Nongenetic reprogramming of a fungal highly reducing polyketide synthase

The biosynthesis of the fungal metabolite tenellin from Beauveria bassiana CBS110.25 was investigated in the presence of the epigenetic modifiers 5-azacytidine and suberoyl bis-hydroxamic acid and under conditions where individual genes from the tenellin biosynthetic gene cluster were silenced. Numerous new compounds were synthesized, indicating that the normal predominant biosynthesis of tenellin is just one outcome out of a diverse array of possible products. The structures of the products reveal key clues about the programming selectivities of the tenellin polyketide synthase.     

A local-MP2 approach to the ab initio study of electron correlation in crystals and to the simulation of vibrational spectra: the case of Ice XI

Wave-function-based computational techniques for describing electron correlation effects in periodic systems have a long history. Among early attempts, the method proposed by Colle and Salvetti (Theor Chim Acta 37:329, 1975) more than 30 years ago is noteworthy for its simplicity, power, and far-reaching consequences. The renewed interest in this topic is due to the well-known failure of techniques based on Density Functional Theory when it comes to obtaining very accurate estimates of some important quantities. Here we present the essential features of an ab initio code, ( CRYSCOR ) recently implemented (Phys Rev B 76: 075101, 075102, 2007), which solves the MP2 equations for crystals by adopting a local-correlation approach and using as a reference the Hartree-Fock solution provided by the CRYSTAL program. As an example of application, we discuss the MP2 corrections to the frequency of some vibrational modes in a proton-ordered structure of water ice (Ice XI).     

Periodic local MP2 method for the study of electronic correlation in crystals: Theory and preliminary applications

A computational technique for solving the MP2 equations for periodic systems using a local-correlation approach and implemented in the CRYSCOR code is presented. The Hartree-Fock solution provided by the CRYSTAL program is used as a reference. The motivations for the implementation of the new code are discussed, and the techniques adopted are briefly recalled. With respect to the original formulation (Pisani et al., J Chem Phys 2005, 122, 094113), many new features have been introduced in CRYSCOR to improve its efficiency and robustness. In particular, an adaptation of the density fitting scheme to translationally periodic systems is described, based on Fourier transformation techniques. Three examples of application are provided, concerning the CO(2) crystal, proton transfer in ice XI, and the adsorption of methane on MgO (001). The results obtained with the periodic LMP2 method for these systems appear more reliable than the ones obtained using density functional theory.     

Periodic ab initio estimates of the dispersive interaction between molecular nitrogen and a monolayer of hexagonal BN

The ab initio determination of the leading long-range term of pairwise additive dispersive interactions, based on the independent analysis of the response properties of the interacting objects, is here considered in the case where these are part of a periodic system. The interaction of a nitrogen molecule with a thin film of hexagonal BN has been chosen as a case study for identifying some of the problems involved, and for proposing techniques for their solution. In order to validate the results so obtained, the interaction energy between N(2) and a BN monolayer at different distances has been estimated following a totally different approach, namely by performing post-Hartree-Fock (MP2) supercell calculations using the Crystal+Cryscor suite of programs. The results obtained with the two approaches closely agree over a long range, while the limit of validity of the purely dispersive regime can be clearly assessed.