{D}^*$\end{document} meson is investigated using lattice QCD with \begin{document}$N_f=2+1+1$\end{document} twisted mass fermion configurations. The calculation is performed in the coupled-channel Lüscher finite-size formalism. The study focuses on the channel with \begin{document}$I^G(J^{PC})=1^+(1^{+-})$\end{document} where the resonance-like structure \begin{document}$Z_c(3900)$\end{document} was discovered. We first identify the two most relevant channels and the lattice study is performed in the two-channel scattering model. Combined with the two-channel Ross-Shaw theory, scattering parameters are extracted from the energy levels by solving the generalized eigenvalue problem. Our results for the scattering length parameters suggest that for the particular lattice parameters that we studied, the best fit parameters do not correspond to the peak in the elastic scattering cross-section near the threshold. Furthermore, in the zero-range Ross-Shaw theory, the scenario of a narrow resonance close to the threshold is disfavored beyond the 3\begin{document}$\sigma$\end{document} level.     

Direct Numerical Simulation of Head-On Quenching of Statistically Planar Turbulent Premixed Methane-Air Flames Using a Detailed Chemical Mechanism

A three-dimensional compressible Direct Numerical Simulation (DNS) analysis has been carried out for head-on quenching of a statistically planar stoichiometric methane-air flame by an isothermal inert wall. A multi-step chemical mechanism for methane-air combustion is used for the purpose of detailed chemistry DNS. For head-on quenching of stoichiometric methane-air flames, the mass fractions of major reactant species such as methane and oxygen tend to vanish at the wall during flame quenching. The absence of \(\text {OH}\) at the wall gives rise to accumulation of carbon monoxide during flame quenching because \(\text {CO}\) cannot be oxidised anymore. Furthermore, it has been found that low-temperature reactions give rise to accumulation of \(\text {HO}_{2}\) and \(\mathrm {H}_{2}\mathrm {O}_{2}\) at the wall during flame quenching. Moreover, these low temperature reactions are responsible for non-zero heat release rate at the wall during flame-wall interaction. In order to perform an in-depth comparison between simple and detailed chemistry DNS results, a corresponding simulation has been carried out for the same turbulence parameters for a representative single-step Arrhenius type irreversible chemical mechanism. In the corresponding simple chemistry simulation, heat release rate vanishes once the flame reaches a threshold distance from the wall. The distributions of reaction progress variable c and non-dimensional temperature T are found to be identical to each other away from the wall for the simple chemistry simulation but this equality does not hold during head-on quenching. The inequality between c (defined based on \(\text {CH}_{4}\) mass fraction) and T holds both away from and close to the wall for the detailed chemistry simulation but it becomes particularly prominent in the near-wall region. The temporal evolutions of wall heat flux and wall Peclet number (i.e. normalised wall-normal distance of \(T = 0.9\) isosurface) for both simple and detailed chemistry laminar and turbulent cases have been found to be qualitatively similar. However, small differences have been observed in the numerical values of the maximum normalised wall heat flux magnitude \(\left ({\Phi }_{\max } \right )_{\mathrm {L}}\) and the minimum Peclet number \((Pe_{\min })_{\mathrm {L}}\) obtained from simple and detailed chemistry based laminar head-on quenching calculations. Detailed explanations have been provided for the observed differences in behaviours of \(\left ({\Phi }_{\max }\right )_{\mathrm {L}}\) and \((Pe_{\min })_{\mathrm {L}}\). The usual Flame Surface Density (FSD) and scalar dissipation rate (SDR) based reaction rate closures do not adequately predict the mean reaction rate of reaction progress variable in the near-wall region for both simple and detailed chemistry simulations. It has been found that recently proposed FSD and SDR based reaction rate closures based on a-priori DNS analysis of simple chemistry data perform satisfactorily also for the detailed chemistry case both away from and close to the wall without any adjustment to the model parameters.     

Defined Poly[styrene‐block‐(ferrocenylmethyl methacrylate)] Diblock Copolymers via Living Anionic Polymerization

Ferrocenylmethyl methacrylate (FMMA) is one of the very few metallocene‐based monomers that are promising candidates for truly living anionic polymerization. Nevertheless, FMMA homopolymers with a narrow polydispersity, or block copolymerization studies that result in satisfying blocking efficiencies, are unknown so far. Here we describe a procedure that leads to highly regular FMMA‐based polymers for the first time, characterized by polydispersity indices (PDI) of less that 1.05 and very high blocking efficiencies (>95%) in sequential copolymerization with styrene. Some of the obtained poly[styrene‐block‐(ferrocenylmethyl methacrylate)]s show unusual microphase morphologies, presumably the consequence of high T_gs causing ‘frustrated’ non‐equilibrium states.

     

Networks that optimize a trade-off between efficiency and dynamical resilience

In this Letter we study networks that have been optimized to realize a trade-off between communication efficiency and dynamical resilience. While the first is related to the average shortest pathlength, we argue that the second can be measured by the largest eigenvalue of the adjacency matrix of the network. Best efficiency is realized in star-like configurations, while enhanced resilience is related to the avoidance of short loops and degree homogeneity. Thus crucially, very efficient networks are not resilient while very resilient networks lack in efficiency. Networks that realize a trade-off between both limiting cases exhibit core-periphery structures, where the average degree of core nodes decreases but core size increases as the weight is gradually shifted from a strong requirement for efficiency and limited resilience towards a smaller requirement for efficiency and a strong demand for resilience. We argue that both, efficiency and resilience are important requirements for network design and highlight how networks can be constructed that allow for both.     

On the Algebraic Index for Riemannian Étale Groupoids

In this paper, we construct an explicit quasi-isomorphism to study the cyclic cohomology of a deformation quantization over a Riemannian étale groupoid. Such a quasi-isomorphism allows us to propose a general algebraic index problem for Riemannian étale groupoids. We discuss solutions to that index problem when the groupoid is proper or defined by a constant Dirac structure on a 3-dimensional torus.     

Oligoporphyrin Arrays Conjugated to [60]Fullerene: Preparation,NMR Analysis,and Photophysical and Electrochemical Properties

We report the synthesis and physical properties of novel fullerene–oligoporphyrin dyads. In these systems, the C‐spheres are singly linked to the terminal tetrapyrrolic macrocycles of rod‐like meso,meso‐linked or triply‐linked oligoporphyrin arrays. Monofullerene–mono(Zn^II porphyrin) conjugate 3 was synthesized to establish a general protocol for the preparation of the target molecules (Scheme 1). The synthesis of the meso,meso‐linked oligopophyrin–bisfullerene conjugates 4 – 6 , extending in size up to 4.1 nm ( 6 ), was accomplished by functionalization (iodination followed by Suzuki cross‐coupling) of the two free meso‐positions in oligomers 21 – 23 (Schemes 2 and 3). The attractive interactions between a fullerene and a Zn^II porphyrin chromophore in these dyads was quantified as ΔG=−3.3 kcal mol⁻¹ by variable‐temperature (VT) ¹H‐NMR spectroscopy (Table 1). As a result of this interaction, the C‐spheres adopt a close tangential orientation relative to the plane of the adjacent porphyrin nucleus, as was unambiguously established by ¹H‐ and ¹³C‐NMR (Figs. 9 and 10), and UV/VIS spectroscopy (Figs. 13–15). The synthesis of triply‐linked diporphyrin–bis[60]fullerene conjugate 8 was accomplished by Bingel cyclopropanation of bis‐malonate 45 with two C₆₀ molecules (Scheme 5). Contrary to the meso,meso‐linked systems 4 – 6 , only a weak chromophoric interaction was observed for 8 by UV/VIS spectroscopy (Fig. 16 and Table 2), and the ¹H‐NMR spectra did not provide any evidence for distinct orientational preferences of the C‐spheres. Comprehensive steady‐state and time‐resolved UV/VIS absorption and emission studies demonstrated that the photophysical properties of 8 differ completely from those of 4 – 6 and the many other known porphyrin–fullerene dyads: photoexcitation of the methano[60]fullerene moieties results in quantitative sensitization of the lowest singlet level of the porphyrin tape, which is low‐lying and very short lived. The meso,meso‐linked oligoporphyrins exhibit ¹O₂ sensitization capability, whereas the triply‐fused systems are unable to sensitize the formation of ¹O₂ because of the low energy content of their lowest excited states (Fig. 18). Electrochemical investigations (Table 3, and Figs. 19 and 20) revealed that all oligoporphyrin arrays, with or without appended methano[60]fullerene moieties, have an exceptional multicharge storage capacity due to the large number of electrons that can be reversibly exchanged. Some of the Zn^II porphyrins prepared in this study form infinite, one‐dimensional supramolecular networks in the solid state, in which the macrocycles interact with each other either through H‐bonding or metal ion coordination (Figs. 6 and 7).