The Synthesis and Reactions of Yomogi Alcohol. Conversion of the artemisyl skeleton to the santolinyl skeleton by a 1,2-shift of a vinyl group. Synthesis of santolinatriene

The synthesis of yomogi alcohol (2, 5, 5-trimethylhepta-3,6-dien-2-ol, 2 ) is described, and experiments directed towards its allylic rearrangement to artemisia alcohol detervatives have been carried out. Acidic reagents open the ring of yomogi alcohol epoxide ( 16 ) at with participation of the 6,7-double-bond, a shift of the vinyl group results to yield a compound with the santolinyl skeleton. The same reagents are without effect when this double bond reduced. Action of butyllithium of the benzaldehyde acetal ( 41 ) of 2, 5-dimethyl-4-vinyl-2, dihydroxy-hex-5-ene ( 28 ), obtained by acid-catalyzed ring opening of yomogi alcohol epoxide in the presence of benzaldehyde, leads to santolinatriene ( 42 ). This vinyl shift is not observed in the case of O-acetyl yomogi alcohol epoxide ( 46 ), from white a compound believed to be an oxetan 48 (R ? COCH₃) is formed with concomitent shift of the acetate group. Further unusual reactions of the oxetan are described, and some observation about the epoxidation of sterically hindered allyl alcohols and their acetates are made.     

On the asymptotic behavior of dynamical maps for a finite quantum system

We give some remarks on the dynamical evolution (also nonlinear) of finite quantum system. We are interested int-asymptotic behavior of density matrices in the Liouville space formalism and we show that for nonlinear dynamical semigroups, as well as for the dynamical maps that do not form semigroups, the stationary time evolution may be attained for finite time in contrast to the motion generated by the linear dynamical semigroup. Recently the problem of constructing a nonlinear analog of quantum mechanics with nonlinear wave equation playing the role of the Schrödinger equation has been investigated by some authors; see for example Mielnik (1974), Bergmann (1968). Our work is related to this investigation and gives a characteristic feature of the nonlinear time evolution.     

Thermodynamic quantities for the interaction of SO 4 2− with H+ and Na+ in aqueous solution from 150 to 320°C

The aqueous reactions,

Characteristic of the Ag(bipy) 2 2+ /Ag(bipy) 2 + and Ag(phen) 2 2+ /Ag(phen) 2 + systems in acetonitrile

The values of standard potentials of redox systems formed by the complexes of Ag(II) and Ag(I) with 2,2-bipyridine and 1,10-phenanthroline in acetonitrile have been determined. The properties of the above systems in water and acetonitrile are compared. The possibility of application of these systems for the construction of electrodes with a constant potential in different solvents is discussed.

---

Charakteristik der Systeme Ag(bipy) ₂ ²⁺ /Ag(bipy) ₂ ⁺ und Ag(phen) ₂ ²⁺ /Ag(phen) ₂ ⁺ in Acetonitril

Zusammenfassung Die Standardpotentialwerte der Redoxsysteme, die durch Komplexbildung von Ag(II)- und Ag(I)-Ionen mit 2,2-Bipyridin und 1,10-Phenantrolin gebildet werden, wurden in Acetonitril bestimmt. Die Eigenschaften dieser Redoxsysteme in Wasser und Acetonitril wurden verglichen.Es wurde weiterhin die Möglichkeit der Anwendung dieser Systeme zur Konstruktion einer Elektrode mit unveränderbarem Potential in verschiedenen Lösungsmitteln diskutiert.

     

Monomer basis-set truncation effects in calculations of interaction energies: A model study

Supermolecular interaction energies are analyzed in terms of the symmetry-adapted perturbation theory and operators defining the inaccuracy of the monomer wave functions. The basis set truncation effects are shown to be of first order in the monomer inaccuracy operators. On the contrary, the usual counterpoise correction schemes are of second order in these operators. Recognition of this difference is used to suggest an approach to corrections for basis-set truncation effects. Also earlier claims--that dimer-centered basis sets may lead to interaction energies free of basis-set superposition effects--are shown to be misleading. According to the present study the basis-set truncation contributions, evaluated by means of the symmetry-adapted perturbation theory with monomer-centered basis sets, provide physically and mathematically justified corrections to supermolecular results for interaction energies.     

Single-site mutation and secondary structure stability: an isodesmic reaction approach. The case of unnatural amino acid mutagenesis Ala-->Lac

A method is described to evaluate backbone interactions in proteins via computational unnatural amino acid mutagenesis. Several N-acetyl polyalanyl amides (AcA(n)NH(2)) were optimized in the representative helical (3(10)-, 4(13)-, and a "hybrid" kappa-helix, n = 7, 9, 10, 14) and hairpin (two- and three-stranded antiparallel beta-sheets with type I turns betaalphaalphaepsilon, n = 6, 9, 10) conformations, and extended conformers of N-acetyl polyalanyl methylamides (n = 2, 3) were used to derive multistranded beta-sheet fragments. Subsequently, each residue of every model structure was substituted, one at a time, with l-lactic acid. The resulting mutant structures were again optimized, and group-transfer energies DeltaE(GT) were obtained as heats of the isodesmic reactions: AcA(n)NHR + AcOMe --> AcA(x)LacA(y)NHR + AcNHMe (R = H, CH(3)). These group-transfer energies correlate with the degree of charge polarization of the substituted peptide linkages as measured by the difference Deltae in H and O Mulliken populations in HN-C=O and with the H-bond distances in the "wild-type" structures. A good correlation obtains for the HF/3-21G and B3LYP/6-31G* group-transfer energies. The destabilization effects are interpreted in terms of loss of interstrand and intrastrand H-bonds, decrease in Lewis basicity of the C=O group, and O...O repulsion. On the basis of several comparisons of Ala --> Lac DeltaE(GT)'s with heats of the NH --> CH(2) substitutions, the latter contribution is estimated (B3LYP/6-31G*) to range between 1.5 and 2.4 kcal mol(-1), a figure close to the recent experimental DeltaDeltaG(o) value of 2.6 kcal mol(-1) (McComas, C. C.; Crowley, B. M.; Boger, D. L. J. Am.Chem. Soc. 2003, 125, 9314). The partitioning yields the following maximum values of the electronic association energy of H-bonds in the examined sample of model structures (B3LYP/6-31G* estimates): 3(10)-helix D(e) = -1.7 kcal mol(-1), alpha-helix D(e) = -3.8 kcal mol(-1), beta-sheet D(e) = -6.1 kcal mol(-1). The premise of experimental evaluations of the backbone-backbone H-bonding that Ala --> Lac substitution in proteins is isosteric (e.g., Koh, J. T.; Cornish, V. W.; Schultz, P. G. Biochemistry 1997, 36, 11314) is often but not always corroborated. Examination of the integrity of H-bonding pattern and phi(i), psi(i) distribution identified several mutants with significant distortions of the "wild-type" structure resulting inter alia from the transitions between i, i + 3 and i, i + 4 H-bonding in helices, observed previously in the crystallographic studies of depsipeptides (Ohyama, T.; Oku, H.; Hiroki, A.; Maekawa, Y.; Yoshida, M.; Katakai, R. Biopolymers 2000, 54, 375; Karle, I. L.; Das, C.; Balaram, P. Biopolymers 2001, 59, 276). Thus, the isodesmic reaction approach provides a simple way to gauge how conformation of the polypeptide chain and dimensions of the H-bonding network affect the strength of backbone-backbone C=O...HN bonds. The results indicate that the stabilization provided by such interactions increases on going from 3(10)-helix to alpha-helix to beta-sheet.     

Interactions of porphyrin covalently attached to poly(methacrylic acid) with liposomal membranes

The interactions between the 5-(4-acryloyloxyphenyl)-10,15,20-tritolylporphyrin covalently attached to poly(methacrylic acid) chain (PMA-Po) and phosphatidylcholine liposomes in aqueous solution at different pH values were studied. The binding constants (K(b)) for the liposome- PMA-Po in solutions in the pH range from 6.5 to 9.2 were determined using fluorescence spectroscopy. The binding was found to be efficient. The acid-base properties of the porphyrin chromophores were also studied. Both pK values associated with imine-N protonation of the porphyrin core were found to be 6.4. The quantum yield (Phi(Delta)) of singlet oxygen production by Po in the lipid-PMA-Po system was found to be high (0.88 +/- 0.05).     

Crystal chemistry of protonated 1,2-bis(di-R-aminomethyl)benzenes. Part V. [1,2-bis(diethylaminomethyl)-3,6-dichlorobenzene:1,2-bis(diethylaminomethyl)-3,4,6-trichlorobenzene]perchlorate mixed crystals

The mixed crystals of 1,2-bis(diethylaminomethyl)-3,6-di- and 3,4,6-trichloro-benzene perchlorate at 0.5:0.5 ratio have been studied using X-ray diffraction and FT-IR spectroscopy. The molecules of di- and tri-chloro derivatives are distributed randomly in the crystal lattice; however, this disorder manifested mainly by a partial occupation of the chlorine atom at C(4) and by relatively big atomic temperature parameters even at 99 K, particularly for the oxygens of the perchlorate anion. The proton in the [NHN]⁺ bond refined close to the equidistant position between the nitrogens. The conformations of the diethylaminomethyl substituents are pseudo-symmetrical relative to the plane and twofold axis passing through the midpoint of the hydrogen bond. The IR spectrum of the crystals shows a broad intense band and an intense continuous absorption indicating relatively high proton polarizability in the intramolecular hydrogen bond. In acetonitrile and in chloroform, the proton in the intramolecular hydrogen bond also shows a very high proton polarizability demonstrated by the continuous absorption in the IR spectrum.