Phenyl-triazine oligomers for light-driven hydrogen evolution

The design of stable, yet highly tunable organic photocatalysts which orchestrate multi-step electron transfer reactions is at the heart of the newly emerging field of polymer photocatalysis. Covalent triazine frameworks such as the archetypal CTF-1 have been theorized to constitute a new class of photocatalytically active polymers for light-driven water splitting. Here, we revisit the ionothermal synthesis of CTF-1 by trimerization of 1,4-dicyanobenzene catalyzed by the Lewis acid zinc chloride and demonstrate that the microporous black polymer CTF-1 is essentially inactive for hydrogen evolution. Instead, highly photoactive phenyl-triazine oligomers (PTOs) with higher crystallinity as compared to CTF-1 are obtained by lowering the reaction temperature to 300 °C and prolonging the reaction time to >150 hours. The low reaction temperature of the PTOs largely prevents incipient carbonization and thus results in a carbon-to-nitrogen weight ratio close to the theoretical value of 3.43. The oligomers were characterized by MALDI-TOF and quantitative solid-state NMR spectroscopy, revealing variations in size, connectivity and thus nitrile-to-triazine ratios depending on the initial precursor dilution. The most active PTO samples efficiently and stably reduce water to hydrogen with an average rate of 1076 (±278) μmol h−1 g−1 under simulated sunlight illumination, which is competitive with the best carbon nitride-based and purely organic photocatalysts. The photocatalytic activity of the PTOs is found to sensitively depend on the polymerization degree, thus suggesting a prominent role of the unreacted nitrile moieties in the photocatalytic process. Notably, PTOs even show moderate hydrogen production without the addition of any co-catalyst

Verifying object-oriented programs with higher-order separation logic in Coq

We present a shallow Coq embedding of a higher-order separation logic with nested triples for an object-oriented programming language. Moreover, we develop novel specification and proof patterns for reasoning in higher-order separation logic with nested triples about programs that use interfaces and interface inheritance. In particular, we show how to use the higher-order features of the Coq formalisation to specify and reason modularly about programs that (1) depend on some unknown code satisfying a specification or that (2) return objects conforming to a certain specification. All of our results have been formally verified in the interactive theorem prover Coq

The application of a biometric identification technique for linking community and hospital data in rural Ghana

Background: The reliability of counts for estimating population dynamics and disease burdens in communities depends on the availability of a common unique identifier for matching general population data with health facility data. Biometric data has been explored as a feasible common identifier between the health data and sociocultural data of resident members in rural communities within the Kintampo Health and Demographic Surveillance System located in the central part of Ghana. Objective: Our goal was to assess the feasibility of using fingerprint identification to link community data and hospital data in a rural African setting. Design: A combination of biometrics and other personal identification techniques were used to identify individual's resident within a surveillance population seeking care in two district hospitals. Visits from resident individuals were successfully recorded and categorized by the success of the techniques applied during identification. The successes of visits that involved identification by fingerprint were further examined by age. Results: A total of 27,662 hospital visits were linked to resident individuals. Over 85% of those visits were successfully identified using at least one identification method. Over 65% were successfully identified and linked using their fingerprints. Supervisory support from the hospital administration was critical in integrating this identification system into its routine activities. No concerns were expressed by community members about the fingerprint registration and identification processes. Conclusions: Fingerprint identification should be combined with other methods to be feasible in identifying community members in African rural settings. This can be enhanced in communities with some basic Demographic Surveillance System or census information

Tailor-Made Photoconductive Pyrene-Based Covalent Organic Frameworks for Visible-Light Driven Hydrogen Generation

Covalent organic frameworks (COFs) have emerged as a new class of crystalline porous polymers displaying molecular tunability combined with structural definition. Here, a series of three conjugated, photoactive azine-linked COFs based on pyrene building blocks which differ in the number of nitrogen atoms in the peripheral aromatic units is presented. The structure of the COFs is analyzed by combined experimental and computational physisorption as well as quantum-chemical calculations, which suggest a slipped-stacked arrangement of the 2D layers. Photocurrents of up to 6 mu A cm(-2) with subsecond photoresponse times are measured on thin film samples for the first time. While all COFs are capable of producing hydrogen from water, their efficiency increases significantly with decreasing number of nitrogen atoms. The trending activities are rationalized by photoelectrochemical measurements and quantum-chemical calculations which suggest an increase in the thermodynamic driving force with decreasing nitrogen content to be the origin of the observed differences in hydrogen evolution activities

Charge! - A Framework for Higher-Order Separation Logic in Coq

We present a comprehensive set of tactics for working with a shallow embedding of a higher-order separation logic for a subset of Java in Coq. The tactics make it possible to reason at a level of abstraction similar to pen-and-paper separation-logic proof outlines. In particular, the tactics allow the user to reason in the embedded logic rather than in the concrete model, where the stacks and heaps are exposed. The development is generic in the choice of heap model, and most of the development is also independent of the choice of programming language