Dehydroabietane from the oleoresin of Pinus pallasiana

Summary The known diterpene hydrocarbon dehydroabietane has been isolated from a natural source — the oleoresin of the Crimean pine — for the first time.Institute of Chemistry, Academy of Sciences of the Moldavian SSR. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 20–22, January, 1971.     

Cyclization and rearrangements of diterpenoids. IX. Isomerization of (1R,2S,7S,10S,11R,12S,13S)-2,6,6,10,12-pentamethylpentacyclo[10.2.1.01,10.02,7.011,13]pentadecane by fluorosulfonic acid

It has been shown that the opening of the cyclopropane ring in (1R, 2S, 7S, 10S, 11R, 12S, 13S)-2,6,6,10,12-pentamethylpentacyclo[10.2.1.0^1,10.0^2,7.0^11,13]pentadecane takes place under the action of fluorosulfonic acid at all three carbon-carbon bonds, but at low temperatures the main isomerization product is (1R, 2S, 7S, 10S, 12S, 13S)-2,6,6,10,12-pentamethyltetracyclo[10.2.1.0^1,10.0^2,7]pentadecan-13-ol, and at the ordinary temperature the main products are (1R, 2S, 7S, 11S, 12R, 13R)-2,6,6,11,13-pentamethyltetracyclo[10.2.1.0^1,10.0^2,7]pentadeca-9-ene and (1S, 2R, 11S, 12R, 15R)-2,7,7,11,15-pentamethyltetracyclo[10.2.1.0^2,11.0^3,8]pentadeca-3(8)-ene.     

Adsorption process of phenothiazine solution in dimethyl sulfoxide on graphite electrodes

In this paper, an original solution for the modeling and simulation of the adsorption process of a phenothiazine derivative on graphite electrodes is presented. The adsorption process is considered a distributed parameter one, due to the fact that the adsorbed phenothiazine quantity is a function depending on two independent variables. The structure parameters of the adsorption process, which define the influence of both independent variables, are determined using an experimental identification method. The experimental data are obtained through an experiment which is based on the process step response. In order to simulate the adsorption process, the approximate analytical solution, representing the process model, is determined. The simulation results prove the model generality; it is being simulated in relation to both independent variables.     

Metallaphotoredox Difluoromethylation of Aryl Bromides

Herein, we report a convenient and broadly applicable strategy for the difluoromethylation of aryl bromides by metallaphotoredox catalysis. Bromodifluoromethane, a simple and commercially available alkyl halide, is harnessed as an effective source of difluoromethyl radical by silyl‐radical‐mediated halogen abstraction. The merger of this fluoroalkyl electrophile activation pathway with a dual nickel/photoredox catalytic platform enables the difluoromethylation of a diverse array of aryl and heteroaryl bromides under mild conditions. The utility of this procedure is showcased in the late‐stage functionalization of several drug analogues.     

Redheffer's theorem revisited

Based on the Ben Artzi-Gohberg result concerning the equivalence between the invertibility of theL ²-operator and the exponential dichotomic evolution defined byA(t), the time-varying counterpart of the Redheffer theorem is considered under relaxed conditions.     

Pole dynamics for the flierl-petviashvili equation and zonal flow

Using the method of positions of the complex singularities, we identify a class of new, exact solutions of the Flierl-Petviashvili equation. The solutions are periodic and have the geometry of the zonal flow. We examine the physical properties and find that the solution can reproduce data from experimental observations and numerical simulations.     

Gradient theory for structural forces in thin fluid films near the critical point

We consider a general form of the local gradient theory for structural forces in thin fluid films near the critical point. A complete analytical solution of this problem at separation distances substantially larger than the molecular size is presented. That is, pi= -[330Psi(-4)H(8.8923-Psi) + 384exp(-Psi)H(Psi-8.8923)]H(-Gamma)+[1134.36Psi(-4)H(8.8923-Psi + 192exp(-Psi)H(Psi-8.8923)]H(Gamma) where Gamma <0 for similar (both attractive or both repulsive) and Gamma >0 for dissimilar (one attractive, another repulsive) bounding surfaces. Here pi and Psi are the structural force and the separation distance scaled in a certain way, and H(.) is a unit step function. For binary polymer films, the results are further elaborated to include a scaling dependence of the structural force on polymerization degrees of components.     

Spectrum of coherent structures in a turbulent environment

The statistical properties of the turbulent field consisting of drift waves randomly interacting with a coherent structure are investigated. By using a nonperturbative method (analogous to the "semiclassical" approach in quantum mechanics), we calculate explicitly the generating functional of the correlations.     

Extraction of kinetic information from single-molecule experiments.

We discuss two possible approaches for extracting kinetic information from single-molecule experiments. The first approach is based on computing correlation functions from measured fluorescence signals, and the second on studying the statistics of on and off times of the same fluorescence signal. We show that in both cases it is possible to extract kinetic information about the nature of intramolecular fluctuations of the single molecule. We show that for single-molecule kinetics the intramolecular fluctuations produce stochastic memory effects which lead to new dynamic features that do not exist in traditional chemical kinetics. In particular, we investigate a new type of chemical oscillations in correlation functions observed experimentally by Edman and Rigler (Proc. Natl. Acad. Sci. USA 2000, 97, 8266).     

A new kinetic approach to flowing chemical systems with linearly dependent reactions

A new kinetic approach to flowing chemical system is introduced, based on the elimination of reaction extents attached to linearly dependent reactions. The method is applied to analyze the propagation of acoustic waves in a reacting chemical mixture.

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