A proposal for the mechanism-of-action of diazoparaquinone natural products

Treatment of the representative diazoparaquinone prekinamycin dimethyl ether with Bu3SnH/AIBN in aromatic solvents furnishes moderate-to-good yields of formal aryl adducts wherein a molecule of solvent is attached to the carbon (C(11)) previously bearing the diazo function. Substituent studies provide evidence in support of a radical aromatic substitution mechanism, in which radical addition to the diazoparaquinone function generates an intermediate C(11) vinylic radical.     

Benzo[b]fluorenes via indanone dianion annulation: a short synthesis of prekinamycin

[structure: see text]. A rapid construction of benzo[b]fluorenones via reaction of 1-indanone dianions with phthalate diesters is described. Its utility is illustrated with a concise synthesis of prekinamycin.     

Syntheses of Prekinamycin and a Tetracyclic Quinone from Common Synthetic Intermediates

Towards total synthesis of a series of kinamycin and related antibiotics via common synthetic intermediates, total synthesis of prekinamycin was achieved via Suzuki coupling of naphthaleneboronic acid and bromobenzene derivative, intramolecular Friedel? Crafts reaction of 2‐(naphthalen‐2‐yl)benzoic acid, and diazotization in ten steps from 3,5‐dimethylphenol. Synthetic studies towards kinamycin antibiotics was also examined, and the tetracyclic quinone core for kinamycins was synthesized. Palladium‐catalyzed site‐selective hydroxylation of a benzoic acid derivative with the AB‐D ring part was successfully applied to the selective D‐ring functionalizations.     

On the mechanism of the formation of ozonides of the alkali metals

Conclusions A mechanism of the formation of ozonides of alkali metals was proposed on the basis of data obtained in an investigation of the reaction of oxygen-labeled KOH with ozone, the reaction of KOH with atomic oxygen, and the reaction of KOH with ozone; this mechanism is based upon: the catalytic decomposition of ozone on the surface of the solid alkalies into molecular and atomic oxygen, the interaction of the latter with the hydroxide, forming a superperoxide, and an interaction of the superperoxide with ozone, forming the ozonide.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1183–1187, June, 1967.     

On the role of the conserved aspartate in the hydrolysis of the phosphocysteine intermediate of the low molecular weight tyrosine phosphatase

The usual rate-determining step in the catalytic mechanism of the low molecular weight tyrosine phosphatases involves the hydrolysis of a phosphocysteine intermediate. To explain this hydrolysis, general base-catalyzed attack of water by the anion of a conserved aspartic acid has sometimes been invoked. However, experimental measurements of solvent deuterium kinetic isotope effects for this enzyme do not reveal a rate-limiting proton transfer accompanying dephosphorylation. Moreover, base activation of water is difficult to reconcile with the known gas-phase proton affinities and solution phase pK(a)'s of aspartic acid and water. Alternatively, hydrolysis could proceed by a direct nucleophilic attack by a water molecule. To understand the hydrolysis mechanism, we have used high-level density functional methods of quantum chemistry combined with continuum electrostatics models of the protein and the solvent. Our calculations do not support a catalytic activation of water by the aspartate. Instead, they indicate that the water oxygen directly attacks the phosphorus, with the aspartate residue acting as a H-bond acceptor. In the transition state, the water protons are still bound to the oxygen. Beyond the transition state, the barrier to proton transfer to the base is greatly diminished; the aspartate can abstract a proton only after the transition state, a result consistent with experimental solvent isotope effects for this enzyme and with established precedents for phosphomonoester hydrolysis.     

Effects of the composition of the reaction mixture and the nature of the template on the structure of mesoporous aluminosilicates formed in the presence of lecithin

It has been established that supramolecular structures of lecithin can act as templates in the synthesis of mesoporous aluminosilicates. Mesoporous substances, with pore dimensions up to 100 Å and biporous materials can be obtained when various combinations of lecithin with cetyltrimethylammonium bromide or octadecylamine are used as template agents in the aluminosilicate system.     

Dependence of the reactivity of allophanates on the conformation of the main chain

The CNDO/2 method was used to investigate the conformation and structure of alkylsubstituted allophanates. The possibility of the existence of isomers both with coplanar and with noncoplanar main chains NCNC was studied. It was shown that the formation of conformers with a cis-structure of the ester group is more probable. On the basis of an analysis of the dependence of the reactivity on the structure of the main chain, hypotheses were advanced on the role of the more stable conformers in various channels of polyaddition of isocyanates.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 22, No. 3, pp. 360–363, May–June, 1986.     

Influence of the structure of the diol on the properties of aromatic polyesterimides

A series of aromatic polyesterimides with ester bonds in the side-chains has been obtained by the partial esterification of a polyamic acid prepared from pyromellitic dianhydride and 4,4′-diaminodiphenyl ether with the following aromatic diols: 4,4′-di(2-hydroxyethoxy)-1,1′-binaphthyl, 2,2′-di(2-hydroxyethoxy)-1,1′-binaphthyl.di(2-hydroxyethoxy-1 -naphthyl)methane,2,2-di[4-(2-hydroxyethoxy)phenyl] propane.Influence of the structure of the diol on the thermal, mechanical and dielectric properties of resultant polymer foils has been studied. Properties of these foils have been compared with those obtained for the polypyromellitimide film of the 4,4′-diaminodiphenyl ether.     

Synthesis of the amide of the C-terminal tetrapeptide of the sequence of oxytocin

The synthesis has been effected of the amide of the tetrapeptide forming the sequence 6–9 of oxytocin with the use of benzyl protection of the thiol function of cysteine by two main schemes 1+3 and 2+2. The advantageousness of performing the synthesis by the 2+2 scheme has been shown. The overall yield of tetrapeptide using the method of condensation with the formation of mixed anhydrides amounted to 51% by the scheme proposed.All-Union Scientific-Research Institute of the Technology of Blood Substitutes and Hormone Preparations, Moscow. Translated from Khimiya Prirodnykh Soedinenii, Nos. 3,4, pp. 393–400, May–August, 1992.     

Influence of the structure of the alcoholic modifier on the enantioselective separation of nadolol

The influence of the structure of the alcoholic modifier of the mobile phase on the liquid chromatographic separation of the optical isomers of nadolol on a Pirkle-type chiral stationary phase was investigated. The isomers were separated as their chiral 1-naphthylureides on a column consisting of 3,5-dinitrobenzoyl- -leucine covalently bound to 3-μm aminopropylsilica, using an eluent consisting of n-hexane modified with an alcohol. A number of straight-chain, branched and unsaturated alcohols with carbon numbers ranging from 1 to 8 were evaluated. The choice of alcohol influenced both retention and selectivity, with optimum stereoselectivity being observed for C₃. The alcoholic modifiers selectively affected the retention and resolution of the two pairs of enantiomers that constitute nadolol. Thus chromatograms displaying two, three or four peaks could be obtained, depending on which modifier was employed. The best separation of all four isomers was achieved with ethanol as the modifier.     

On the volume-dependence of the index of refraction from the viewpoint of the complex dielectric function and the Kramers-Kronig relation

How indices of refraction n(omega) of insulating solids are affected by the volume dilution of an optical entity and the mixing of different, noninteracting simple solid components was examined on the basis of the dielectric function epsilon(1)(omega) + iepsilon(2)(omega). For closely related insulating solids with an identical composition and the formula unit volume V, the relation [epsilon(1)(omega) - 1]V = constant was found by combining the relation epsilon(2)(omega)V = constant with the Kramers-Kronig relation. This relation becomes [n(2)(omega) - 1]V = constant for the index of refraction n(omega) determined for the incident light with energy less than the band gap (i.e., h omega < E(g)). For a narrow range of change in the formula unit volume, the latter relation is well approximated by a linear relation between n and 1/V.     

On the mechanism of the photocyclization of azadienes

The photocyclization of azadienes to yield quinolines has been studied by means of CASPT2//CASSCF calculations. In order to study this extensive family of compounds, a minimal model system keeping the fundamental key features of this kind of compounds have been analyzed with the aim of explaining the general behavior of azadienes found experimentally. We show that, although several conformers of the reacting molecule are populated on the ground-state at room temperature, there is only one capable of successfully yield the products. It is shown that photocyclization takes place with fast relaxation in both S₂ and S₁ excited states, in agreement with the experimental lack of fluorescence. This fact, together with the presence of reaction paths that allow effective recovery of the starting molecule, explains not only the experimental photocyclization of azadienes under UV radiation, but also accounts for the low efficiency of the process. The mechanistic information obtained allows to provide an explanation of the found reaction outcome and to suggest some modifications to improve the synthetic utility of these reactions.     

Effect of the choice of the pressure coupling method on the spontaneous aggregation of DPPC molecules

The self-assembly of DPPC molecules starting from a random, solution-like configuration in the presence of water molecules is described in the present MD simulation study. Simulations were performed with either anisotropic or isotropic pressure coupling. Use of anisotropic pressure coupling led to the formation of a bilayer/bilayerlike aggregate; the features of the bilayer are in agreement with those reported from earlier simulation and experimental studies. In contrast, simulating the same system with isotropic pressure coupling led to the formation of a cylindrical micelle/lamellar structure with a large water hole. The formation of micelles seems unrealistic since diacylphosphatidylcholines having hydrocarbon tails with nine or more carbon atoms have been shown to form only bilayers. Simulations were also performed with preformed bilayerlike configurations with either anisotropic or isotropic pressure coupling. The bilayer characteristics deduced from simulations using anisotropic pressure coupling are in better agreement with those reported from earlier experimental and simulation studies. Thus, the choice of the pressure coupling method has a significant effect on the spontaneous aggregation of DPPC molecules but makes relatively lesser effect if the bilayer has formed already.     

Koopmans-like approximation in the Kohn-Sham method and the impact of the frozen core approximation on the computation of the reactivity parameters of the density functional theory

A Koopmans-like approximation is introduced in the spin-polarized version of the Kohn-Sham (KS) density functional theory to obtain a relation between KS orbital energies and vertical ionization potential and electron affinity. Expressions for reactivity indexes (like electronegativity, hardness, electrophilicity, and excitation energies) include KS frontier orbital energies and additional contributions associated with the self-interaction correction. Those reactivity parameters were computed with different exchange-correlation functionals to test the approach for a set of small molecules. The results show that the present approximation provides a better way to estimate hardness, electronegativity, and electrophilicity than just the use of frontier orbital energy values. However KS HOMO and LUMO energy gap gives a better agreement with excitation energies.     

Influence of the polarity of the microenvironment of pyrene on the intensity of its solid-phase luminescence

The sorption of pyrene by a filter paper modified with lead acetate is studied by luminescence methods. Based on changes in the vibrational structure of fluorescence spectra of pyrene, it was found that the polarity of the microenvironment of pyrene adsorbed from solutions in ethanol increases with the concentration of acetic or hydrochloric acid in these solutions. It was revealed that, when an acid is added, pyrene fluoresces and phosphoresces more intensely at room temperature. It is shown that this is associated with a more efficient sorption of pyrene by the filter paper from acid solutions in ethanol.     

FTIR study of the mode of binding of the reactants on the Pd nanoparticle surface during the catalysis of the Suzuki reaction

In the Suzuki reaction between phenylboronic acid and iodobenzene catalyzed by palladium nanoparticles, our previous studies suggested that the phenylboronic acid adsorbs on the nanoparticle surface and then interacts with the iodobenzene that is present in solution. In the present study, FTIR is used to examine the change in the vibrational frequencies of phenylboronic acid in films with and without the addition of palladium nanoparticles. The large change in the B-O stretching frequency of phenylboronic acid from 1348 to 1376 cm(-1) in the presence of sodium acetate and palladium nanoparticles strongly suggests that the mode of binding of phenylboronic acid to the Pd nanoparticle surface involves a B-O-Pd type of bonding. Shifts in the B-C stretching mode and the out-of-plane phenyl C-C ring deformation bands associated with phenylboronic acid provide additional confirmations of the binding process. It is also shown that the phenylboronic acid needs to be in the deprotonated form in the presence of sodium acetate (phenylboronate anion) to bind to the palladium nanoparticle surface. No changes in the characteristic bands of iodobenzene were observed in films made in the presence of the palladium nanoparticles. The FTIR studies provide proof of the mode of binding that occurs in the nanoparticle surface for the first time and also confirms the mechanism of the Suzuki reaction that we proposed previously.     

Determination of hydroxyproline in tissues and the evaluation of the collagen content of the tissues

The concentrations of hydroxyproline (an amino acid specific of collagen) in a number of connective tissues were determined. Two procedures were compared. In one of them, amino acids were preseparated by chromatography and then determined on a standard amino acid analyzer. In the other procedure, hydroxyproline was selectively oxidized without amino acid separation and determined by a spectrophotometric reaction with Ehrlich’s reagent. Data obtained for purified collagen preparations in accordance with the two procedures were consistent with each other. The results can be somewhat different in unpurified preparations and tissues because of the presence of polysaccharide components in the tissues.     

Molecular simulation study of the effect of pressure on the vapor-liquid interface of the square-well fluid

We examine a model system to study the effect of pressure on the surface tension of a vapor-liquid interface. The system is a two-component mixture of spheres interacting with the square-well (A-A) and hard-sphere (B-B) potentials and with unlike (A-B) interactions ranging (for different cases) from hard sphere to strongly attractive square well. The bulk-phase and interfacial properties are measured by molecular dynamics simulation for coexisting vapor-liquid phases for various mixture compositions, pressures, and temperatures. The variation of the surface tension with pressure compares well to values given by surface-excess formulas derived from thermodynamic considerations. We find that surface tension increases with pressure only for the case of an inert solute (hard-sphere A-B interactions) and that the presence of A-B attractions strongly promotes a decrease of surface tension with pressure. An examination of density and composition profiles is made to explain these effects in terms of surface-adsorption arguments.     

Re-examination of the Kinetics of the Thermal Dehydroxylation of Goethite

The kinetics of thermal dehydroxylation of aluminuous goethites [1] synthesised from a ferrous salt has been re-examined using the general reaction order kinetic law. The utilised data processing was based on the procedures employed by dissolution kinetics. Recalculation of the activation energies E_A of the dehydroxylation yielded the values 130, 132, 128, and 123 kJ mol⁻¹ for pure goethite, goethite with 10, 20, and 30 mol% Al substitution, respectively. The values of E_A are in a good agreement with those given for goethite in literature. The E_A values are linearly related with the chemically bound excess H₂O/OH⁻ in the crystal lattice that is apparently influenced by Al substitution. This revised version was published online in August 2006 with corrections to the Cover Date.     

The influence of the structure of the surface of functional organosilicas on the adsorption of cholic acid

High-dispersity silica was modified by functional groups capable of protonating or carrying a constant positive charge. IR and UV spectroscopy, temperature-programmed thermogravimetry, pH metry, and quantitative analysis of grafted compounds were used to determine the structure of the surface of functional organosilicas. The adsorption of primary bile (cholic) acid on silica adsorbents and cholestiramine was studied. The adsorption of cholic acid from solutions with pH 2–8 was substantially higher on adsorbents with positively charged surfaces. The silica adsorbents synthesized were shown to have higher cholic acid adsorption parameters compared with adsorbents used in medicine.