Experimental evidence of guided-resonances in photonic crystals with aperiodically ordered supercells

We report on the first experimental evidence of guided resonances (GRs) in photonic crystal slabs based on aperiodically ordered supercells. Using Ammann-Beenker (quasiperiodic, eightfold symmetric) tiling geometry, we present our study on the fabrication, experimental characterization, and full-wave numerical simulation of two representative structures (with different filling parameters) operating at near-IR wavelengths (1300-1600 nm). Our results show a fairly good agreement between measurements and numerical predictions and pave the way for the development of new strategies (based on, e.g., the lattice symmetry breaking) for GR engineering.     

Cloaked near-field scanning optical microscope tip for noninvasive near-field imaging

Near-field imaging is a well-established technique in biomedical measurements, since closer to the detail of interest it is possible to resolve subwavelength details otherwise unresolved by regular lenses. A near-field scanning optical microscope (NSOM) tip may indeed overcome the resolution limits of far-field optics, but its proximity inherently perturbs the measurement. Here, we apply the recent concept of a "cloaked sensor" to an NSOM device in collection mode, showing theoretically how a proper plasmonic cover applied to an NSOM tip may drastically improve its overall measurement capabilities.     

Cycloolefin Copolymers by Early and Late Transition Metal Catalysts

The complex [Pd(κ²‐P,O‐{2‐(2‐MeOC₆H₄)₂P}C₆H₄SO₃)Me(dmso)] ( 1 ) is investigated for the copolymerization of (E) with norbornene (N) and functionalized N derivatives affording P(E‐co‐N) in excellent yields. Copolymer molar masses are higher than those of PE and increase with N concentration. In addition, the complex [Ti(κ²‐N,O‐{2,6‐F₂C₆H₃N = C(Me)C(H) = C(CF₃)O})₂Cl₂] ( 2 ) is evaluated as catalyst for living E‐co‐N copolymerization upon activation with dried methylaluminoxane between 25 and 90 °C. Copolymerization at different [N]/[E] feed ratios affords stereoirregular alternating high molar mass P(E‐co‐N) with narrow molar mass distribution. P(E‐co‐N) living copolymerization is demonstrated by kinetics at 50 °C. Block copolymers are synthesized and fully characterized.

     

Synthesis of Different 3,5‐Diazidofuranoses: A New and General Synthesis Pathway

Diamino‐ and diazidofuranoses represent useful precursors, for example, for the synthesis of substituted nucleosides and metal complexes, respectively. Known procedures for their synthesis lack the availability of cheap starting materials, adequate yields, and the access to all possible diastereomeres. Therefore, 3,5‐diazido‐3,5‐dideoxy‐ and ‐2,3,5‐trideoxyfuranoses both with ribo‐ and xylo‐configuration were prepared using different approaches.     

Higher-order Sobolev embeddings and isoperimetric inequalities

Optimal higher-order Sobolev type embeddings are shown to follow via isoperimetric inequalities. This establishes a higher-order analogue of a well-known link between first-order Sobolev embeddings and isoperimetric inequalities. Sobolev type inequalities of any order, involving arbitrary rearrangement-invariant norms, on open sets in Rⁿ${\mathbb{R}}^n$, possibly endowed with a measure density, are reduced to much simpler one-dimensional inequalities for suitable integral operators depending on the isoperimetric function of the relevant sets. As a consequence, the optimal target space in the relevant Sobolev embeddings can be determined both in standard and in non-standard classes of function spaces and underlying measure spaces. In particular, our results are applied to any-order Sobolev embeddings in regular (John) domains of the Euclidean space, in Maz'ya classes of (possibly irregular) Euclidean domains described in terms of their isoperimetric function, and in families of product probability spaces, of which the Gauss space is a classical instance.     

Investigating Membrane-Mediated Antimicrobial Peptide Interactions with Synchrotron Radiation Far-Infrared Spectroscopy

Synchrotron radiation-based Fourier transform infrared spectroscopy enables access to vibrational information from mid over far infrared to even terahertz domains. This information may prove critical for the elucidation of fundamental bio-molecular phenomena including folding-mediated innate host defence mechanisms. Antimicrobial peptides (AMPs) represent one of such phenomena. These are major effector molecules of the innate immune system, which favour attack on microbial membranes. AMPs recognise and bind to the membranes whereupon they assemble into pores or channels destabilising the membranes leading to cell death. However, specific molecular interactions responsible for antimicrobial activities have yet to be fully understood. Herein we probe such interactions by assessing molecular specific variations in the near-THz 400–40 cm⁻¹ range for defined helical AMP templates in reconstituted phospholipid membranes. In particular, we show that a temperature-dependent spectroscopic analysis, supported by 2D correlative tools, provides direct evidence for the membrane-induced and folding-mediated activity of AMPs. The far-FTIR study offers a direct and information-rich probe of membrane-related antimicrobial interactions.     

From Si nanowires to porous silicon: the role of excitonic effects

We show that the electronic and optical properties of silicon nanowires, with different size and orientation, are dominated by important many-body effects. The electronic and excitonic gaps, calculated within first principles, agree with the available experimental data. Huge excitonic effects, which depend strongly on wire orientation and size, characterize the optical spectra. Modeling porous silicon as a collection of interacting nanowires, we find an absorption spectrum which is in very good agreement with experimental measurements only when the electron-hole interaction is included.     

Influence of the birefringence autocorrelation function on the polarization mode dispersion of constantly spun fibers

We show that the polarization mode dispersion of a constantly spun, single-mode fiber is strongly influenced by the autocorrelation function of its birefringence. In particular, under probable conditions, the mean square differential group delay of the spun fiber may even be higher than the delay that the same fiber would have if it were not spun.     

Mukaiyama–Michael Reactions with trans‐2,5‐Diarylpyrrolidine Catalysts: Enantioselectivity Arises from Attractive Noncovalent Interactions,Not from Steric Hindrance

The scope of the enantioselective Mukaiyama–Michael reactions catalyzed by trans‐2,5‐diphenylpyrrolidine has been expanded to include both α‐ and β‐substituted enals. However, the rationalization of the observed enantioselectivity is far from obvious since the catalyst is not very sterically hindered. DFT calculations were carried out to rationalize the observed stereoselectivities. Transition states of the C?C bond formation between iminium intermediates and silyloxyfurans were located and their relative energies were used to estimate the stereoselectivity data. We find excellent agreement between the predicted and observed stereoselectivities. The analysis of intermolecular forces reveals that the enantioselectivity is mostly due to stabilizing noncovalent interactions between the reacting partners, not due to steric hindrance. The role of attractive noncovalent interactions in enantioselective catalysis may be underappreciated.