Engineering Homochiral Metal–Organic Frameworks by Spatially Separating 1D Chiral Metal–Peptide Ladders: Tuning the Pore Size for Enantioselective Adsorption

The reaction of the chiral dipeptide glycyl‐L(S)‐glutamate with Co^II ions produces chiral ladders that can be used as rigid 1D building units. Spatial separation of these building units with linkers of different lengths allows the engineering of homochiral porous MOFs with enhanced pore sizes, pore volumes, and surface areas. This strategy enables the synthesis of a family of isoreticular MOFs, in which the pore size dictates the enantioselective adsorption of chiral molecules (in terms of their size and enantiomeric excess).     

Roe‐type Riemann solvers for general hyperbolic systems

We present a Roe‐type weak formulation Riemann solver where the average coefficient matrix is computed numerically. The novelty of this approach is that it is general enough that can be applied to any hyperbolic system while retaining the accuracy of the original Roe solver. We show applications to the compressible Euler equations with general equation of state. An alternative version of the method uses directly the eigenvectors in the averaging process, simplifying the algorithm. These new solvers are applied in conservative and path‐conservative schemes with high‐order accuracy and on unstructured meshes. Copyright © 2014 John Wiley & Sons, Ltd.     

Reactivity Studies of Iridium Pyridylidenes [TpMe2Ir(C6H5)2(C(CH)3C(R)NH] (R=H,Me, Ph)

The reactivity of a series of iridium? pyridylidene complexes with the formula [Tp^Me2Ir(C₆H₅)₂(C(CH)₃C(R)N H] ( 1 a – 1 c ) towards a variety of substrates, from small molecules, such as H₂, O₂, carbon oxides, and formaldehyde, to alkenes and alkynes, is described. Most of the observed reactivity is best explained by invoking 16 e^? unsaturated [Tp^Me2Ir(phenyl)(pyridyl)] intermediates, which behave as internal frustrated Lewis pairs (FLPs). H₂ is heterolytically split to give hydride? pyridylidene complexes, whilst CO, CO₂, and H₂C?O provide carbonyl, carbonate, and alkoxide species, respectively. Ethylene and propene form five‐membered metallacycles with an IrCH₂CH(R)N (R=H, Me) motif, whereas, in contrast, acetylene affords four‐membered iridacycles with the IrC(?CH₂)N moiety. C₆H₅(C?O)H and C₆H₅C?CH react with formation of Ir? C₆H₅ and Ir? C?CPh bonds and the concomitant elimination of a molecule of pyridine and benzene, respectively. Finally the reactivity of compounds 1 a – 1 c against O₂ is described. Density functional theory calculations that provide theoretical support for these experimental observations are also reported.     

Structural Changes Induced by Quinones: High-Resolution Microwave Study of 1,4-Naphthoquinone

1,4-Naphthoquinone (1,4-NQ) is an important product of naphthalene oxidation, and it appears as a motif in many biologically active compounds. We have investigated the structure of 1,4-NQ using chirped-pulse Fourier transform microwave spectroscopy and quantum chemistry calculations. The rotational spectra of the parent species, and its ¹³C and ¹⁸O isotopologues were observed in natural abundance, and their spectroscopic parameters were obtained. This allowed the determination of the substitution r_s, mass-weighted r_m and semi-experimental r_e^SE structures of 1,4-NQ. The obtained structural parameters show that the quinone moiety mainly changes the structure of the benzene ring where it is inserted, modifying the C−C bonds to having predominantly single or double bond character. Furthermore, the molecular electrostatic surface potential reveals that the quinone ring becomes electron deficient while the benzene ring remains a nucleophile. The most electrophilic areas are the hydrogens attached to the double bond in the quinone ring. Knowledge of the nucleophilic and electrophilic areas in 1,4-NQ will help understanding its behaviour interacting with other molecules and guide modifications to tune its properties.     

The smallest absorption refrigerator: the thermodynamics of a system with quantum local detailed balance

We study the thermodynamics of a quantum system interacting with different baths in the repeated interaction framework. In an appropriate limit, the evolution takes the Lindblad form and the corresponding thermodynamic quantities are determined by the state of the full system plus baths. We identify conditions under which the thermodynamics of the open system can be described only by system properties and find a quantum local detailed balance condition with respect to an equilibrium state that may not be a Gibbs state. The three-qubit refrigerator introduced in Linden et al. [Phys. Rev. Lett. 105, 130401 (2010)] and Skrzypczyk et al. [J. Phys. A: Math. Theory 44, 492002 (2011)] is an example of such a system. From a repeated interaction microscopic model we derive the Lindblad equation that describes its dynamics and discuss its thermodynamic properties for arbitrary values of the internal coupling between the qubits. We find that external power (proportional to the internal coupling strength) is required to bring the system to its steady state, but once there, it works autonomously as discussed in Linden et al. [Phys. Rev. Lett. 105, 130401 (2010)] and Skrzypczyk et al. [J. Phys. A: Math. Theory 44, 492002 (2011)].     

Extraction and analysis of ellagic acid from novel complex sources

Ellagic acid (EA) was quantified by reversed-phase high-performance liquid chromatography (RPHPLC) coupled with photodiode array detection (DAD) in five fine-powdered plants collected from the semiarid region of Mexico. Samples analysed included Jatropha dioica branches (Dragon’s blood), Euphorbia antisyphyllitica branches (Candelilla), Turnera diffusa Willd leaves (Damiana), Flourensia cernua leaves (hojasén) and Punica granatum husk (pomegranate) at two maturity stages (“turning” or intermediate and maturated fruit, considered as positive controls). The results demonstrated high EA concentrations in all tested samples which are novel sources of this natural antioxidant. The method developed for the EA analysis is fast and it showed an excellent linearity range, repeatability, intra-and inter-day precision and accuracy with respect to the methods reported for the EA analysis.     

Semistable extremal ground states for nonlinear evolution equations in unbounded domains

In this paper we show that dissipative reaction-diffusion equations in unbounded domains posses extremal semistable ground states equilibria, which bound asymptotically the global dynamics. Uniqueness of such positive ground state and their approximation by extremal equilibria in bounded domains is also studied. The results are then applied to the important case of logistic equations.