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.

Dark Photocatalysis: Storage of Solar Energy in Carbon Nitride for Time-Delayed Hydrogen Generation

While natural photosynthesis serves as the model system for efficient charge separation and decoupling of redox reactions, bio-inspired artificial systems typically lack applicability owing to synthetic challenges and structural complexity. We present herein a simple and inexpensive system that, under solar irradiation, forms highly reductive radicals in the presence of an electron donor, with lifetimes exceeding the diurnal cycle. This radical species is formed within a cyanamide-functionalized polymeric network of heptazine units and can give off its trapped electrons in the dark to yield H$_{2}$ , triggered by a co-catalyst, thus enabling the temporal decoupling of the light and dark reactions of photocatalytic hydrogen production through the radical's longevity. The system introduced here thus demonstrates a new approach for storing sunlight as long-lived radicals, and provides the structural basis for designing photocatalysts with long-lived photo-induced states.This work was supported by the Deutsche Forschungsgemeinschaft (project LO1801/1-1) and an ERC Starting Grant (B.V.L., grant number 639233), the Max Planck Society, the cluster of excellence Nanosystems Initiative Munich (NIM), and the Center for Nanoscience (CeNS). We acknowledge support by the Christian Doppler Research Association (Austrian Federal Ministry of Science, Research and Economy, National Foundation for Research, Technology and Development) and the OMV Group (H.K., E.R.). V.W.-h.L. gratefully acknowledges a postdoctoral scholarship from the Max Planck Society

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

Aggressiveness of human melanoma xenograft models is promoted by aneuploidy-driven gene expression deregulation.

Melanoma is a devastating skin cancer characterized by distinct biological subtypes. Besides frequent mutations in growth- and survival-promoting genes like BRAF and NRAS, melanomas additionally harbor complex non-random genomic alterations. Using an integrative approach, we have analysed genomic and gene expression changes in human melanoma cell lines (N=32) derived from primary tumors and various metastatic sites and investigated the relation to local growth aggressiveness as xenografts in immuno-compromised mice (N=22). Although the vast majority >90% of melanoma models harbored mutations in either BRAF or NRAS, significant differences in subcutaneous growth aggressiveness became obvious. Unsupervised clustering revealed that genomic alterations rather than gene expression data reflected this aggressive phenotype, while no association with histology, stage or metastatic site of the original melanoma was found. Genomic clustering allowed separation of melanoma models into two subgroups with differing local growth aggressiveness in vivo. Regarding genes expressed at significantly altered levels between these subgroups, a surprising correlation with the respective gene doses (>85% accordance) was found. Genes deregulated at the DNA and mRNA level included well-known cancer genes partly already linked to melanoma (RAS genes, PTEN, AURKA, MAPK inhibitors Sprouty/Spred), but also novel candidates like SIPA1 (a Rap1GAP). Pathway mining further supported deregulation of Rap1 signaling in the aggressive subgroup e.g. by additional repression of two Rap1GEFs. Accordingly, siRNA-mediated down-regulation of SIPA1 exerted significant effects on clonogenicity, adherence and migration in aggressive melanoma models. Together our data suggest that an aneuploidy-driven gene expression deregulation drives local aggressiveness in human melanoma

Properties of Physical Systems: Transient Singularities on Borders and Surface Transitive Zones

Certain alternative properties of physical systems are describable by supports of arguments of response functions (e.g. light cone, borders of media) and expressed by projectors; corresponding equations of restraints lead to dispersion relations, theorems of counting, etc. As supports are measurable, their absolutely strict borders contradict the spirit of quantum theory and their quantum evolution leading to appearance of subtractions or certain needed flattening would be considered. Flattening of projectors introduce transitive zones that can be examined as a specification of adiabatic hypothesis or the Bogoliubov regulatory function in QED. For demonstration of their possibilities the phenomena of refraction and reflection of electromagnetic wave are considered; they show, in particular, the inevitable appearing of double electromagnetic layers on all surfaces that formerly were repeatedly postulated, etc. Quantum dynamics of projectors proves the neediness of subtractions that usually are artificially adding and express transient singularities and zones in squeezed forms.Comment: 12 p

Relaxed Current Matching Requirements in Highly Luminescent Perovskite Tandem Solar Cells and Their Fundamental Efficiency Limits.

Perovskite-based tandem solar cells are of increasing interest as they approach commercialization. Here we use experimental parameters from optical spectroscopy measurements to calculate the limiting efficiency of perovskite-silicon and all-perovskite two-terminal tandems, employing currently available bandgap materials, as 42.0% and 40.8%, respectively. We show luminescence coupling between subcells (the optical transfer of photons from the high-bandgap to low-bandgap subcell) relaxes current matching when the high-bandgap subcell is a luminescent perovskite. We calculate that luminescence coupling becomes important at charge trapping rates (≤106 s-1) already being achieved in relevant halide perovskites. Luminescence coupling increases flexibility in subcell thicknesses and tolerance to different spectral conditions. For maximal benefit, the high-bandgap subcell should have the higher short-circuit current under average spectral conditions. This can be achieved by reducing the bandgap of the high-bandgap subcell, allowing wider, unstable bandgap compositions to be avoided. Lastly, we visualize luminescence coupling in an all-perovskite tandem through cross-section luminescence imaging.ARB acknowledges funding from a Winton Studentship, Oppenheimer Studentship the Engineering and Physical Sciences Research Council (EPSRC) Doctoral Training Centre in Photovoltaics (CDT-PV). ARB thanks Luis Pazos-Outón for supplying data for MAPbI3 solar cells. FL acknowledges financial support from the Alexander Von Humboldt Foundation via the Feodor Lynen program and thanks Prof. Sir R. Friend for supporting his Fellowship at the Cavendish Laboratory. Y-HC acknowledges the funding from Taiwan Cambridge Scholarship. AJ-S gratefully acknowledges a postdoctoral scholarship from the Max Planck Society. KF acknowledges a George and Lilian Schiff Studentship, Winton Studentship, the Engineering and Physical Sciences Research Council (EPSRC) studentship, Cambridge Trust Scholarship, and Robert Gardiner Scholarship. GE was funded by NREL’s LDRD program. ER acknowledges the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation programme (HYPERION, Grant Agreement Number 756962) and the EPSRC for a DTP Part Studentship. MA-J acknowledges funding support from EPSRC through the program grant: EP/M005143/1. MA-J thanks Cambridge Materials Limited for their funding and technical support. MA acknowledges funding from the European Research Council (ERC) (grant agreement No. 756962 [HYPERION]) and the Marie Skłodowska-Curie actions (grant agreement No. 841386) under the European Union’s Horizon 2020 research and innovation programme. BVL acknowledges funding from the Max Planck Society, the Cluster of Excellence e-conversion and the Center for Nanoscience (CeNS). SDS acknowledges the Royal Society and Tata Group (UF150033) and the EPSRC (EP/R023980/1, EP/T02030X/1, EP/S030638/1). We thank Axel Palmstrom and William Nemeth at NREL for depositing some of the layers in the tandem stack

Bottom-up Formation of Carbon-Based Structures with Multilevel Hierarchy from MOF-Guest Polyhedra.

Three-dimensional carbon-based structures have proven useful for tailoring material properties in structural mechanical and energy storage applications. One approach to obtain them has been by carbonization of selected metal-organic frameworks (MOFs) with catalytic metals, but this is not applicable to most common MOF structures. Here, we present a strategy to transform common MOFs, by guest inclusions and high-temperature MOF-guest interactions, into complex carbon-based, diatom-like, hierarchical structures (named for the morphological similarities with the naturally existing diatomaceous species). As an example, we introduce metal salt guests into HKUST-1-type MOFs to generate a family of carbon-based nano-diatoms with two to four levels of structural hierarchy. We report control of the morphology by simple changes in the chemistry of the MOF and guest, with implications for the formation mechanisms. We demonstrate that one of these structures has unique advantages as a fast-charging lithium-ion battery anode. The tunability of composition should enable further studies of reaction mechanisms and result in the growth of a myriad of unprecedented carbon-based structures from the enormous variety of currently available MOF-guest candidates.The project was funded through a European Research Council (ERC) grant to S.K.S. (grant number: EMATTER 280078). A.K.C. and Y.W. thank the Ras Al Khaimah Center for Advanced Materials (RAK-CAM). T.W. thanks the China Scholarship Council (CSC) for funding and EPSRC Centre for Doctoral Training in Sensor Technologies and Applications (EP/L015889/1 and 1566990) for support. W.L. acknowledges the EPSRC grants (EP/L011700/1 and EP/N004272/1). Financial support by the Max Planck Society is gratefully acknowledged. K.D.F. acknowledges support from the Winston Churchill Foundation of the United States. C.Y. thanks the Cambridge Commonwealth, European and International Trust for funding

Dirac cone protected by non symmorphic symmetry and three dimensional Dirac line node in ZrSiS

Materials harbouring exotic quasiparticles, such as massless Dirac and Weyl fermions, have garnered much attention from physics and material science communities due to their exceptional physical properties such as ultra high mobility and extremely large magnetoresistances. Here, we show that the highly stable, non toxic and earth abundant material, ZrSiS, has an electronic band structure that hosts several Dirac cones that form a Fermi surface with a diamond shaped line of Dirac nodes. We also show that the square Si lattice in ZrSiS is an excellent template for realizing new types of two dimensional Dirac cones recently predicted by Young and Kane. Finally, we find that the energy range of the linearly dispersed bands is as high as 2 amp; 8201;eV above and below the Fermi level; much larger than of other known Dirac materials. This makes ZrSiS a very promising candidate to study Dirac electrons, as well as the properties of lines of Dirac node