Hydrogen bonding and dimeric self-association of 2-pyrrolidinone: An ab initio study

Ab initio calculations on the different associated structures of 2-pyrrolidinone with water and with itself were carried out using 3-21G and 6-31G^* basis sets at the Hartree–Fock level, including electron correlation using second-order Møller–Plesset perturbation theory. The calculated free energy changes for the intermolecular hydrogen bonded dimer and hydrated species indicated that the molecular systems with cyclic dimerization and association with two water molecules are dominant. The results are compared to the available experimental data in the literature.     

Hydrogen bonding of 1-cyclohexyluracil with acetylglycine N-methylamide

I.r. spectroscopy was used to determine the enthalpy of hydrogen bond complex formation of 1-cyclohexyluracil with acetylglycine N-methylamide, in chloroform solution. Enthalpy of association is found to be −5.4 Kcal/mole for the dimer of acetylglycine _N-methylamide and −4.7 Kcal/mole for the mixed dimers of this dipeptide with 1-cyclohexyluracil. These thermodynamic parameters and the i.r. spectra of the solutions suggest that the structures of these dimers are cyclic.     

Self-assembly of 1-D organic semiconductor nanostructures

This review focuses on the molecular design and self-assembly of a new class of crowded aromatics that form 1-D nanostructures via hydrogen bonding and pi-pi interactions. These molecules have a permanent dipole moment that sums as the subunits self assemble into molecular stacks. The assembly of these molecular stacks can be directed with electric fields. Depending on the nature of the side-chains, molecules can obtain the face-on or edge-on orientation upon the deposition onto a surface via spin cast technique. Site-selective steady state fluorescence, time-resolved fluorescence, and various types of scanning probe microscopy measurements detail the intermolecular interactions that drive the aromatic molecules to self-assemble in solution to form well-ordered columnar stacks. These nanostructures, formed in solution, vary in their number, size, and structure depending on the functional groups, solvent, and concentration used. Thus, the substituents/side-groups and the proper choice of the solvent can be used to tune the intermolecular interactions. The 1-D stacks and their aggregates can be easily transferred by solution casting, thus allowing a simple preparation of molecular nanostructures on different surfaces.     

Ordered complex nanostructures from bimodal self-assemblies of diblock copolymer micelles with solvent annealing

We report the formation of ordered complex nanostructures from single-layered films of mixtures of polystyrene-poly(2-vinylpyridine) (PS-P2VP) and polystyrene-poly(4-vinylpyridine) (PS-P4VP) diblock copolymer micelles by THF (tetrahydrofuran) annealing. We first examined the influence of THF vapor on PS-P2VP and PS-P4VP micelles in their single-layered films. Due to the different solubility of PS-P2VP and PS-P4VP copolymers in THF, a hexagonal array of PS-P2VP micelles was changed into cylindrical nanodomains, but that of PS-P4VP micelles was not changed. The different influence of THF on PS-P2VP and PS-P4VP micelles was combined in single-layered films of mixtures of both micelles. For the purpose, we prepared mixture solutions of independently prepared small PS-P2VP and large PS-P4VP micelles. Then, bimodal self-assemblies of micelles were prepared from the mixtures, for which the hexagonal array of large PS-P4VP micelles was surrounded by small PS-P2VP micelles. When the bimodal self-assembly was annealed by THF vapor, PS-P2VP micelles were transformed into cylindrical nanodomains, but their reorganization was guided by hexagonally arranged PS-P4VP micelles. As a result, we were able to produce ordered complex nanostructures in the form of a hexagonal array of PS-P4VP micelles surrounded by PS-P2VP cylinders, which was further utilized for the synthesis of Au nanoparticles.     

Hydrogen bonding with mono- and di-carbonyls

The electronic absorption and i.r. spectroscopic studies are reported for the hydrogen bonding systems involving alcohol and various ketones. It is shown that the hydrogen bonding abilities of ketones are determined by the extent of delocalization of the lone pair electrons in their non-bonding molecular orbitals. Evidence for the formation of very weak intermolecular hydrogen bonds between alcohol and the π-electron part of the dicarbonyls has also been presented from the i.r. studies in the 3400–3700 cm⁻¹ region.     

Hydrogen bonding of 1- and 2-substituted tetrazoles with conventional proton donors

Dissociation constants of H-complexes formed by 1- and 2-substituted tetrazoles with 4-fluorophenol in carbon tetrachloride and methylene chloride were determined by Fourier-transform IR spectroscopy. The nature of substituents on the endocyclic nitrogen and carbon atoms was found to weakly affect the pK _HB value. By contrast, the position of the N-substituent is significant. For example, 1-methyl-5-phenyl-1H-tetrazole (pK _HB = 0.66 in CH₂Cl₂) is a stronger proton acceptor than 2-methyl-5-phenyl-2H-tetrazole (pK _HB = 0.05 in CH₂Cl₂). The proton affinity of the examined compounds appreciably decreases in going from less polar carbon tetrachloride to more polar methylene chloride. No general correlation was revealed between the pK _HB values of substituted 1H- and 2H-tetrazoles and shifts of the OH stretching vibration frequency of methanol (Δν) upon formation of H-complexes.     

Hydrothermal synthesis of ZnO microspheres and hexagonal microrods with sheetlike and platelike nanostructures

Unusual ZnO microspheres constructed of interconnected sheetlike nanostructures were prepared by the hydrothermal synthesis approach. These microspheres possess high surface areas (28.9 m(2)/g) and are amorphous. Trisodium citrate plays a key role in directing the formation of these microstructures. By increasing the reaction time, these microspheres gradually dissolved to form short hexagonal microrods with stacked nanoplate or nanosheet structure. The microrods were also formed under the influence of trisodium citrate. They are crystalline and show a strong (002) X-ray diffraction peak of wurtzite ZnO structure. Both microsphere and microrod samples show near-band-edge emission at approximately 385 nm, but only the microrod sample exhibits yellow luminescence at approximately 560 nm. Due to their high surface areas, these ZnO microstructures were examined for their ability to photodecompose phenol. The as-prepared samples did not display photocatalytic activity due to possible surface adsorption of solution species. However, microspheres with heat treatment to 300 degrees C can substantially enhance the photodecomposition of phenol under direct sunlight irradiation and still maintain their high surface area nanosheet structure.     

Catalyst-nanostructure interaction in the growth of 1-D ZnO nanostructures

Vapor-liquid-solid is a well-established process in catalyst guided growth of 1-D nanostructures, i.e., nanobelts and nanowires. The catalyst particle is generally believed to be in the liquid state during growth, and is the site for impinging molecules. The crystalline structure of the catalyst may not have any influence on the structure of the grown nanostructures. In this work, using Au guided growth of ZnO, we show that the interfaces between the catalyst droplet and the nanostructure grow in well-defined mutual crystallographic relationships. The nanostructure defines the crystallographic orientation of the solidifying Au droplet. Possible alloy, intermetallic, or eutectic phase formation during catalysis are elucidated with the help of a proposed ternary Au-Zn-O phase diagram.     

Controlled synthesis of 2-D and 3-D dendritic platinum nanostructures

Seeding and autocatalytic reduction of platinum salts in aqueous surfactant solution using ascorbic acid as the reductant leads to remarkable dendritic metal nanostructures. In micellar surfactant solutions, spherical dendritic metal nanostructures are obtained, and the smallest of these nanodendrites resemble assemblies of joined nanoparticles and the nanodendrites are single crystals. With liposomes as the template, dendritic platinum sheets in the form of thin circular disks or solid foamlike nanomaterials can be made. Synthetic control over the morphology of these nanodendrites, nanosheets, and nanostructured foams is realized by using a tin-porphyrin photocatalyst to conveniently and effectively produce a large initial population of catalytic growth centers. The concentration of seed particles determines the ultimate average size and uniformity of these novel two- and three-dimensional platinum nanostructures.     

Hydrogen bonding in phenol, water, and phenol-water clusters

Structure, stability, and hydrogen-bonding interaction in phenol, water, and phenol-water clusters have been investigated using ab initio and density functional theoretical (DFT) methods and using various topological features of electron density. Calculated interaction energies at MP2/6-31G level for clusters with similar hydrogen-bonding pattern reveal that intermolecular interaction in phenol clusters is slightly stronger than in water clusters. However, fusion of phenol and water clusters leads to stability that is akin to that of H(2)O clusters. The presence of hydrogen bond critical points (HBCP) and the values of rho(r(c)) and nabla(2)rho(r(c)) at the HBCPs provide an insight into the nature of closed shell interaction in hydrogen-bonded clusters. It is shown that the calculated values of total rho(r(c)) and nabla(2)rho(r(c)) of all the clusters vary linearly with the interaction energy.     

Hydrogen bonding of water, hydrogen sulphide and related acceptors with electron donors

Properties of hydrogen bonds formed by 1:1 interaction of H₂O with oxygen, nitrogen, sulphur and other electron donors have been evaluated by extended Hückel and CNDO methods and the results are discussed in relation to the experimental data. A detailed analysis of the variation of the dissociation energies and charge densities with bond distances is presented for the amine-water system. 1:2 complexes of water with donors are found to contain weaker hydrogen bonds than 1:1 complexes. Results of molecular orbital calculations on the hydrogen bonding of H₂S and CH₃SH with some donors are presented. The theoretical value of hydrogen bond dissociation energy varies linearly with the overlap population, and stretching force constant of the hydrogen bond as well as with the experimental O—H frequency shift.     

Hydrogen bonding interactions of phenol with cyclic ketones

Complexes of phenol with cyclohexanone, 2-cyclohexan-1- one, δ-valerolactone, 5,6-dihydro-2H-pyran-2-one, cyclopentanone, 2-cyclopenten-1-one, γ-valerolactone and γ-butyrolactone have been studied by i.r. spectroscopy. The thermodynamic data for the 1 : 1 association have been determined. When the complexes are classified into phenol-cycloketones and phenol-lactones, the variation of the enthalphy for the complex formation in each group has been found to be consistent with those of the free energy change, the equilibrium constant, and the dipole moment of the bases in gas phase. The sites of intermolecular interactions and the relationship of the interaction strength with the dipole moment of the proton acceptor are discussed.     

Synthesis,structure, and bonding of the hexagonal form of the oxide carbide ScAlOC

Red single crystals of a hexagonal form of ScAlOC were obtained as a by-product from the synthesis of ScAl₃C₃ by reacting scandium and carbon in an aluminium melt at 1820 °C. The crystal structure (hP8, space group P6₃mc, Z = 2, a = 3.24793(3) Å, c = 10.1739(1) Å, 629 refl., 15 param., R₁(F) = 0.010, wR₂(F²) = 0.023) can directly be derived from the binary nitrides AlN and ScN or the oxide carbides Sc(O,C) and Al(O,C), respectively. ScAlOC-II or h-ScAlOC represents a new structure type with simple closest packing of alternating layers of oxygen and carbon. The stacking sequence is ABAC (=(hc)₂) with oxygen in a cubic and carbon in a hexagonal sequence. According to the difference in size Sc occupies octahedral voids between every second layer leading to layers of edge-sharing ScO₃C₃ octahedra. Aluminium is located in half of the tetrahedral voids. The AlOC₃-tetrahedra are connected to layers by common corners of the carbon atoms. h-ScAlOC continues the row of the rare examples of oxide carbides with ordered anion distribution. Band structure calculations by FP-(L)APW methods revealed that ScAlOC is electron precise with a band gap of 1.2 eV. Calculations of charges by the Bader-method reveal values of Sc^+1.87, Al^+2.33, O^−1.52 and C^−2.67. Together with the charge densities and the values of the Laplacian this stands for a mainly ionic bonding containing significant covalent contributions, too. Despite the close similarity to rhombohedral ScAlOC (r-ScAlOC) there is a striking difference in colour, as r-ScAlOC is black. This is confirmed and explained by the results of the P-DOS, because the lowest states of the conduction band are determined by Sc-d-states. These are significantly lower in r-ScAlOC with ScC₆ and ScO₆ octahedra than in h-ScAlOC leading to a calculated band gap of 0.3 eV.     

Hydrogen bonding,tautomerism and normal vibrations of thiol acids

Hydrogen bonding in thiolformic, thiolacetic and dithioformic acids has been investigated by CNDO/2 and extended Hückel methods. In thiol acids, hydrogen bonds formed by both the hydroxy and the thiol forms are examined. Cyclic dimers of the hydroxy form are more stable, as in carboxylic acids, while the open dimers are more stable in the case of the thiol form. Dithioformic acid forms very weak hydrogen bonds compared to thiol acids. Vibrational assignments have been made for the hydroxy and thiol forms of thiolformic acid as well as for the thioformate ion based on normal vibration analysis.     

Hydrogen bonding,mobility, and structural transitions in aliphatic polyamides

Some salient results in nylon research are reviewed to identify the fundamental principles that are applicable to other strongly interacting or hydrogen‐bonded polymers, including proteins. The effects of hydrogen bonds on stress‐, heat‐, and solvent‐induced changes in macroscopic properties are discussed. These data provide a window into the chain mobility and linkages between the crystalline and amorphous domains, both of which are important for any predictive model. The changes in the characteristics of the amorphous phase with the crystallinity and orientation require that it be modeled with at least two components: a rigid/immobile/anisotropic component and a soft/mobile/isotropic component. The deformation and shrinkage behavior of these polymers are discussed in terms of the relative contributions of the amorphous and crystalline domains and of the interactions between them. The premelting crystalline transition is accompanied by the merging of intersheet and intrasheet diffraction peaks in some nylons, as observed by Brill, and not in others even though the underlying mechanism that gives rise to these transitions, the onset of volume‐increasing librational motion of the crystalline stems, is the same. Because the effects of the temperature, deformation, and solvent have a common origin associated with mobility, a fictive temperature can be associated with a given solvent activity or stress level. The magnitude of this fictive temperature is the amount by which the glass or Brill transition temperature is reduced in the presence of solvents (～50 °C) or stress or by which the annealing temperature can be reduced in the presence of a solvent (or active stress) to achieve the same structural state as that of a dry (or static) polymer. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1763–1782, 2006