ESI‐MS/MS of expanded porphyrins: a look into their structure and aromaticity

Electrospray mass spectrometry/mass spectrometry was used to investigate the gas‐phase properties of protonated expanded porphyrins, in order to correlate those with their structure and conformation. We have selected five expanded meso‐pentafluorophenyl porphyrins, respectively, a pair of oxidized/reduced fused pentaphyrins (22 and 24 π electrons), a pair of oxidized/reduced regular hexaphyrins (26 and 28 π electrons) and a regular doubly N‐fused hexaphyrin (28 π electrons). The gas‐phase behavior of the protonated species of oxidized and reduced expanded porphyrins is different. The oxidized species (aromatic Hückel systems) fragment more extensively, mainly by the loss of two HF molecules. The reduced species (Möbius aromatic or Möbius‐like aromatic systems) fragment less than their oxidized counterparts because of their increased flexibility. The protonated regular doubly fused hexaphyrin (non‐aromatic Hückel system) shows the least fragmentation even at higher collision energies. In general, cyclization through losses of HF molecules decreases from the aromatic Hückel systems to Möbius aromatic or Möbius‐like aromatic systems to non‐aromatic Hückel systems and is related to an increase in conformational distortion. Copyright © 2016 John Wiley & Sons, Ltd.     

Synthesis, spectral and oxidase studies of a new diamide copper(II) complex with pendant benzimidazolyl groups

A new benzimidazole-based diamide ligand-N,N'-bis(alanine-2-benzimidazolyl) hexanediamide (ABHA) has been synthesized and utilized to prepare Cu(II) complexes of general composition [Cu(ABHA)X2].nH2O,where X is an exogenous anionic ligand (X=Cl-,NO3-). Low temperature EPR spectra has been obtained that shows gparallel>gperpendicular>2.0024, indicating a tetragonal geometry in the solution state. The complexes display a quasi-reversible redox wave due to the Cu(II)/Cu(I) reduction process. E1/2 values shift anodically as NO3-相似文献   

A novel one-pot conversion of amines to homologated esters in poly(ethylene glycol)

The first deaminative homologation of amines (-CH₂NH₂) to esters (-CH₂CH₂COOEt) in one-pot is reported. The reaction proceeds through, formation of an aldehyde from an amine in the presence of Pd/C as catalyst followed by Wittig reaction and catalytic hydrogenation using poly(ethylene glycol) as the solvent in one-pot.     

g-factor measurements in stable Hg isotopes

The g-factor of the first 2⁺ state in¹⁹⁸Hg,²⁰⁰Hg and²⁰²Hg has been measured using the thin foil Transient Field technique. The values were calibrated to the known g-factor of the first 5/2⁻ state in¹⁹⁹Hg. The levels were Coulomb excited by 217 MeV nickel ions with gadolinium acting as ferromagnetic medium. The obtained values are rather constant and contradict a previously observed dip at²⁰⁰Hg. Two other g-factors have been remeasured in¹⁹⁹Hg.     

Chemistry of 2-nitroglycals: a one-pot three-component stereoselective approach toward 2-C-branched O-galactosides

A convenient one-pot three-component approach for the synthesis of 2-C-branched O-glycosides has been developed from 2-nitroglycals. These 2-C-branched sugars have been shown to be precursors for a variety of biologically and synthetically relevant molecules.     

General Entropic Approximations for Canonical Systems Described by Kinetic Equations

In this paper we extend the general construction of entropic approximation for kinetic operators modelling canonical systems. More precisely, this paper aims at pursuing to thermalized systems the works of Levermore, Schneider and Junk on moments problems relying on entropy minimization in order to construct BGK approximations and moments based equations.     

A BGK Model for Gas Mixtures

The aim of this article is to construct a BGK operator for gas mixtures starting from the true Navier-Stokes equations. That is the ones having transport coefficients given by the hydrodynamical limit of the Boltzmann equation(s). Here the same hydrodynamical limit is obtained by introducing relaxation coefficients on certain moments of the distribution functions. Next the whole model is set by using entropy minimization under moments constraints. In our case the BGK operator allows to recover the exact Fick and Newton laws and satisfy the fundamental properties of the Boltzmann equations for inert gas mixtures.     

First description of B chromosomes in the family Auchenipteridae,Parauchenipterus galeatus (Siluriformes) of the São Francisco River basin (MG,Brazil)

B chromosomes are considered additional and non-essential; they likely originate from A chromosomes and follow a distinct evolution. In fish, approximately half of the Neotropical species with B chromosomes are Characiformes and 35% are Siluriformes. There has been no report of B chromosomes in Auchenipteridae until this moment. B chromosomes found in a population of Parauchenipterus galeatus from the São Francisco River basin in the state of Minas Gerais (Brazil) were small, metacentric, totally heterochromatic and exhibited intra-individual and inter-individual variation. The diploid number was 58 chromosomes (22 metacentric, 16 submetacentric, 12 subtelocentric and 8 acrocentric). The nucleolar organizing regions were simple and the heterochromatin intercalated in the ribosomal sites, characterized by CMA₃ and DAPI fluorochromes, was of a GC-rich constitution. The 5S rDNA genes were located in an intercalary position in only one chromosome pair. An hypothesis about the origin of the B chromosomes in P. galeatus and a review on B chromosomes in catfish are also presented in this study.     

Catalytic chameleon dendrimers

Dendrimers with boronic ester end-groups and an iron porphyrin core were synthesized and characterized. The dendrimer termini were reversibly exchanged by the addition of appropriate diol molecules. According to molecular dynamics (MD) simulations, the exchange of termini may lead to changes in the conformational behavior of the dendrimer, specifically regarding the average position of the end groups relative to the core. The spatial steric disposition attained with different termini was shown to significantly affect epoxidation reaction activity and selectivity with various alkenes, thus allowing for an original way to control and adjust catalytic behavior under alternating environments.     

g-factor of the first excited 4+ states in156Gd and158Gd

Relative g-factor of the first 2⁺ and 4⁺ states have been measured with the transient field technique in¹⁵⁶Gd and¹⁵⁸Gd. The precession of gamma rays depopulating the levels under study were observed, after passing through thin polarized gadolinium. The observed values agree with the predictions of the rotational model, i.c. g(4⁺)= g(2⁺), while contrasting the hypothesis that in¹⁵⁶Gd the g-factor of the 4⁺ is reduced with respect to the 2⁺, because of rotational alignment.