Metal organic frameworks showing hydrocarbon adsorption properties commensurate with their pore structure

Commensurate adsorption occurs when the number of molecules adsorbed per unit cell relates to the symmetry of the framework and its topology. While rare in zeolite materials, commensurate adsorption has been observed in several MOF materials. In some MOF materials, several molecules having dimensions within a limited size range show this effect. This paper describes the commensurate adsorption properties of three MOF materials and also two MOFs showing unusual combined structure-composition adsorption features.     

Surface tension-driven shape-recovery of micro/nanometer-scale surface features in a Pt57.5Ni5.3Cu14.7P22.5 metallic glass in the supercooled liquid region: A numerical modeling capability

Recent experiments in the literature show that micro/nano-scale features imprinted in a Pt-based metallic glass, Pt_57.5Ni_5.3Cu_14.7P_22.5, using thermoplastic forming at a temperature above its glass transition temperature, may be erased by subsequent annealing at a slightly higher temperature in the supercooled liquid region (Kumar and Schroers, 2008). The mechanism of shape-recovery is believed to be surface tension-driven viscous flow of the metallic glass. We have developed an elastic-viscoplastic constitutive theory for metallic glasses in the supercooled liquid temperature range at low strain rates, and we have used existing experimental data in the literature for Pt_57.5Ni_5.3Cu_14.7P_22.5 (Harmon et al., 2007) to estimate the material parameters appearing in our constitutive equations. We have implemented our constitutive model for the bulk response of the glass in a finite element program, and we have also developed a numerical scheme for calculating surface curvatures and incorporating surface tension effects in finite element simulations. By carrying out full three-dimensional finite-element simulations of the shape-recovery experiments of Kumar and Schroers (2008), and using the independently determined material parameters for the bulk glass, we estimate the surface tension of Pt_57.5Ni_5.3Cu_14.7P_22.5 at the temperature at which the shape-recovery experiments were conducted. Finally, with the material parameters for the underlying elastic-viscoplastic bulk response as well as a value for the surface tension of the Pt-based metallic glass fixed, we validate our simulation capability by comparing predictions from our numerical simulations of shape-recovery experiments of Berkovich nanoindents, against corresponding recent experimental results of Packard et al. (2009) who reported shape-recovery data of nanoindents on the same Pt-based metallic glass.     

The critical velocity of mode-I fracture in a non-linear lattice in the absence of viscosity

The high-velocity regime of mode-I fracture is interesting, especially because of the instability of the steady-state propagating crack to a more complex dynamics (such as micro-branching). In this article, we study mode-I fracture in a non-linear lattice in the absence of a viscous force. In earlier study, we had studied the effects of the bond potential parameters, including Kelvin viscous force, on the macroscopic behavior of the crack, including the high velocity regime instability. Recently, a new study has appeared using a very similar non-linear force but claiming quite different results. In this article, we seek to discover an explanation of these differences. We find that they do not result from the viscosity present in our previous study. At least part of the differences are attributable, rather, to the very wide system used in the recent study, which leads to long transients and a failure to probe the steady-state behavior. Our results confirm our previously claimed lack of agreement with the Yoffe prediction for the critical velocity of a steady-state crack, and neither do they match the predictions of Gao’s model.     

Aerodynamic interference between high-speed slender bodies

Under supersonic flow conditions, slender bodies in close proximity induce aerodynamic interference effects. This paper aims to quantify the magnitude of the resulting interference loads and to understand the underlying flow-physics mechanisms that cause them. A pair of identical slender bodies are investigated through a series of wind-tunnel experiments and supporting computational fluid dynamics (CFD) predictions. The bodies induce a complex interference flowfield, which tends to be bespoke to each configuration. The flow features include impinging shock and expansion waves, conical shock reflections, strong skewing of the boundary-layer flows and shock diffraction. The effects of axial stagger, lateral separation and the strength of the primary disturbance flow field are evaluated. The interference loads are found to be most sensitive to the initial location of the primary disturbance but are also affected by its strength. In addition, maximum interference loads which equate to an effective incidence of up to 6° are observed. Finally, very good agreement is found between the measurements and the CFD predicted normal force and pitching moment.     

Prebiotically Plausible Autocatalytic Peptide Amyloids

The prebiotic emergence of molecules capable both of self-replication and of storing information was a defining event at the dawn of life. Still, no plausible prebiotic self-replication of biologically relevant molecules has been demonstrated. Building upon the known templating nature of amyloids, we present two systems in which the products of a peptide-bond-forming reaction act as self-replicators to enhance the yield and stereoselectivity of their formation. This first report of an amino acid condensation that can undergo autocatalysis further supports the potential role of amyloids in prebiotic molecular evolution as an environment-responsive and information-coding system capable of self-replication.     

Quadrupolar Ultrafast Charge Transfer in Diaminoazobenzene-Bridged Perylenediimide Triads

Strong push-pull interactions between electron donor, diaminoazobenzene (azo), and an electron acceptor, perylenediimide (PDI), entities in the newly synthesized A−D−A type triads (A=electron acceptor and D=electron donor) and the corresponding A−D dyads are shown to reveal wide-band absorption covering the entire visible spectrum. Electrochemical studies revealed the facile reduction of PDI and relatively easier oxidation of diaminoazobenzene in the dyads and triads. Charge transfer reversal using fluorescence-spectroelectrochemistry wherein the PDI fluorescence recovery upon one-electron oxidation, deterring the charge-transfer interactions, was possible to accomplish. The charge transfer state density difference and the frontier orbitals from the DFT calculations established the electron-deficient PDI to be an electron acceptor and diaminoazobenzene to be an electron donor resulting in energetically closely positioned PDI ^δ− -Azo ^δ+ -PDI ^δ− quadrupolar charge-transfer states in the case of triads and Azo ^δ+ -PDI ^δ− dipolar charge-transfer states in the case of dyads. Subsequent femtosecond transient absorption spectral studies unequivocally proved the occurrence of excited-state charge transfer in these dyads and triads in benzonitrile wherein the calculated forward charge transfer rate constants, k_f, were limited to instrument response factor, meaning >10¹² s⁻¹ revealing the occurrence of ultrafast photo-events. The charge recombination rate constant, k_r, was found to depend on the type of donor-acceptor conjugates, that is, it was possible to establish faster k_r in the case of triads (∼10¹¹ s⁻¹) compared to dyads (∼10¹⁰ s⁻¹). Modulating both ground and excited-state properties of PDI with the help of strong quadrupolar and dipolar charge transfer and witnessing ultrafast charge transfer events in the studied triads and dyads is borne out from the present study.     

Polycations Stabilised by Borosulfates: [Au3Cl4][B(S2O7)2] and the One-Dimensional Metal [Au2Cl4][B(S2O7)2](SO3)

(SO₄)-rich silicate analogue borosulfates are able to stabilise cationic cluster-like and chain-like aggregates. Single crystals of [Au₃Cl₄][B(S₂O₇)₂] and [Au₂Cl₄][B(S₂O₇)₂](SO₃) were obtained by solvothermal reaction with SO₃, and the electronic properties were investigated by means of density functional theory–based calculations. [Au₃Cl₄][B(S₂O₇)₂] exhibits a cluster-like cation, and the cationic gold-chloride strands in [Au₂Cl₄][B(S₂O₇)₂](SO₃) are found to resemble one-dimensional metallic wires. This is confirmed by polarisation microscopy.     

Tuning Deazaflavins Towards Highly Potent Reducing Photocatalysts Guided by Mechanistic Understanding – Enhancement of the Key Step by the Internal Heavy Atom Effect

Deazaflavins are well suited for reductive chemistry acting via a consecutive photo-induced electron transfer, in which their triplet state and semiquinone – the latter is formed from the former after electron transfer from a sacrificial electron donor – are key intermediates. Guided by mechanistic investigations aiming to increase intersystem crossing by the internal heavy atom effect and optimising the concentration conditions to avoid unproductive excited singlet reactions, we synthesised 5-aryldeazaflavins with Br or Cl substituents on different structural positions via a three-component reaction. Bromination of the deazaisoalloxazine core leads to almost 100 % triplet yield but causes photo-instability and enhances unproductive side reactions. Bromine on the 5-phenyl group in ortho position does not affect the photostability, increases the triplet yield, and allows its efficient usage in the photocatalytic dehalogenation of bromo- and chloroarenes with electron-donating methoxy and alkyl groups even under aerobic conditions. Reductive powers comparable to lithium are achieved.     

Adamantyl Side Chains as Anti-Aggregating Moieties in Dyes for Dye-Sensitized Solar Cells

Designing and evaluating novel dye concepts is crucial for the development of the field of dye-sensitized solar cells (DSSCs). In our recent report, the novel concept of tethering the anti-aggregation additive chenodeoxycholic acid (CDCA) to dyes for DSSC was introduced. Based on the performance improvements seen for this modification, the aim of this study is to see if a simplified anti-aggregation unit could achieve similar results. The following study reports the synthesis and photovoltaic characterization of two novel dyes decorated with the steric ethyladamantyl moiety on the π-spacer, and on the triarylamine donor. This modification is demonstrated to be successful in increasing the photovoltages in devices employing copper-based electrolytes compared to the non-modified reference dye. The best photovoltaic performance is achieved by a device prepared with the adamantyl decorated donor dye and CDCA, this device achieves a power conversion efficiency of 6.1 % (Short-circuit current=8.3 mA cm⁻², Open-circuit voltage=1054 mV, Fill factor=0.69). The improved photovoltaic performance seen for the adamantyl decorated donor demonstrate the potential of ethyladamantyl side chains as a tool to ensure surface protection of TiO₂.     

Encapsulated Neutral Ruthenium Catalyst for Substrate-Selective Oxidation of Alcohols

The neutral complex dichloro-{diethyl[(5-phenyl-1,3,4-oxadiazol-2-ylamino)-(4-trifluoro-methylphenyl)methyl]phosphonate} (p-cymene)-ruthenium(II) was encapsulated inside a self-assembled hexameric host obtained upon reaction of 2,8,14,20-tetra-undecyl-resorcin[4]arene and water. The formation of an inclusion complex was inferred from a combination of spectral measurements (MS, UV/Vis spectroscopy, ¹H and DOSY NMR). The ³¹P and ¹⁹F NMR spectra are consistent with motions of the ruthenium complex inside the self-assembled capsule. Molecular dynamics simulations carried out on the inclusion complex confirmed these intra-cavity movements and highlighted possible supramolecular interactions between the ruthenium first coordination sphere ligands and the inner part (aromatic rings) of the capsule. The embedded ruthenium complex was assessed in the catalytic oxidation (using NaIO₄ as oxidant) of mixtures of three arylmethyl alcohols into the corresponding aldehydes. The reaction kinetics were shown to vary as a function of the substrates’ size, with the oxidation rate varying in the order benzylalcohol >4-phenyl-benzylalcohol >9-anthracenemethanol. Control experiments realized in the absence of hexameric capsule did not allow any discrimination between the substrates.