Superposition of quantum and classical rotational motions in Sc2C2@C84 fullerite.

The superposition of the quantum rotational motion (tunneling) of the encapsulated Sc(2)C(2) complex with the classical rotational motion of the surrounding C(84) molecule in a powder crystal of Sc(2)C(2)@C(84) fullerite is investigated by theory. Since the quantum rotor is dragged along by the C(84) molecule, any detection method which couples to the quantum rotor (in casu the C(2) bond of the Sc(2)C(2) complex) also probes the thermally excited classical motion (uniaxial rotational diffusion and stochastic meroaxial jumps) of the surrounding fullerene. The dynamic rotation-rotation response functions in frequency space are obtained as convolutions of quantum and classical dynamic correlation functions. The corresponding Raman scattering laws are derived, and the overall shape of the spectra and the width of the resonance lines are studied as functions of temperature. The results of the theory are confronted with experimental low-frequency Raman spectra on powder crystals of Sc(2)C(2)@C(84) [M. Krause et al., Phys. Rev. Lett. 93, 137403 (2004)]. The agreement of theory with experiment is very satisfactory in a broad temperature range.

Anisotropic packing and one-dimensional fluctuations of C60 molecules in carbon nanotubes.

The confinement of a C60 molecule encapsulated in a cylindrical nanotube depends on the tube radius. In small tubes with radius RT approximately < 7 A, a fivefold axis of the molecule coincides with the tube axis. The interaction between C60 molecules in the nanotube is then described by a O2-rotor model on a 1D liquid chain with coupling between orientational and displacive correlations. This coupling leads to chain contraction. The structure factor of the 1D liquid is derived. In tubes with a larger radius the molecular centers of mass are displaced off the tube axis. The distinction of two groups of peapods with on- and off-axis molecules suggests an explanation of the apparent splitting of Ag modes of C60 in nanotubes measured by resonant Raman scattering.

Superexchange and electron correlations in alkali fullerides AC60, A=K, Rb, Cs.

Superexchange interactions in alkali fullerides AC(60) are derived for C(60) molecular ions separated by interstitial alkali-metal ions. We use a multiconfiguration approach which comprises the lowest molecular orbital states of the C(60) molecule and the excited s and d states of the alkali-metal atom A. Interactions are described by the valence bond (Heitler-London) method for a complex (C(60)-A-C(60))(-) with two valence electrons. The electronic charge transfer between the alkali-metal atom and a neighboring C(60) molecule is not complete. The occupation probability of excited d and s states of the alkali atom is not negligible. In correspondence with the relative positions of the C(60) molecules and A atoms in the polymer crystal, we consider 180 degrees and 90 degrees (angle) superexchange pathways. For the former case the ground state is found to be a spin singlet separated from a triplet at approximately 20 K. For T<20 K there appear strong spin correlations for the 180 degrees superexchange pathway. The results are related to spin lattice relaxation experiments on CsC(60) in the polymerized and in the quenched cubic phase.

Theory of distinct crystal structures of polymerized fullerides AC60, A = K, Rb, Cs: the specific role of alkalis.

The polymer phases of AC60 form distinct crystal structures characterized by the mutual orientations of the (C( -)(60))(n) chains. We show that the direct electric quadrupole interaction between chains always favors the orthorhombic structure Pmnn with alternating chain orientations. However, the specific quadrupolar polarizability of the alkali metal ions leads to an indirect interchain coupling which favors the monoclinic structure I2/m with equal chain orientations. The competition between direct and indirect interactions explains the structural difference between KC60 and RbC60, CsC60.

Synthesis of new analogs of echinocandin B by enzymatic deacylation and chemical reacylation of the echinocandin B peptide: synthesis of the antifungal agent cilofungin (LY121019).

The antifungal antibiotic, echinocandin B (ECB), was modified by a sequential procedure in which the initial step involved enzymatic removal of the native N-linoleoyl group from the N-terminus using an Actinoplanes utahensis culture. The resulting product, ECB nucleus, was reacylated using active esters or acid halides of various substituted acids to give a series of ECB analogs. These analogs possessed anti-Candida activity both in vitro and in vivo (mice). Other studies have shown that one of these, cilofungin, the 4-n-octyloxybenzoyl-ECB analog (LY121019), has excellent anti-Candida activity, low toxicity and is superior to other available antifungal antibiotics.

Isolation and characterization of A41030, a complex of novel glycopeptide antibiotics. Application of the Michel-Miller high performance low pressure liquid chromatography system.

A new antibiotic complex, designated A41030, has been isolated from the fermentation broth of Streptomyces virginiae. Factors A, B, C, D, E, F and G were separated by an efficient preparative high performance low pressure liquid chromatography system. The apparatus offers economic reversed phase separations on glass columns. The A41030 factors are members of the general class of glycopeptide antibiotics and are active in vitro and in vivo vs. Gram-positive bacteria.

The discovery, fermentation, isolation, and structure of antibiotic A33853 and its tetraacetyl derivative.

The structure of antibiotic A33853, isolated from the culture broth of Streptomyces sp., NRRL 12068, is reported. The structure was deduced from an X-ray crystallographic study of its tetraacetyl derivative. Tetraacetyl A33853 is unique because it contains an anhydride moiety, an unexpected product from the reaction of A33853 with acetic anhydride and pyridine.

A35512, a complex of new antibacterial antibiotics produced by Streptomyces candidus. I. Isolation and characterization.

The new antibiotic complex A35512 produced by Streptomyces candidus was isolated from the filtered fermentation broth. The individual factors A, B, C, E, and H were separated and purified by column chromatography. A35512B, the major factor, was isolated as the dihydrochloride salt, a white crystalline compound with an approximate empirical formula of C90H101 N8O39Cl.2HCl. The A35512 antibiotics belong to the glycopeptide class of antibiotics and possess high in vitro and in vivo activity against Gram-positive bacteria.

The isolation and structure elucidation of macrocyclic lactone antibiotic, A26771B.

The isolation, biological properties and structure elucidation of a sixteen-membered macrocyclic lactone antibiotic, designated A26771B (1), obtained from Penicillium turbatum are discussed.

New azasteroidal antifungal antibiotics from Geotrichum flavo-brunneum. II. Isolation and characterization.

A novel group of antibiotics, comprising microbiologically-active structurally-related factors A25822A, B, D, H, L, M and N, produced by culturing Geotrichum flavo-brunneum NRRL 3862 under submerged aerobic fermentation conditions was isolated by extraction. The individual factors were separated and purified by chromatography and crystallization. The major factor, A25822B, a 15-aza-24-methylene-D-homocholestadiene is a white crystalline compound, C25H45NO. The antibiotics are highly active against fungi and marginally active against bacteria.