Synthetic routes toward MOF nanomorphologies.

As metal–organic frameworks (MOFs) are coming of age, their structural diversity, exceptional porosity and inherent functionality need to be transferred into useful applications. Fashioning MOFs into various shapes and at the same time controlling their size constitute an essential step toward MOF-based devices. Moreover, downsizing MOFs to the nanoscale triggers a whole new set of properties distinguishing nanoMOFs from their bulk counterparts. Therefore, dimensionality-controlled miniaturization of MOFs enables the customised use of nanoMOFs for specific applications where suitable size and shape are key prerequisites. In this feature article we survey the burgeoning field of nanoscale MOF synthesis, ranging from classical protocols such as microemulsion synthesis all the way to microfluidic-based techniques and template-directed epitaxial growth schemes. Along these lines, we will fathom the feasibility of rationally designing specific MOF nanomorphologies—zero-, one- and two-dimensional nanostructures—and we will explore more complex “second-generation” nanostructures typically evolving from a high level of interfacial control. As a recurring theme, we will review recent advances made toward the understanding of nucleation and growth processes at the nanoscale, as such insights are expected to further push the borders of nanoMOF science

Fresnel laws at curved dielectric interfaces of microresonators

We discuss curvature corrections to Fresnel's laws for the reflection and transmission of light at a non-planar refractive-index boundary. The reflection coefficients are obtained from the resonances of a dielectric disk within a sequential-reflection model. The Goos-H\"anchen effect for curved light fronts at a planar interface can be adapted to provide a qualitative and quantitative extension of the ray model which explains the observed deviations from Fresnel's laws.Comment: submitted to Phys. Rev.

Prediction of persistent post-surgery pain by preoperative cold pain sensitivity : biomarker development with machine-learning-derived analysis

Background. To prevent persistent post-surgery pain, early identification of patients at high risk is a clinical need. Supervised machine-learning techniques were used to test how accurately the patients' performance in a preoperatively performed tonic cold pain test could predict persistent post-surgery pain. Methods. We analysed 763 patients from a cohort of 900 women who were treated for breast cancer, of whom 61 patients had developed signs of persistent pain during three yr of follow-up. Preoperatively, all patients underwent a cold pain test (immersion of the hand into a water bath at 2-4 degrees C). The patients rated the pain intensity using a numerical ratings scale (NRS) from 0 to 10. Supervised machine-learning techniques were used to construct a classifier that could predict patients at risk of persistent pain. Results. Whether or not a patient rated the pain intensity at NRS=10 within less than 45 s during the cold water immersion test provided a negative predictive value of 94.4% to assign a patient to the "persistent pain" group. If NRS=10 was never reached during the cold test, the predictive value for not developing persistent pain was almost 97%. However, a low negative predictive value of 10% implied a high false positive rate. Conclusion. Results provide a robust exclusion of persistent pain in women with an accuracy of 94.4%. Moreover, results provide further support for the hypothesis that the endogenous pain inhibitory system may play an important role in the process of pain becoming persistent.Peer reviewe

Photocatalytic hydrogen production using polymeric carbon nitride with a hydrogenase and a bioinspired synthetic Ni catalyst.

Solar-light-driven H2 production in water with a [NiFeSe]-hydrogenase (H2ase) and a bioinspired synthetic nickel catalyst (NiP) in combination with a heptazine carbon nitride polymer, melon (CN(x)), is reported. The semibiological and purely synthetic systems show catalytic activity during solar light irradiation with turnover numbers (TONs) of more than 50,000 mol H2(mol H2ase)(-1) and approximately 155 mol H2 (mol NiP)(-1) in redox-mediator-free aqueous solution at pH 6 and 4.5, respectively. Both systems maintained a reduced photoactivity under UV-free solar light irradiation (λ>420 nm).This is the final version. It was first published in Angewandte Chemie International Edition at http://onlinelibrary.wiley.com/doi/10.1002/anie.201406811/abstract

Thermal Conversion of Guanylurea Dicyanamide into Graphitic Carbon Nitride via Prototype CNx Precursors

Guanylurea dicyanamide, [(H2N)C(-O)NHC(NH2)2][N(CN)2], has been synthesized by ion exchange reaction in aqueous solution and structurally characterized by single-crystal X-ray diffraction (C2/c, a = 2249.0(5) pm, b = 483.9(1) pm, c = 1382.4(3) pm, β = 99.49(3)°, V = 1483.8(5) × 106 pm3, T = 130 K). The thermal behavior of the molecular salt has been studied by thermal analysis, temperature-programmed X-ray powder diffraction, FTIR spectroscopy, and mass spectrometry between room temperature and 823 K. The results were interpreted on a molecular level in terms of a sequence of thermally induced addition, cyclization, and elimination reactions. As a consequence, melamine (2,4,6-triamino-1,3,5-triazine) is formed with concomitant loss of HNCO. Further condensation of melamine yields the prototypic CNx precursor melem (2,6,10-triamino-s-heptazine, C6N7(NH2)3), which alongside varying amounts of directly formed CNxHy material transforms into layered CNxHy phases without significant integration of oxygen into the core framework owing to the evaporation of HNCO. Thus, further evidence can be added to melamine and its condensation product melem acting as “key intermediates” in the synthetic pathway toward graphitic CNxHy materials, whose exact constitution is still a point at issue. Due to the characteristic formation process and hydrogen content a close relationship with the polymer melon is evident. In particular, the thermal transformation of guanylurea dicyanamide clearly demonstrates that the formation of volatile compounds such as HNCO during thermal decomposition may render a large variety of previously not considered molecular compounds suitable CNx precursors despite the presence of oxygen in the starting material

Molecular Insights into Carbon Dioxide Sorption in Hydrazone-Based Covalent Organic Frameworks with Tertiary Amine Moieties

Tailorable sorption properties at the molecular level are key for efficient carbon capture and storage and a hallmark of covalent organic frameworks (COFs). Although amine functional groups are known to facilitate CO2 uptake, atomistic insights into CO2 sorption by COFs modified with amine-bearing functional groups are scarce. Herein, we present a detailed study of the interactions of carbon dioxide and water with two isostructural hydrazone-linked COFs with different polarities based on the 2,5-diethoxyterephthalohydrazide linker. Varying amounts of tertiary amines were introduced in the COF backbones by means of a copolymerization approach using 2,5-bis(2-(dimethylamino)ethoxy)terephthalohydrazide in different amounts ranging from 25 to 100% substitution of the original DETH linker. The interactions of the frameworks with CO2 and H2O were comprehensively studied by means of sorption analysis, solid-state NMR spectroscopy, and quantum-chemical calculations. We show that the addition of the tertiary amine linker increases the overall CO2 sorption capacity normalized by the surface area and of the heat of adsorption, whereas surface areas and pore size diameters decrease. The formation of ammonium bicarbonate species in the COF pores is shown to occur, revealing the contributing role of water for CO2 uptake by amine-modified porous frameworks

Nanofabrication by self-assembly

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Rational Design of Covalent Cobaloxime–Covalent Organic Framework Hybrids for Enhanced Photocatalytic Hydrogen Evolution

Covalent organic frameworks (COFs) display a unique combination of chemical tunability, structural diversity, high porosity, nanoscale regularity, and thermal stability. Recent efforts are directed at using such frameworks as tunable scaffolds for chemical reactions. In particular, COFs have emerged as viable platforms for mimicking natural photosynthesis. However, there is an indisputable need for efficient, stable, and economical alternatives for the traditional platinum-based cocatalysts for light-driven hydrogen evolution. Here, we present azide-functionalized chloro(pyridine)cobaloxime hydrogen-evolution cocatalysts immobilized on a hydrazone-based COF-42 backbone that show improved and prolonged photocatalytic activity with respect to equivalent physisorbed systems. Advanced solid-state NMR and quantum-chemical methods allow us to elucidate details of the improved photoreactivity and the structural composition of the involved active site. We found that a genuine interaction between the COF backbone and the cobaloxime facilitates recoordination of the cocatalyst during the photoreaction, thereby improving the reactivity and hindering degradation of the catalyst. The excellent stability and prolonged reactivity make the herein reported cobaloxime-tethered COF materials promising hydrogen evolution catalysts for future solar fuel technologies