Synthesis of heteroannular mercury derivatives of acetoxy- and methoxyferrocene

Conclusions The synthesis of 1,1-(acetoxy)chloromercuryferrocene, di-1(1-acetoxyferrocenyl)mercury, 1,1-(methoxy)chloromercuryferrocene, and di-1-(1-methoxyferrocenyl)mercury from ferrocenylboric acids was described.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2574–2575, November, 1967.     

Dynamic equations for time-averaged coordinates at thermal equilibrium

The Hamilton variational principle with coarse variation (over a limited number of parameters introduced into the coordinates) is used to find relations for the time-averages of defined functions of the coordinates and velocities. The dynamic equations for the parameters characterizing the average behavior of the coordinates are then found by orthogonalization of the coordinates. It is shown that the entropy of the dynamic system is expressed in terms of these averaged parameters, and the dynamic equations and stability conditions may be found by minimization of the defined function of the motion, which is constructed like the thermodynamic potential. A perturbation procedure is suggested for solving the dynamic equations.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 4, pp. 87–94, April, 1991.     

4-Hydroxylindole-acetic acid — The microbiological transformation product of indole-3-acetic acid

Conclusions The isolation of an unknown intermediary in the microbiological transformation of indole-3-acetic acid to 4-hydroxyindole-3-acetic acid may help us to determine the structure of 4-hydroxyindole-3-acetic acid.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1155–1158, May, 1975.The authors express their gratitude to G. K. Skryabin and M. N. Kolosov for assistance in carrying out the present work.     

Fluctuations and a rigorous uncertainty relation of trigonometric operators of the phase and the number of photons of an electromagnetic field for general quantum superpositions of coherent states

The quantum-statistical properties of states of an electromagnetic field of general superpositions of coherent states of the form of N _α,β(α?+e ^iξ β? are investigated. Formulas for the fluctuations (variances) of Hermitian trigonometric phase field operators ? ≡ côs φ, ? ≡ sîn φ (the so-called “Susskind–Glogower operators”) are found. Expressions for the rigorous uncertainty relations (Cauchy inequalities) for operators of the number of photons and trigonometric phase operators, as well as for operators ? and ?, are found and analyzed. The states of amplitude \({N_{\alpha ,\beta }}\left( {\left| {{{\sqrt {ne} }^{i\varphi }}\rangle + {e^{i\xi }}\left| {{{\sqrt {{n_\beta }e} }^{i\varphi }}\rangle } \right.} \right.} \right)\), φ = φ_α = φ_β, and phase \({N_{\alpha ,\beta }}\left( {\left| {{{\sqrt {ne} }^{i{\varphi _\alpha }}}\rangle + {e^{i\xi }}\left| {{{\sqrt {ne} }^{i{\varphi _\beta }}}\rangle } \right.} \right.} \right)\), n = n _α = n _β, superpositions of coherent states are considered separately. The types of quantum superpositions of meso- and macroscales (n _α, n _β » 1) are found for which the sines and/or cosines of the phase of the field can be measured accurately, since, under certain conditions, the quantum fluctuations of these quantities are close to zero. A simultaneous accurate measurement of cosφ and sinφ is possible for amplitude superpositions, while an accurate measurement of one of these trigonometric phase functions is possible in the case of certain phase superpositions. Amplitude superpositions of coherent states with a vacuum state are quantum states of the field with a “maximum” level of the quantum uncertainty both in the case of a mesoscopic scale and in the case of a macroscopic scale of the field with an average number of photons n _α/β ≈ 0, n _β/α » 1.     

A Ring Opening–Annulation Reaction of Anthra[1,2-d][1,2,3]triazine-4,7,12(3H)-trione in the Presence of Pyridines as an Efficient Approach to the Construction of Naphtho[2,3-H]pyrido(quinolino)[2,1-b]quinazoline System

The [1,2,3]triazin-4(3H)-one ring is a synthetically important molecular platform for a variety of chemical transformations. Despite this, currently, there has been little research on the reaction of the thermal opening of the [1,2,3]triazin-4(3H)-one nucleus. In this work, we describe the synthetic potential of anthra[1,2-d][1,2,3]triazine-4,7,12(3H)-trione in the reaction of the thermal opening of a cycle following the [4+2]-cycloaddition reaction with a number of pyridine derivatives and quinoline. It is shown that this method is effective for the synthesis of the 6H-naphtho[2,3-H]pyrido(quinolino)[2,1-b]quinazoline-6,9,14-trione system. We also investigate the influence of the position of substituents in the structure of pyridine on the formation characteristics of the target products.     

Two-photon absorption enhancement of polymer-templated porphyrin-based J-aggregates

Supramolecular structures based on organized assemblies of macrocyclic chromophores, particularly porphyrin-based dyes, have attracted widespread interest as components of molecular devices with potential applications in molecular electronics, artificial light harvesting, and pharmacology. We report the formation of J-aggregates of two porphyrin-based dyes, 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin (TSPP, 4) and an amino tris-sulfonate analogue (5) in water using a functionalized norbornene-based homopolymer, synthesized by ring-opening metathesis polymerization (ROMP). Ionic interactions of the cationic side chains (ammonium groups) of the polymer under acidic conditions with the negatively charged sulfonate groups of the porphyrins facilitated polymer template enhanced J-aggregation of the porphyrin dyes. J-Aggregation behavior was investigated photophysically by UV-vis absorption along with steady-state and time-resolved fluorescence studies. Two-photon absorption (2PA) was enhanced by about an order of magnitude for the J-aggregated TSPP relative to its free base. Significantly, the 2PA cross section of the polymer-templated TSPP J-aggregate was up to three times higher than the J-aggregated TSPP in the absence of the polymer template while the 2PA cross section for polymer-templated J-aggregates of 5 increased substantially, up to ca. 10,000 GM, suggesting a prominent role of polymer-templating to facilitate porphyrin aggregation and greatly enhance nonlinear absorption.     

Direct and initiated halogenation of carbon nanomaterials at low temperatures

Cryochemical reactions of the direct and initiated (by photolysis and radiolysis) halogenation of carbon nanomaterials (C₆₀ fullerene, nanotubes, and nanofibers) at 77–240 K were investigated by the ESR, IR spectroscopy, and elemental analysis techniques. A high reactivity of C₆₀ in reactions with fluorine and chlorine with the formation of corresponding derivatives was shown. High concentrations of radical intermediates indicating the radical chain halogenation of C₆₀ were detected (the kinetic chain length for the chlorination process reaches 10⁴–10⁶ units). The amount of chlorine attached to fullerene is ～35% and practically does not depend on the initiation mode (UV or γ-irradiation at doses up to 350 kGy). The mechanism of the cryochemical halogenation of C₆₀ is considered within the limits of the model of multicenter synchronous transitions in a molecular complex consisting of several reactant molecules including molecular fluorine or chlorine and ensuring a net exothermic effect. The amount of chlorine added to nanotubes and nanofibers did not exceed 2.5–8%, thereby indicating a low reactivity of these materials under cryogenic conditions.     

A superfluorescent fluorenyl probe with efficient two-photon absorption

The linear photophysical, excited state absorption (ESA), superfluorescence, and two-photon absorption (2PA) properties of 4,4'-(1E,1'E)-2,2'-(7,7'(1E,1'E)2,2'(4,4'-sulfonylbis(4,1-phenylene))bis(ethane-2,1-diyl)bis(9,9-didecy-9H-fluorene7,2-diyl))bis(ethane-2,1-diyl)bis(N,N-diphenylaniline) (1) were investigated in organic and aqueous media with respect to its potential application in biological imaging. The analysis of linear photophysical properties revealed a rather complex nature of the main one-photon absorption band, strong solvatochromic effects in the steady-state fluorescence spectra, single-exponential fluorescence decay, and high fluorescence quantum yields in organic solvents (≈1.0). The ESA spectra of 1 suggested potential for light amplification in nonpolar media while efficient superfluorescence in cyclohexane was demonstrated. The degenerate 2PA spectra of 1 were obtained over a broad spectral range (640-900 nm), using a standard two-photon induced fluorescence method under 1 kHz femtosecond excitation. Two well defined 2PA bands with maximum 2PA cross sections up to 1700 GM in the higher energy, short wavelength band and ≈1200 GM in the lower energy, long wavelength band of 1 were shown. The potential use of 1 in bioimaging was demonstrated via one- and two-photon in vitro fluorescence imaging of HCT 116 cells.     

Synthesis of new-type 1,3,6-triazocine via intramolecular reactions of iodocyclization and [3+2] azido cycloaddition

Selective iodocyclization of 6-(alkenylamino)-1-allylpyrazolo[3,4-d]pyrimidines provided hydrogenated derivatives of 1-allyl-8(9)-iodomethylimidazo(pyrimido)[1,2-a]pyrazolo[4,3-e]pyrimidines which were further reacted with NaN₃ at 75°С to 80°С to give a series of new-type 1,3,6-triazocines annulated with the pyrazole, pyrimidine, imidazole (or pyrimidine), and 1,2,3-triazole rings. The compounds synthesized were structurally characterized by analytical, spectral (IR, ¹H and ¹³C NMR, HPLC-mass), and X-ray diffraction data.     

Mixed-ligand complexation of iron(III) ethylenediaminetetraacetate with iminodiacetate and ethylenediamine in aqueous solution

The formation of the heteroleptic complexes FeEdtaIda³⁻ and FeEdtaEn⁻(Ida²⁻ is the iminodiacetate anion and En is ethylenediamine) was examined by direct calorimetry, pH potentiometry, and spectrophotometry at 298.15 K and the ionic strength I = 0.5 (KNO₃). A possible way of coordination of the ligands in the heteroleptic complexes was discussed.