Ab initio molecular orbital calculations of the cobalt porphine complex. I. LCAO SCF MO calculation of low-spin,high-spin,and π-ionized states of Co-porphine

Ab initio LCAO SCF MO calculations are carried out on planar Co-porphine with a basis set of roughly double zeta quality for Co and N and of single zeta quality for C and H. The net charge on Co and N and the overlap population between them are 1.78, ?0.57, and 0.06, respectively, in the ²A_1g, state, which is known to be the ground state by experiment. The bonding in this complex is thus largely ionic. The first and second calculated ionization potentials are 6.51 and 6.77 eV, respectively, and are in reasonable agreement with the observed ionization potentials of 6.44 and 6.62 eV for Ni-tetraphenylporphine. CI calculations within the framework of the ligand field theory are also performed. The calculated order of the five lowest states is ⁴B_2g ≈ ⁴E_g, ⁴A_2g, ²A_1g, ⁴E_g from below and is not in agreement with the semiempirical order of ²A_1g ≈ ⁴B_2G, ⁴A_2g, ²E_g, ⁴E_g determined by Lin.     

A Novel Synthesis of 1-Isochromanols via Hetero Diels-Alder Reaction of Carbonyl Compounds with 1-Trimethylsilyloxy-benzocyclobutene as a Precursor of α-Oxy-o-Quinodimethane Under Mild Condition

Reaction of 1-trimethylsilyloxybenzocyclobutene(1) with carbonyl compounds catalyzed by tris(dimethylamino)sulfur (trimethylsilyl)difluoride (TASF) at room temperature gave 1-isochromanol derivatives as corresponding hetero Diels-Alder adducts in good yields.     

A smooth‐particle mesh Ewald method for DL_POLY molecular dynamics simulation package on the Fujitsu VPP700

An N⋅ log (N) smooth‐particle mesh Ewald method has been incorporated into the DL_POLY molecular dynamics simulation package. The performance of the new code has been tested on a Fujitsu VPP700 for several DL_POLY‐specific benchmark systems. The new method is highly vectorizable, and makes use of the extremely efficient Fast Fourier Transforms on the Fujitsu vector machine. In calculations of the coulombic forces in periodic systems requiring large reciprocal space vectors, the new code was found to be considerably faster than the conventional Ewald method. © 2000 John Wiley & Sons, Inc. J Comput Chem 21: 1187–1191, 2000     

Semiempirical calculation of electronic spectra of organic compounds by using the improved method of new-γ electron repulsion integral. Part 2. Polycyclic aromatic hydrocarbons (PAHs)

Excitation energies of 123 polycyclic aromatic hydrocarbons were calculated by incorporating the improved method of new-γ for the two-center electron repulsion integral into two semiempirical molecular orbital methods (CNDO/S and INDO/S). This variable method well reproduced experimental excitation energies of them. The average error of the improvement is about 0.162 (CNDO/S) or 0.237 eV (INDO/S) though the average error without the improvement is about 0.541 (CNDO/S) or 0.536 eV (INDO/S). The improvement was useful for the calculations of other organic compounds including hetero atoms, such as organic dye.     

Samarium(II) iodide mediated radical/polar crossover reactions of cyclobutenes. An efficient approach to the BCD ring system of the penitrems

[reaction: see text] Radical/polar crossover reactions of derivatives of 1-(2-cyclobutenyl)-2-(2-iodoaryl)ethanones with acetone promoted by samarium diiodide and HMPA provide 1-(1-hydroxy-1-methylethyl)-2,2a,4,8b-tetrahydro-1H-cyclobuta[a]naphthalen-3-one derivatives in about 50% isolated yield. This reaction shows promise for construction of the BCD ring fragment of the penitrems.     

Dipeptide-induced chirality organization

This review describes an outline of dipeptide-induced chirality organization by using molecular scaffolds. A variety of ferrocene-dipeptide conjugates as bioorganometallics are designed to induce chirality-organized structures of peptides. The ferrocene serves as a reliable organometallic scaffold with a central reverse-turn unit for the construction of protein secondary structures via intramolecular hydrogen bondings, wherein the attached dipeptide strands are constrained within the appropriate dimensions. Another interesting feature of ferrocene-dipeptide conjugates is their strong tendency to self-assemble through contribution of available hydrogen bonding sites for helical architectures in solid states. Symmetrical introduction of two dipeptide chains into a urea molecular scaffold is performed to induce the formation of the chiral hydrogen-bonded duplex, wherein each hydrogen-bonded duplex is connected by continuous intermolecular hydrogen bonds to form a double helix-like arrangement.     

trans-2,2'-Bi(1-phenyladamantylidene): the most twisted biadamantylidene

The Grignard coupling of 2,2-dibromo-1-phenyladamantane gave trans-2,2'-bi(1-phenyladamantylidene) (1-Ph). Single-crystal X-ray analysis indicated that 1-Ph has a 23.2 degrees twisted double bond, which is much more distorted than that of parent 2,2'-biadamantylidene (1-H) and that of the ethyl-substituted derivative (1-Et). A cyclic voltammogram showed a reversible electron oxidation wave at 0.87 V vs Fc/Fc(+), which is 0.19 V lower than 1-H, indicating a significant increase in the HOMO energy level due to the distortion. The reaction of 1-Ph with 0.9 equiv of bromine gave an intramolecular Friedel-Crafts alkylation product, while bromination of 1-H and 1-Me has been reported to give a bridged bromonium ion and a rearranged product, 2-(1-methyl-2-adamantylidene)-4-bromotricyclo[5,3,1,0(3.9)]undec-4-ene, respectively.     

Synthesis,properties, and gas permeability of novel poly(diarylacetylene) derivatives

Poly(diphenylacetylene)s having various silyl groups are soluble in common solvents, from whose membranes poly(diphenylacetylene) membranes can be obtained by desilylation. The oxygen permeability coefficients of the desilylated polymers are quite different from one another (120–3300 barrers) irrespective of the same polymer structure. When bulkier silyl groups are removed, the oxygen permeability increases to larger extents. Poly[1-aryl-2-p-(trimethylsilyl)phenylacetylene]s are soluble in common solvents, and afford free-standing membranes. These Si-containing polymer membranes are desilylated to give the membranes of poly[1-aryl-2-phenylacetylene]s. Both of the starting and desilylated polymers show very high thermal stability and high gas permeability. 1-Phenyl-2-p-(t-butyldimethylsiloxy)phenylacetylene polymerizes into a high-molecular-weight polymer. This polymer is soluble in common organic solvents to provide a free-standing membrane. Desilylation of this membrane yields a poly(diphenylacetylene) having free hydroxyl groups, which is the first example of a highly polar group-carrying poly(diphenylacetylene). The P/P and P/P permselectivity ratios of poly(1-phenyl-2-p-hydroxylphenylacetylene) membrane are as large as 47.8 and 45.8, respectively, while keeping relatively high P of 110 barrers. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5028–5038, 2006     

Discrimination of hairpin polyamides with an alpha-substituted-gamma-aminobutyric acid as a 5'-TG-3' reader in DNA minor groove

Pyrrole-imidazole (Py-Im) polyamides containing stereospecifically alpha-amino- or alpha-hydroxyl-substituted gamma-aminobutyric acid as a 5'-TG-3' recognition element were synthesized by machine-assisted Fmoc solid-phase synthesis. Their binding properties to predetermined DNA sequences containing a core binding site of 5'-TGCNCA-3'/3'-ACGN'GT-5' (N.N' = A.T, T.A, G.C, and C.G) were then systematically studied by surface plasmon resonance (SPR). SPR results revealed that the pairing of stereospecifically alpha-amino-/alpha-hydroxyl-substituted gamma-aminobutyric acids, (R or S)-alpha,gamma-diaminobutyric acid (gammaRN or gammaSN) and (R or S)-alpha-hydroxyl-gamma-aminobutyric acid (gammaRO or gammaSO), side-by-side with beta-alanine (beta) in such polyamides significantly influenced the DNA binding affinity and recognition specificity of hairpin polyamides in the DNA minor groove compared with beta/beta, beta/gamma, and gamma/beta pairings. More importantly, the polyamide Ac-Im-gammaSO-ImPy-gamma-ImPybetaPy-beta-Dp (beta/gammaSO) favorably binds to a hairpin DNA containing a core binding site of 5'-TGCNCA-3'/3'-ACGN'GT-5' (N.N' = A.T) with dissociation equilibrium constant (K(D)) of 1.9 x 10(-)(7) M over N.N' = T.A with K(D) = 3.7 x 10(-)(6) M, with a 19-fold specificity. By contrast, Ac-Im-gammaSN-ImPy-gamma-ImPybetaPy-beta-Dp (beta/gammaSN) binds to the above sequence with N.N' = A.T with K(D) = 8.7 x 10(-)(7) M over N.N' = T.A with K(D) = 8.4 x 10(-)(6) M, with a 9.6-fold specificity. The results also show that the stereochemistry of the alpha-substituent, as well as the alpha-substituent itself may greatly alter binding affinity and recognition selectivity of hairpin polyamides to different DNA sequences. Further, we carried out molecular modeling studies on the binding by an energy minimization method, suggesting that alpha-hydroxyl is very close to N3 of the 3'-terminal G to induce the formation of hydrogen bonding between hydroxyl and N3 in the recognition event of the polyamide Ac-Im-gammaSO-ImPy-gamma-ImPybetaPy-beta-Dp (beta/gammaSO) to 5'-TGCNCA-3'/3'-ACGN'GT-5' (N.N' = A.T). Therefore, SPR assays and molecular modeling studies collectively suggest that the (S)-alpha-hydroxyl-gamma-aminobutyric acid (gammaSO) may act as a 5'-TG-3' recognition unit.