Waveguide arrays as plasmonic metamaterials: transmission below cutoff

Since the work of Ebbesen et al. [Nature (London) 391, 667 (1998)], there has been immense interest in the optical properties of subwavelength holes in metal layers. While the enhanced transmission observed is generally associated with surface plasmon polaritons (SPPs), theoretical predictions suggest a similar response with perfectly conducting materials. However, Pendry et al. [Science 305, 847 (2004)] proposed that, if textured on a subwavelength scale, even perfect conductors support surface modes. Here, using microwave radiation incident upon an array of metal waveguides, we observe peaks in the transmissivity below cutoff and confirm the crucial role of these SPP-like modes in the mechanism responsible.     

Constraints on light dark matter from core-collapse supernovae

We show that light (approximately or = 1-30 MeV) dark matter particles can play a significant role in core-collapse supernovae, if they have relatively large annihilation and scattering cross sections, as compared to neutrinos. We find that if such particles are lighter than approximately or = 10 MeV and reproduce the observed dark matter relic density, supernovae would cool on a much longer time scale and would emit neutrinos with significantly smaller energies than in the standard scenario, in disagreement with observations. This constraint may be avoided, however, in certain situations for which the neutrino-dark-matter scattering cross sections remain comparatively small.     

Renormalization of polygon exchange maps arising from corner percolation

We describe a family {Ψ _α,β } of polygon exchange transformations parameterized by points (α,β) in the square $[0, {\frac{1}{2}}]\times[0, {\frac{1}{2}}]$ . Whenever α and β are irrational, Ψ _α,β has periodic orbits of arbitrarily large period. We show that for almost all parameters, the polygon exchange map has the property that almost every point is periodic. However, there is a dense set of irrational parameters for which this fails. By choosing parameters carefully, the measure of non-periodic points can be made arbitrarily close to full measure. These results are powered by a notion of renormalization which holds in a more general setting. Namely, we consider a renormalization of tilings arising from the Corner Percolation Model.     

1,2-Diphosphinobenzene as a synthon for the 1,2,3-triphospha- and 2-arsa-1,3-diphosphaindenyl anions and a stable organo derivative of the P8 unit of Hittorf's phosphorus

The electronic structure of the 1,2,3-triphosphaindenyl ligand suggests that it should exhibit enhanced pi-acceptor properties when compared to the eta(5)-indenyl system; this insight encouraged us to develop a simple synthetic pathway from 1,2-diphosphinobenzene to the 1,2,3-C(6)H(4)P(3) and 2-As-1,3-C(6)H(4)P(2) anions, both of which have been structurally characterised by X-ray crystallography; as a bonus from these studies we also obtained the first structurally characterised organo derivative of the P(8) unit present in Hittorf's phosphorus.     

Simultaneous Determination of Glucose and L‐Glutamate Using a Capillary Enzyme Reactor with Electrochemical Detection

An electrophoresis capillary that incorporates two enzymes for the simultaneous determination of glucose and L ‐glutamate is described. The enzymes deposited along the separation capillary walls react with their respective substrate as they are separated during the electrophoresis to produce hydrogen peroxide that is detected by amperometry as the hydrogen peroxide zone emerges from the end of the capillary. Even though both enzyme reactions produce a common product, hydrogen peroxide, the hydrogen peroxide produced by each enzyme reaction stays in narrow zones that migrate the length of the capillary at different rates. The rate of migration for the individual H₂O₂ zones is consistent with the expected mobility of neutral glucose and of anionic L ‐glutamate, respectively. This property allows each enzyme substrate to be characterized in a single experiment and in the presence of other electroactive substances.     

Evidence for a SN2-type pathway for phosphine exchange in phosphine-phosphenium cations, [R2P--PR'3]+

Abstraction of a Cl(-) ion from the P-chlorophospholes, R4C4PCl (R=Me, Et), produced the P--P bonded cations [R4C4P--P(Cl)C4R4]+, which reacted with PPh3 to afford X-ray crystallographically characterised phosphine-phosphenium cations [R4C4P(PPh3)]+ (R=Me, Et). Examination of the 31P-{1H} NMR spectrum of a solution (CH2Cl(2)) of [Et4C4P-(PPh3)]+ and PPh3 revealed broadening of the resonances due to both free and coordinated PPh3, and importantly it proved possible to measure the rate of exchange between PPh3 and [Et4C4P-(PPh3)]+ by line shape analysis (gNMR programmes). The results established second-order kinetics with DeltaS( not equal)=(-106.3+/-6.7) J mol(-1) K(-1), DeltaH( not equal)=(14.9+/-1.6) kJ mol(-1) and DeltaG( not equal) (298.15 K)=(46.6+/-2.6) kJ mol(-1), values consistent with a SN2-type pathway for the exchange process. This result contrasts with the dominant dissociative (S(N)1-type) pathway reported for the analogous exchange reactions of the [ArNCH2CH2N(Ar)P(PMe3)]+ ion, and to understand in more detail the factors controlling these two different reaction pathways, we have analysed the potential energy surfaces using density functional theory (DFT). The calculations reveal that, whilst phosphine exchange in [Et4C4P(PPh3)]+ and [ArNCH2CH2N(Ar)P(PMe3)](+) is superficially similar, the two cations differ significantly in both their electronic and steric requirements. The high electrophilicity of the phosphorus center in [Et4C4P]+, combined with strong pi-pi interactions between the ring and the incoming and outgoing phenyl groups of PPh3, favours the SN2-type over the SN1-type pathway in [Et4C4P(PPh3)]+. Effective pi-donation from the amide groups reduces the intrinsic electrophilicity of [ArNCH2CH2N(Ar)P]+, which, when combined with the steric bulk of the aryl groups, shifts the mechanism in favour of a dissociative SN1-type pathway.