EPR evidence for a single electron transfer mechanism in reactions of aromatic ketones with lithium amides

Direct spectroscopic evidence (EPR) supporting a single electron transfer mechanism in the reaction of lithium amides with aromatic ketones is presented.     

One-pot regioselective synthesis of dihydronaphthofurans and dibenzofurans

A regioselective approach for the synthesis of substituted naphthofurans and dibenzofurans has been demonstrated through a ring transformation reaction of suitably functionalized 2H-pyran-2-ones by reaction with 6,7-dihydro-5H-benzofuran-4-one and 7-methoxybenzofuran-3-one, respectively, in high yields. The novelty of the procedure lies in the creation of an aromatic ring transformed by 2H-pyran-2-one involving the -COCH₂- moiety of a cyclic ketone.     

IR and thermal studies on a new oxomolybdenum(VI) oxalato complex

A new molybdenum(VI) oxalato complex K₄(NH₄)₁₀[Mo₁₄O₄₂(C₂O₄)₇] (PAMO) was prepared and characterized by chemical analysis, IR spectral and X-ray studies. Its thermal decomposition was studied using TG, DTA and DTG techniques. The compound is anhydrous and decomposes between 235° and 335°C in three steps. The first and the second steps occur in the temperature ranges 235°–290°C and 290–310°C to give the intermediate compounds having the tentative compositions K₄(NH₄)₈[Mo₁₄O₄₂(C₂O₄)₆] and K₂(NH₄)₂[Mo₁₄O₄₂(C₂O₄)₃], respectively, the later than decomposing to give a mixture of potassium tetramolybdate and molybdenum trioxide at 335°C. DTA also shows a peak at 530°C which corresponds to the melting of potassium tetramolybdate. An examination of the products obtained at 340° and 535°C by chemical analysis, IR spectra and X-ray studies reveals them to be identical.The authors are grateful to Dr. M. C. Jain, Head of the Department of Chemistry, for providing research facilities.     

Metal derivatives of amidoximes I. Mono-, bis- and tris-(trimethylsilyl)amidoximes

The preparation and properties of mono-, bis- and tris-(trimethylsilyl)amidoximes are described.     

Fluoroaryl-substituted ketiminate complexes of aluminum

The ketiminate complex AlCl[OC(Me)CHC(Me)N(p-C₆H₄F)]₂ (4) has been prepared from the β-aminoenone, OC(Me)CHC(Me)N(H)(p-C₆H₄F) (3) by lithiation of 3 with n-BuLi, followed by reaction with AlCl₃ and by the reaction of 3 with Me₂AlCl. A second compound, [AlCl₂{OC(Me)CHC(Me)N(H)(p-C₆H₄F)}₄][AlCl₄] (5), was also isolated from the AlCl₃ reaction. The structures of 4 and 5 were determined by X-ray diffraction analysis.     

Effect of lithium chloride on the palisade layer of the Triton-X-100 micelle: two sites for lithium ions as revealed by solvation and rotational dynamics studies

Dynamic Stokes' shift measurements using coumarin 153 as the fluorescence probe have been carried out to explore the effect of added electrolyte, lithium chloride (LiCl), on solvation dynamics in the Triton-X-100 (TX-100) micelle and thus to understand the changes in micellar Palisade layer, especially the entrapped water structures in the Palisade layer. At all concentrations of LiCl, the spectral shift correlation function shows biexponential decay. At lower LiCl concentrations, the longer solvation time is seen to decrease, although the shorter solvation time is not affected much. At higher LiCl concentrations, both longer and shorter solvation times increase with electrolyte concentration. The present observations have been rationalized assuming two possible modes of interaction of the Li+ ions in the micellar palisade layer. For LiCl concentrations below about 1.5 M, the Li+ ions appear to bind preferably to the ether groups of surfactant molecules, and the increased micellar hydration with the added salt effectively makes the solvation dynamics faster. At higher LiCl concentrations, available ether binding sites for the Li+ ions seem to get occupied effectively and the excess Li+ ions start remaining in the Palisade layer as strongly hydrated free ions. Because of strong hydration of the Li+ ions, the mobility of the entrapped water molecules in the micellar Palisade layer decreases significantly, causing the solvation dynamics to slow at higher LiCl concentrations. The fluorescence anisotropy results in the present systems are also in support of the above inferences drawn from solvation dynamics results. The present results with LiCl salt are found to be substantially different than those obtained in our earlier study (Kumbhakar et al. J. Phys. Chem. B 2005, 109, 14168) with salts such as NaCl, KCl, and CsCl. These differences are attributed mainly to the binding of the Li+ ions with the surfactant ether groups, which seems to be unlikely for the other alkali cations.     

Odd-even variations in the wettability of n-alkanethiolate monolayers on gold by water and hexadecane: a molecular dynamics simulation study

Molecular dynamics (MD) simulations were performed to investigate odd-even chain length dependencies in the wetting properties of self-assembled monolayers (SAMs) of n-alkanethiols [CH3(CH2)n-1SH] on gold by water and hexadecane. Experimentally, the contact angle of hexadecane on the SAMs depends on whether n is odd or even, while contact angles for water show no odd-even dependence. Our MD simulations of this system included a microscopic droplet of either 256 water molecules or 60 hexadecane molecules localized on an n-alkanethiolate SAM on gold with either an even or odd chain length. Contact angles calculated for these nanoscopic droplets were consistent with experimentally observed macroscopic trends in wettability, namely, that hexadecane is sensitive to structural differences between odd- and even-chained SAMs while water is not. Structural properties for the SAMs (including features such as chain tilt, chain twist, and terminal methyl group tilt) were calculated during the MD simulations and used to generate IR spectra of these films that compared favorably with experimental spectra. MD simulations of SAMs in contact with slabs of water and hexadecane revealed that the effects of these solvents on the structure of the SAM was restricted to the chain terminus and had no effect on the inner structure of the SAM. The density profiles for water and hexadecane on the SAMs were different in that water displayed a significant depletion in its density at the liquid/SAM interface from its bulk value, while no such depletion occurred for hexadecane. This difference in contact may explain the lack of an odd-even variation in the wetting characteristics of water on these surfaces, because the water molecules are positioned further away from the surface and, therefore, are not sensitive to the structural differences in the average orientations for the terminal methyl groups in odd- and even-chained SAMs. In contrast, the differences in the wetting properties of hexadecane on the odd- and even-chained SAMs may reflect the closer proximity of these molecules to the SAM surface and a resulting greater sensitivity to the differences in the terminal methyl group orientations in the SAMs. SAM-solvent interaction energies were calculated during the MD simulations, yielding interaction energies that differed on the even- and odd-chained surfaces by approximately 10% for hexadecane and negligibly for water, in accord with estimates using experimental wetting results.     

Design of peptides with α,β-dehydro-residues: Synthesis and crystal structure of a tetrapeptide Boc-Ala-ΔPhe-ΔPhe-Phe-OCH<Subscript>3</Subscript>

In order to develop general rules of peptide design with α,β-dehydro-residues, a peptide, Boc-Ala-ΔPhe-ΔPhe-Phe-OCH₃, was synthesized. The peptide was crystallized from its solution in an acetone:water mixture (70:30). The crystals belong to orthorhombic space group P2₁2₁2₁ with a = 9.403(1) Å, b = 16.871(1) Å, c = 21.638(1) Å, and Z = 4. The peptide adopts a conformation with two overlapping types II′ and III β-turns having dihedral angles, φ₁ = 53.7(6)^°, ψ₁ = ?135.9(4)^°, φ₂ = ?59.2(5)^°, ψ₂ = ?17.9(5)^°, φ₃ = ?68.4(5)^°, ψ₃ = ?18.8(6)^°. The conformation was further characterized by two intramolecular 4 → 1 hydrogen bonds involving imino nitrogen atoms of ΔPhe³ and Phe⁴ as donors and carbonyl oxygen atoms of blocking group Boc and Ala¹ as acceptors. The packing of the molecules in the unit cell is stabilized by an intermolecular hydrogen bond, N₂–H₂?s O′₃ [?x, y+1/2, ?z+1/2] = 2.894 Å and van der Waals forces involving aromatic side chains.     

XPS study of glassy Pd80Ge20

An X-ray photoemission and Auger electron spectroscopy study of the electronic structure of Pd₈₀Ge₂₀ alloy in its glassy and crystalline states is reported. The glassy state shows some modifications in the valence band structure, symmetry of the Pd $\text{3}\text{d}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}\text{?3}\text{d}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ spin-orbit doublet and a shift in M₄₅-V-V Auger transition of Pd. Analysis of the chemical shifts in the core-level binding energies of the constituents indicates negligible charge transfer from the metalloid atom (Ge) to d-band of the Pd.     

Bispidine as a β-strand nucleator: from a β-arch to self-assembled cages and vesicles

The development of synthetic scaffolds that nucleate well-folded secondary structures is highly challenging. Herein, we designed and synthesized a series of core-modified peptides (F1, F2, F3, and F4) that fold into β-strand structures. These bispidine-scaffolded peptides were studied by CD, IR, NMR, single crystal XRD, and Molecular Dynamics (MD) simulations to investigate their conformational preferences. Solid-state and solution studies revealed that bispidine is a versatile scaffold that could be placed either at the terminal or at the middle of the peptide strand for nucleating the β-strand structure. Scaffolds that nucleate an isolated β-strand conformation are rare. Bispidine placed at the C-terminus of the peptide chain could nucleate a β-strand conformation, while bispidine placed at the middle resulted in a β-arch conformation. This nucleation activity stems from the ability to restrict the psi torsion angle (ψ) through intramolecular C5 hydrogen bonding between the equatorial hydrogen(s) of bispidine and the carbonyl oxygen(s) of the amino acid close to the scaffold. Furthermore, the bispidine peptidomimetic with a super secondary structure, namely β-arch, assembled into single-hole submicron cages and spherical vesicles as evident from microscopic studies. The design logic defined here will be a significant strategy for the development of β-strand mimetics and super secondary structures.

Bispidine is a versatile scaffold that could be placed either at the terminal or at the middle of the peptide strand for nucleating β-strand structures. These β-strand mimetics self-assemble to single hole submicron cages and vesicles.