CONTRA: improving the performance of dynamic investigations in natural abundance organic solids by mirror-symmetric constant-time CODEX

We present a minor but essential modification to the CODEX 1D-MAS exchange experiment. The new CONTRA method, which requires minor changes of the original sequence only, has advantages over the previously introduced S-CODEX, since it is less sensitive to artefacts caused by finite pulse lengths. The performance of this variant, including the finite pulse effect, was confirmed by SIMPSON calculations and demonstrated on a number of dynamic systems.     

Catalyst‐Free Reductive Coupling of Aromatic and Aliphatic Nitro Compounds with Organohalides

A rare reductive coupling of nitro compounds with organohalides has been realized. The reaction is initiated by a partial reduction of the nitro group to a nitrenoid intermediate. Therefore, not only aromatic but also aliphatic nitro compounds are efficiently transformed into monoalkylated amines, with organohalides as the alkylating agent. Given the innate reactivity of the nitrenoid, a catalyst is not required, resulting in a high tolerance for aryl halide substituents in both starting materials.     

Transient Phosphenium and Arsenium Ions versus Stable Stibenium and Bismuthenium Ions

Fluoride abstraction from bis-m-terphenylelement fluorides (2,6-Mes₂C₆H₃)₂EF (E=P, As) generated the highly reactive phosphenium ion [(2,6-Mes₂C₆H₃)₂P]⁺ and the arsenium ion [(2,6-Mes₂C₆H₃)₂As]⁺, which immediately underwent intramolecular electrophilic substitution and formation of an 1,2,4-trimethyl-6-mesityl-5-m-terphenyl-benzo[b]phospholium ion and an 1,2,4-trimethyl-6-mesityl-5-m-terphenyl-benzo[b]arsolium ion, respectively. The formation of the latter involved a methyl group migration from the ortho-position of a flanking mesityl group to the meta-position. This reactivity of [(2,6-Mes₂C₆H₃)₂E]⁺ (E=P, As) is in sharp contrast to the related stibenium ion [(2,6-Mes₂C₆H₃)₂Sb]⁺ and bismuthenium ion [(2,6-Mes₂C₆H₃)₂Bi]⁺, which have been recently isolated and fully characterized (Angew. Chem. Int. Ed. 2018, 57 , 10080–10084). On the basis of DFT calculations, a mechanism for the rearrangement of the phosphenium and arsenium ions into the phospholium and arsolium ions is proposed, which is not feasible for the stibenium and bismuthenium ions.     

On the restabilization of protein-covered latex colloids at high ionic strengths

Recent experiments on restabilization of protein-covered latex colloids at high ionic strengths reported by Lopez-Leon et al.(1) revealed strong specific anion effects. The same authors also emphasized that a recent polarization model, which involves both hydration and double layer forces, can account only for some of their experimental results but are in disagreement with other experimental results. The aim of the present paper is to show that most experimental results of ref 1 can be described, more than qualitatively, when the association equilibria for all the ions (with both the acidic and basic sites of the protein) are taken into account. As the traditional Poisson-Boltzmann approach, the polarization model neglects additional interactions between ions, and ions and surfaces, not included in the "mean field" electrical potential; therefore, a complete quantitative agreement should not be expected. While many of the discrepancies between calculations and experiment occur at low ionic strengths (10(-)(4)-10(-)(2) M), in the range of validity of the traditional DLVO theory, the latter can neither explain them. It is suggested that the structural modifications of the protein configuration induced by the electrolyte are responsible for some of the disagreements between experiment and calculations.     

Distinct gaps between fractional parts of sequences

Let be a real number, a positive integer and a subset of . We give an upper bound for the number of distinct lengths of gaps between the fractional parts .

     

Quantifying nonclassicality of one-mode Gaussian states of the radiation field

We define the degree of nonclassicality of a one-mode Gaussian state of the quantum electromagnetic field in terms of the Bures distance between the state and the set of all classical one-mode Gaussian states. We find the closest classical Gaussian state and the degree of nonclassicality using a recently established expression for the Uhlmann fidelity of two single-mode Gaussian states. The decrease of nonclassicality under thermal mapping is carefully analyzed. Along the same lines, we finally present the evolution of nonclassicality during linear amplification.     

Enhancement of two-photon emission in photonic crystals

We report the influence of photonic stopgaps on two-photon excited emission from highly efficient nonlinear chromophores infiltrated into high-quality photonic crystals. We have observed a sharp decrease (filter effect) in emission within the frequency range and direction of the stopgap as well as sharp enhancement of the two-photon excited emission associated with the stopgap's edge. This effect may be important for the development of low-threshold upconversion lasers.     

What is an observable?

The concept of generalized observable in the scheme of Hilbert quantum mechanics is discussed. We give an example of a possible ambiguity of this notion. The role of interpretation and the strong connection with concrete experimental procedures in the discussion of generalized observables are stressed to explain the above ambiguity.Dedicated to Professor Peter Mittelstaedt on the occasion of his 60th birthday.Humboldt fellow, on leave from the Institute of Physics, Nicholas Copernicus University, Torun, Poland.     

Nonisomorphic graphs with identical atomic counts of self-returning walks: Isocodal graphs

On the basis of endospectral graphs, we present a graphical method for obtaining pairs of nonisomorphic graphs with identical atomic counts of self-returning walks.