Nonlinear evolution of anisotropic cosmological power

There has been growing interest in the possibility of testing more precisely the assumption of statistical isotropy of primordial density perturbations. If it is to be tested with galaxy surveys at distance scales < or = 10 Mpc, then nonlinear evolution of anisotropic power must be understood. To this end, we calculate the angular dependence of the power spectrum to third order in perturbation theory for a primordial power spectrum with a quadrupole dependence on the wave vector direction. Our results suggest that primordial power anisotropies will be suppressed by < or = 7% in the quasilinear regime. We also show that the skewness in the statistically anisotropic theory differs by no more than 1% from that in the isotropic theory.     

Nanoscopic Porous Iridium/Iridium Dioxide Superstructures (15 nm): Synthesis and Thermal Conversion by In Situ Transmission Electron Microscopy

Porous particle superstructures of about 15 nm diameter, consisting of ultrasmall nanoparticles of iridium and iridium dioxide, are prepared through the reduction of sodium hexachloridoiridate(+IV) with sodium citrate/sodium borohydride in water. The water-dispersible porous particles contain about 20 wt % poly(N-vinylpyrrolidone) (PVP), which was added for colloidal stabilization. High-resolution transmission electron microscopy confirms the presence of both iridium and iridium dioxide primary particles (1–2 nm) in each porous superstructure. The internal porosity (≈58 vol%) is demonstrated by electron tomography. In situ transmission electron microscopy up to 1000 °C under oxygen, nitrogen, argon/hydrogen (all at 1 bar), and vacuum shows that the porous particles undergo sintering and subsequent compaction upon heating, a process that starts at around 250 °C and is completed at around 800 °C. Finally, well-crystalline iridium dioxide is obtained under all four environments. The catalytic activity of the as-prepared porous superstructures in electrochemical water splitting (oxygen evolution reaction; OER) is reduced considerably upon heating owing to sintering of the pores and loss of internal surface area.     

Electrochemical and Scalable Dehydrogenative C(sp3)−H Amination via Remote Hydrogen Atom Transfer in Batch and Continuous Flow

A hydrogen atom transfer-directed electrochemical intramolecular C−H amination has been developed in which the N-radical species are generated at the anode, and the base required for the reaction is generated at the cathode. A broad range of valuable pyrrolidines were prepared in good yields and with high chemoselectivity. The reaction was easily scaled up in both batch and continuous flow systems.     

Biomimetic Approach for Highly Selective Artificial Water Channels Based on Tubular Pillar[5]arene Dimers

Artificial water channels mimicking natural aquaporins (AQPs) can be used for selective and fast transport of water. Here, we quantify the transport performances of peralkyl-carboxylate-pillar[5]arenes dimers in bilayer membranes. They can transport ≈10⁷ water molecules/channel/second, within one order of magnitude of the transport rates of AQPs, rejecting Na⁺ and K⁺ cations. The dimers have a tubular structure, superposing pillar[5]arene pores of 5 Å diameter with twisted carboxy-phenyl pores of 2.8 Å diameter. This biomimetic platform, with variable pore dimensions within the same structure, offers size restriction reminiscent of natural proteins. It allows water molecules to selectively transit and prevents bigger hydrated cations from passing through the 2.8 Å pore. Molecular simulations prove that dimeric or multimeric honeycomb aggregates are stable in the membrane and form water pathways through the bilayer. Over time, a significant shift of the upper vs. lower layer occurs initiating new unexpected water permeation events through toroidal pores.     

Multi-scale simulation reveals that an amino acid substitution increases photosensitizing reaction inputs in Rhodopsins

Evaluating the availability of molecular oxygen (O₂) and energy of excited states in the retinal binding site of rhodopsin is a crucial challenging first step to understand photosensitizing reactions in wild-type (WT) and mutant rhodopsins by absorbing visible light. In the present work, energies of the ground and excited states related to 11-cis-retinal and the O₂ accessibility to the β-ionone ring are evaluated inside WT and human M207R mutant rhodopsins. Putative O₂ pathways within rhodopsins are identified by using molecular dynamics simulations, Voronoi-diagram analysis, and implicit ligand sampling while retinal energetic properties are investigated through density functional theory, and quantum mechanical/molecular mechanical methods. Here, the predictions reveal that an amino acid substitution can lead to enough energy and O₂ accessibility in the core hosting retinal of mutant rhodopsins to favor the photosensitized singlet oxygen generation, which can be useful in understanding retinal degeneration mechanisms and in designing blue-lighting-absorbing proteic photosensitizers.     

There is no (95, 40, 12, 20) strongly regular graph

We show that there is no (95, 40, 12, 20) strongly regular graph and, consequently, there is no (96, 45, 24, 18) strongly regular graph, no nontrivial regular two‐graph on 96 vertices, and no partial geometry pg(4, 9, 2). The main idea of the result is based on the star complement technique and requires a moderate amount of computation.     

The maximum size of short character sums

The Ramanujan Journal - In the present note, we prove new lower bounds on large values of character sums $$varDelta (x,q):=max _{chi ne chi _0} big vert sum _{nle x} chi (n)big vert $$...     

An Activatable Lanthanide Luminescent Probe for Time‐Gated Detection of Nitroreductase in Live Bacteria

Herein we report the development of a turn‐on lanthanide luminescent probe for time‐gated detection of nitroreductases (NTRs) in live bacteria. The probe is activated through NTR‐induced formation of the sensitizing carbostyril antenna and resulting energy transfer to the lanthanide center. This novel NTR‐responsive trigger is virtually non‐fluorescent in its inactivated form and features a large signal increase upon activation. We show that the probe is capable of selectively sensing NTR in lysates as well as in live bacteria of the ESKAPE family which are clinically highly relevant multiresistant pathogens responsible for the majority of hospital infections. The results suggest that our probe could be used to develop diagnostic tools for bacterial infections.     

Raman Spectroscopic Signature of Ectoine Conformations in Bulk Solution and Crystalline State

Recent crystallographic results revealed conformational changes of zwitterionic ectoine upon hydration. By means of confocal Raman spectroscopy and density functional theory calculations, we present a detailed study of this transformation process as part of a Fermi resonance analysis. The corresponding findings highlight that all resonant couplings are lifted upon exposure to water vapor as a consequence of molecular binding processes. The importance of the involved molecular groups for water binding and conformational changes upon hydration is discussed. Our approach further shows that the underlying rapid process can be reversed by carbon dioxide saturated atmospheres. For the first time, we also confirm that the conformational state of ectoine in aqueous bulk solution coincides with crystalline ectoine in its dihydrate state, thereby highlighting the important role of a few bound water molecules.