Dynamical versus variational symmetries: understanding Noether's first theorem

It is argued that awareness of the distinction between dynamical and variational symmetries is crucial to understanding the significance of Noether's 1918 work. Special attention is paid, by way of a number of striking examples, to Noether's first theorem, which establishes a correlation between dynamical symmetries and conservation principles.     

Synthesis of 5,10,15,20-tetra[6' -nitro-1,3,3-trimethylspiro- (indolino-2,2' -2H-chromen-5-yl)]porphyrin and its metal complexes

A new 5,10,15,20-tetrasubstituted porphyrin containing four 6’-nitro-1,3,3-trimethylspiro(indolino-2,2’-2H-chromene) substituents and its complexes with Zn²⁺ and Cu²⁺ ions were prepared and characterized by physicochemical methods of analysis.     

Electrochemical Characterization and Voltammetric Determination of Benzoyl Derivatives of Phenobarbital Using Glassy Carbon Electrode

The electrochemical behavior of a number of benzoyl barbiturates was studied using a glassy carbon electrode (GCE). The kinetics of the electrode process is determined, the contribution of physical adsorption to the electrochemical process is estimated, and the mechanism of the possible electrochemical reaction is proposed. It is shown that the electrochemical reduction potentials of benzoyl phenobarbital derivatives are determined by the LUMO energies, calculated by the B3LYP 6‐311+G method. It is established that the process is quasi‐reversible, complicated by adverse reactions. The influence of halogen type and its position in the benzoyl residue of the studied substances on the analytical signal is established. The effective values of the dissociation constants of various forms of benzoyl derivatives were calculated using the example of halonal, for which the values 3.16 ? 10^?8 and 6.31 ? 10^?12, respectively, were found.     

Peculiar Photoinduced Electron Transfer in Porphyrin–Fullerene Akamptisomers

Porphyrin–fullerene dyads are promising candidates for organic photovoltaic devices. The electron-transfer (ET) properties of the molecular devices depend significantly on the mutual position of the donor and acceptor. Recently, a new type of molecular isomerism (akamptisomerism) has been discovered. In the present study, we explore how photoinduced ET can be modulated by passing from one akamptisomer to another. To this aim, four akamptisomers of the quinoxalinoporphyrin–[60]fullerene complex are selected for computational study. The most striking finding is that, depending on the isomer, the porphyrin unit in the dyad can act as either electron donor or electron acceptor. Thus, the stereoisomeric diversity allows one to change the direction of ET between the porphyrin and fullerene moieties. To understand the effect of akamptisomerism on the photoinduced ET processes, a detailed analysis of initial and final states involved in the ET is performed. The computed rate for charge separation is estimated to be in the region of 1–10 ns⁻¹. The formation of a long-living quinoxalinoporphyrin anion radical species is predicted.     

Which Stereoinductor Is Better for Asymmetric Functionalization of α-Amino Acids in a Nickel(II) Coordination Environment? Experimental and DFT Considerations

The results of extended comparative investigation of nickel(II) Schiff base complexes (containing various auxiliary chiral moieties) commonly used as a methodological platform for the asymmetric synthesis of tailor-made α-amino acids are provided. The following issues are addressed: 1) redox activity (determining the possibility for electrochemically induced reactions); 2) quantitative estimation of the reactivity of deprotonated complexes towards electrophiles; and 3) quantum-chemical estimation of noncovalent interactions in the metal coordination environment (which shed light on the origin of the stereochemical outcome observed for different stereoinductors). Possible mechanisms that determine the relationship between the stereochemical configuration of a molecule and its electronic structure are discussed. The DFT-calculated HOMO–LUMO energies and localization, as well as relative energies for the (S)- and (R)-alanine derivatives, that determine the stereoinduction efficiency in thermodynamically controlled reactions in nickel(II) coordination are provided. The computational data are supported by experimental results on the monobenzylation of glycine derivatives.     

Annulation of pyrrole ring in 4-acylpyridine-3,5-dicarbonitriles in the presence of ammonia

Chemistry of Heterocyclic Compounds - 4-Acyl-2-amino-6-chloropyridine-3,5-dicarbonitriles underwent heterocyclization in the presence of ammonia in aqueous dioxane medium, involving the...     

Ultrafast Single-Scan 2D NMR Spectroscopic Detection of a PHIP-Hyperpolarized Protease Inhibitor

Two-dimensional NMR spectroscopy is one of the most important spectroscopic tools for the investigation of biological macromolecules. However, due to the low sensitivity of NMR spectroscopy, it takes usually from several minutes to many hours to record such spectra. Here, the possibility of detecting a bioactive derivative of the sunflower trypsin inhibitor-1 (SFTI-1), a tetradecapeptide, by combining parahydrogen-induced polarization (PHIP) and ultrafast 2D NMR spectroscopy is shown. The PHIP activity of the inhibitor was achieved by labeling with O-propargyl-l -tyrosine. In 1D PHIP experiments a signal enhancement of a factor of approximately 1200 compared to standard NMR was found. This enhancement permits measurement of 2D NMR correlation spectra of low-concentrated SFTI-1 in less than 10 seconds, employing ultrafast single-scan 2D NMR detection. As experimental examples PHIP-assisted ultrafast single-scan TOCSY spectra of SFTI-1 are shown.     

Accurate prediction of norbornadiene cycle enthalpies by DLPNO-CCSD(T1)/CBS method

The DLPNO-CCSD(T₁)/CBS method combined with simple reactions containing small reference species leads to an improvement in the accuracy of theoretically evaluated enthalpies of formation of medium-sized polyalicyclic hydrocarbons when compared with the widely used composite approach. The efficiency of the DLPNO-CCSD(T₁)/CBS method is most vividly demonstrated by comparing with the results of G4 calculations for adamantane. The most important factor in choosing appropriate working reaction is the same number of species on both sides of the equation. Among these reactions, the reactions with small enthalpy change usually provide a better cancellation of errors. The DLPNO-CCSD(T₁)/CBS method was used to calculate the enthalpies of formation of compounds belonging to the norbornadiene cycle (norbornadiene, quadricyclane, norbornene, nortricyclane, and norbornane). The most reliable experimental enthalpies of formation are recommended for these compounds by comparing calculated values with conflicting experimental data.     

Photoinduced dynamics of a cyanine dye: parallel pathways of non-radiative deactivation involving multiple excited-state twisted transients

Cyanine dyes are broadly used for fluorescence imaging and other photonic applications. 3,3′-Diethylthiacyanine (THIA) is a cyanine dye composed of two identical aromatic heterocyclic moieties linked with a single methine, –CH. The torsional degrees of freedom around the methine bonds provide routes for non-radiative decay, responsible for the inherently low fluorescence quantum yields. Using transient absorption spectroscopy, we determined that upon photoexcitation, the excited state relaxes along two parallel pathways producing three excited-state transients that undergo internal conversion to the ground state. The media viscosity impedes the molecular modes of ring rotation and preferentially affects one of the pathways of non-radiative decay, exerting a dominant effect on the emission properties of THIA. Concurrently, the polarity affects the energy of the transients involved in the decay pathways and further modulates the kinetics of non-radiative deactivation.