Asymmetric [3+2] Photocycloadditions of Cyclopropanes with Alkenes or Alkynes through Visible‐Light Excitation of Catalyst‐Bound Substrates

The herein reported visible‐light‐activated catalytic asymmetric [3+2] photocycloadditions between cyclopropanes and alkenes or alkynes provide access to chiral cyclopentanes and cyclopentenes, respectively, in 63–99 % yields and with excellent enantioselectivities of up to >99 % ee. The reactions are catalyzed by a single bis‐cyclometalated chiral‐at‐metal rhodium complex (2–8 mol %) which after coordination to the cyclopropane generates the visible‐light‐absorbing complex, lowers the reduction potential of the cyclopropane, and provides the asymmetric induction and overall stereocontrol. Enabled by a mild single‐electron‐transfer reduction of directly photoexcited catalyst/substrate complexes, the presented transformations expand the scope of catalytic asymmetric photocycloadditions to simple mono‐acceptor‐substituted cyclopropanes affording previously inaccessible chiral cyclopentane and cyclopentene derivatives.     

Nonselfadjoint operators generated by the equation of a nonhomogeneous damped string

We consider a one-dimensional wave equation, which governs the vibrations of a damped string with spatially nonhomogeneous density and damping coefficients. We introduce a family of boundary conditions depending on a complex parameter . Corresponding to different values of , the problem describes either vibrations of a finite string or propagation of elastic waves on an infinite string. Our main object of interest is the family of non-selfadjoint operators in the energy space of two-component initial data. These operators are the generators of the dynamical semigroups corresponding to the above boundary-value problems. We show that the operators are dissipative, simple, maximal operators, which differ from each other by rank-one perturbations. We also prove that the operator coincides with the generator of the Lax-Phillips semigroup, which plays an important role in the aforementioned scattering problem. The results of this work are applied in our two forthcoming papers both to the proof of the Riesz basis property of the eigenvectors and associated vectors of the operators and to establishing the exact and approximate controllability of the system governed by the damped wave equation.

     

Amperometric Glucose Determination by Means of Glucose Oxidase Immobilized on a Cellulose Acetate Film: Dependence on the Immobilization Procedures

Glucose microelectrodes were prepared by immobilizing glucose oxidase onto a cellulose acetate film coating a platinum wire. Hexamethylenediamine (HMDA) and Glutaraldehyde (GA) were employed as spacer and coupling agent, respectively. Sensitivities and linear response ranges were studied as a function of the relative amounts of HMDA and GA. The best sensitivity was found when HMDA and GA were 5% and 2.5% in aqueous solutions, respectively. Taking as a reference the functioning of this biosensor, the roles of HMDA and GA percentages appear to be opposed when the extension of the linear response range is considered. Indeed, an increase of one unit in HMDA percentage (from 5 to 6 %) induces an increase in the extension of the linear response range equal to that obtained with a decrease of one unit of GA percentage (from 2.5 to 1.5%).     

Reaction between 2,2′ -dithiodianiline and acetylenic ketones or esters. A new synthesis of 4H-1,4-benzothiazines

The title compounds ( 3a-c ) together with the benzothiazolines ( 4b-c ) were obtained by reaction between 2,2′ -dithiodianiline ( 1 ) and acetylenic ketone ( 2a ) or esters ( 2b-c ). A possible pathway involving the formation and subsequent cyclization to 3 of enamine intermediates A and/or B , is suggested.     

Modelling physico-chemical properties of halogenated benzenes: QSAR optimisation through variables selection

Abstract This paper describes the development of multivariate QSAR models for halogenated benzenes. Four physico-chemical properties have been modelled: Boiling Point (BP), Melting Point (MP), Flash Point (FP) and Density (D). For the multivariate characterisation of this class of compounds 90 topological indices derived from the chemical formula were used. The models were calibrated on training sets selected by a D-optimal design and were optimised by a statistical procedure of selection of the most informative variables. The predictive capacity of the resulting models measured in terms of the parameter SDEP (Standard Deviation of the Errors of Predictions) were as follows; MP: ± 21 ±C (with MP ranging from -48° to 181°C); BP: ±13°C (75° to 286°C); D: ±0.14 (1.02 to 2.52 g/cm(3)); FP: ±17°C (-12 to 126°C). These data were confirmed "experimentally", i.e., on external validation sets of compounds, the experimental values of the standard deviation of prediction errors were in fact as follows; MP: ±30°C; BP: ±16°C D: ±0.18 g/cm(3); FP: ±16°C. The developed models therefore provide a valuable tool for estimating physico-chemical properties relevant to environmental chemistry.     

Intraresidue distribution of energy in proteins

Boltzmann-like distributions appear in many properties and energy-related quantities of proteins. A few examples are hydrophobicity, various types of side-chain/side-chain interactions, proline isomerization, hydrogen bonds, internal cavities, interactions at the level of specific atom types, and the propensity of the phi/'phi' ratio. Here, we conjecture that the Boltzmann hypothesis also holds for the intra-residue energy distribution. We confirm the conjecture by calculating the energies of 41,672 residues of the structures of highly resolved proteins, where at least 12 out of 20 naturally occurring amino acids follow Boltzmann's law. We further examine the entire set of all residue energies and find that the convolution of the individual distributions gives a Poisson function, which is followed by approximately 50% of individual proteins' structures.     

Determination of the enantiomeric composition of phenylalanine samples by chemometric analysis of the fluorescence spectra of cyclodextrin guest-host complexes

A novel strategy for determining the enantiomeric composition of phenylalanine samples that combines ordinary fluorescence spectroscopy, guest-host cyclodextrin chemistry, and multivariate regression modeling is investigated. Partial-least-squares regression (PLS-1) models were developed from fluorescence spectral data obtained with a series of samples containing cyclodextrin guest-host complexes of phenylalanine with different known enantiomeric compositions. The regression models were subsequently validated by determining the enantiomeric composition of a set of independently prepared phenylalanine samples. The ability of the models to correctly predict the enantiomeric compositions of future samples was evaluated in terms of the root-mean-square percent relative error (RMS%RE). The RMS%RE in the mol fraction of D-phenylalanine ranged from 1.3% to 3.0% when beta-cyclodextrin was used as the host molecule for different guest-host concentrations. The RMS%RE in the mol fraction of D-phenylalanine obtained in a similar validation study conducted with gamma-cyclodextrin ranged between 1.8% and 4.0% for different guest-host concentrations. Compared with previous studies done in absorption, fluorescence data were found to be more sensitive and the spectral differences observed as a function of enantiomeric composition were more uniformly spaced, making regression modeling more reliable. As a result, good regression models could be made at lower concentrations than were possible previously when absorption measurements were used.     

Visible spectra of heavy ions with an open 4f shell

We present visible to near-infrared spectra of highly charged Yb (the atomic number 70) and W (74) obtained with a compact electron beam ion trap. By observing the dependence on the electron beam energy, the charge state that should be assigned to the observed lines is determined. For In-like Yb²¹⁺ and W²⁵⁺ and Sn-like W²⁴⁺, the experimental spectra are compared with theoretical calculations done by the CI+all-order method. In each spectrum, the most prominent line is identified as the magnetic dipole transition from the first excited fine structure level to the ground level in the ground electronic configuration, 4f³ for In-like ions and 4f⁴ for Sn-like ions.