Complexes of Phosphorus-containing Cyclophanes and Cryptands with Metals,Anions, and Organic Substrates

Russian Journal of Organic Chemistry - New data since about 2010 concerning complex formation of phosphorus-containing cyclophanes and cryptands with transition metals, as well as guest-host...     

Midinfrared Light-Emitting Diodes Based on А3В5 Heterostructures in Gas-Analyzer-Equipment Engineering: Potential and Applications in 2014–2018

Optics and Spectroscopy - Studies published in the period from 2014 to 2018 that are aimed at creating nondispersive and photoacoustic IR gas analyzers with LED radiation sources based on...     

Origin of the Photoinduced Geometrical Change of Copper(I) Complexes from the Quantum Chemical Topology View

Copper(I) complexes (CICs) are of great interest due to their applications as redox mediators and molecular switches. CICs present drastic geometrical change in their excited states, which interferes with their luminescence properties. The photophysical process has been extensively studied by several time-resolved methods to gain an understanding of the dynamics and mechanism of the torsion, which has been explained in terms of a Jahn–Teller effect. Here, we propose an alternative explanation for the photoinduced structural change of CICs, based on electron density redistribution. After photoexcitation of a CIC (S₀→S₁), a metal-to-ligand charge transfer stabilizes the ligand and destabilizes the metal. A subsequent electron transfer, through an intersystem crossing process, followed by an internal conversion (S₁→T₂→T₁), intensifies the energetic differences between the metal and ligand within the complex. The energy profile of each state is the result of the balance between metal and ligand energy changes. The loss of electrons originates an increase in the attractive potential energy within the copper basin, which is not compensated by the associated reduction of the repulsive atomic potential. To counterbalance the atomic destabilization, the valence shell of the copper center is polarized (defined by ∇²ρ(r) and ∇²V_ne(r)) during the deactivation path. This polarization increases the magnitude of the intra-atomic nuclear–electron interactions within the copper atom and provokes the flattening of the structure to obtain the geometry with the maximum interaction between the charge depletions of the metal and the charge concentrations of the ligand.     

Raman Scattering in Langasite-Family Crystals

Crystallography Reports - Raman scattering spectra have been investigated in La3Ga5SiO14 langasite crystals with Cr and Fe impurities and La3Ga5.25Ta0.25Si0.5O14 crystalline solid solution. It is...     

Introducing the Petasis Reaction for Late‐Stage Multicomponent Diversification,Labeling, and Stapling of Peptides

For the first time, the Petasis (borono‐Mannich) reaction is employed for the multicomponent labeling and stapling of peptides. The report includes the solid‐phase derivatization of peptides at the N‐terminus, Lys, and N^?‐MeLys side‐chains by an on‐resin Petasis reaction with variation of the carbonyl and boronic acid components. Peptides were simultaneously functionalized with aryl/vinyl substituents bearing fluorescent/affinity tags and oxo components such as dihydroxyacetone, glyceraldehyde, glyoxylic acid, and aldoses, thus encompassing a powerful complexity‐generating approach without changing the charge of the peptides. The multicomponent stapling was conducted in solution by linking N^?‐MeLys or Orn side‐chains, positioned at i, i+7 and i, i+4, with aryl tethers, while hydroxy carbonyl moieties were introduced as exocyclic fragments. The good efficiency and diversity oriented character of these methods show prospects for peptide drug discovery and chemical biology.     

Alkylation of 6-Polyfluoroalkyl-2-thiouracils with Haloalkanes

Russian Journal of Organic Chemistry - The structure of 6-polyfluoroalkyl-2-thiouracils and reactivity of nucleophilic centers in their molecules were analyzed by quantum chemical calculations....     

Extraction-chromatographic behavior of Zr(IV) and Hf(IV) on TRU and LN resins in mixtures of HNO3 and HF

The behavior of group-4 homologs Zr and Hf on extraction-chromatographic sorbents LN resin and TRU resin in mixtures of HF and HNO₃ is considered. Distribution coefficients of the elements in the mixtures of 5·10⁻⁴ M–1 M HF and 0.01 M–5 M HNO₃ are determined. Strong retention of both elements was found on LN resin in the range of concentrations c(HF) ≤ 0.01 M for all concentrations of HNO₃. Retention tends to gradually disappear while increasing c(HF) to 0.5 M. On TRU resin retention is observed only in solutions with c(HNO₃) ≥ 2 M and c(HF) ≤ 0.01 M. The possibility of separating Zr(IV) and Hf(IV) on LN resin is illustrated in two different acid mixtures, whereas their separation on TRU resin under the conditions studied in this work is difficult. The results obtained can be used to isolate analytes from multicomponent mixtures during analytical tasks, as well as to separate them from each other.

     

α-Diphenylphosphino-N-(pyrazin-2-yl)glycine as a ligand in Ni-catalyzed ethylene oligomerization

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A Combined Immunofluorescence and Fluorescent Viability Cocktail Staining Procedure for Rapid Microscopic Detection and Enumeration of Live Legionella pneumophila

Journal of Fluorescence - This report describes a combined immunofluorescence and fluorescence viability stain applied as one staining solution for rapid detection of live Legionella...