Locating Gases in Porous Materials: Cryogenic Loading of Fuel‐Related Gases Into a Sc‐based Metal–Organic Framework under Extreme Pressures

An alternative approach to loading metal organic frameworks with gas molecules at high (kbar) pressures is reported. The technique, which uses liquefied gases as pressure transmitting media within a diamond anvil cell along with a single‐crystal of a porous metal–organic framework, is demonstrated to have considerable advantages over other gas‐loading methods when investigating host–guest interactions. Specifically, loading the metal–organic framework Sc₂BDC₃ with liquefied CO₂ at 2 kbar reveals the presence of three adsorption sites, one previously unreported, and resolves previous inconsistencies between structural data and adsorption isotherms. A further study with supercritical CH₄ at 3–25 kbar demonstrates hyperfilling of the Sc₂BDC₃ and two high‐pressure displacive and reversible phase transitions are induced as the filled MOF adapts to reduce the volume of the system.     

Patterning functional materials using channel diffused plasma-etched self-assembled monolayer templates

A simple and cost-effective methodology for large-area micrometer-scale patterning of a wide range of metallic and oxidic functional materials is presented. Self-assembled monolayers (SAM) of alkyl thiols on Au were micropatterned by channel-diffused oxygen plasma etching, a method in which selected areas of SAM were protected from plasma oxidation via a soft lithographic stamp. The patterned SAMs were used as templates for site-selective electrodeposition, electroless deposition and solution-phase deposition of functional materials such as ZnO, Ni, Ag thin films, and ZnO nanowires. The patterned SAMs and functional materials were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), atomic force microscopy (AFM), and tunneling AFM (TUNA).     

Nanopatterning of functional materials by gas phase pattern deposition of self-assembled molecular thin films in combination with electrodeposition

We present a general methodology to pattern functional materials on the nanometer scale using self-assembled molecular templates on conducting substrates. A soft lithographic gas phase edge patterning process using poly(dimethylsiloxane) molds was employed to form electrically isolating organosilane patterns of a few nanometer thickness and a line width that could be tuned by varying the time of deposition. Electrodeposition was employed to deposit patterns of Ni and ZnO on these prepatterned substrates. Deposition occurred only on patches of the substrate where no organosilane monolayer was present. The process is simple, inexpensive, and scalable to large areas. We achieved formation of metallic and oxide material patterns with a lateral resolution of 80 nm.     

Pyridinium derivatives of histamine are potent activators of cytosolic carbonic anhydrase isoforms I, II and VII

A series of positively-charged derivatives has been prepared by reaction of histamine with substituted pyrylium salts. These pyridinium histamine derivatives were investigated as activators of the zinc enzyme carbonic anhydrase (CA, EC 4.2.1.1) and more precisely the human isoforms hCA I, II and VII. Activities from the subnanomolar to the micromolar range were detected for these compounds as activators of the three isoforms, confirming the validity of current and previous designs. The substitution pattern at the pyridinium ring was the main factor influencing activity, the three isoforms showing different structural requirements for good activity, related with the number of pyridinium substituting groups and their nature, among various alkyl, phenyl and para-substituted styryl moieties. We were successful in identifying nanomolar potent and selective activators for each isozyme and also activators with a relatively good activity against all isozymes tested--valuable lead compounds for physiology and pathology studies involving these isozymes.     

Determination of decamethylcyclopentasiloxane in river and estuarine sediments in the UK

Robust analytical procedures for the measurement of decamethylcyclopentasiloxane (D₅) in river and estuarine sediments and their application in determining environmental concentrations in the UK are presented for the first time in this work. Novel approaches to minimise commonly reported artefacts are utilised, improving the confidence in the concentrations of D₅ reported. Accelerated solvent extraction (ASE) and liquid–solid extraction methods are compared. Both methods use on-column injection gas chromatography/mass spectrometry (GC/MS). Measurements of D₅ concentrations in sediments sampled from the river Great Ouse and from the Humber estuary (UK) are also reported. ASE was suitable to measure concentrations of D₅ in sediments obtained from the river Great Ouse, UK (186–1450 ng g⁻¹, dry weight) and octamethyltetracyclosiloxane (D₄, 12–24 ng g⁻¹, dry weight). C₁₂ linear alkybenzene (C₁₂ LAB), which can be used as a chemical marker for sewage effluent related emissions, was also measured in this analysis. Liquid–solid extraction was optimised to provide more confidence in the lower D₅ concentrations measured in the Humber estuary, UK (49–256 ng g⁻¹, dry weight). A Limit of quantitation (LOQ) for D₅ of 57–110 and 4 ng g⁻¹ dry weight was determined for ASE and liquid–solid extraction, respectively.     

A Stark future for quantum control

We present an overview of developments using the nonresonant dynamic Stark effect within the fields of time-resolved molecular dynamics and quantum control, drawing on examples from our own recent work. Particular emphasis is placed on the notion that "dynamics" and "control" are not distinct disciplines and that a clear synergy exits between these areas which has, up to now, been somewhat underexploited. The dynamic Stark effect is a universal interaction which we expect to have broad applicability.