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81.
Infrared absorption, vibrational circular dichroism, and two-dimensional infrared pump-probe and photon echo spectra of acetylproline solutions are theoretically calculated and directly compared with experiments. In order to quantitatively determine interpeptide interaction-induced amide I mode frequency shifts, high-level quantum chemistry calculations were performed. The solvatochromic amide I mode frequency shift and fluctuation were taken into account by carrying out molecular dynamics simulations of acetylproline dissolved in liquids water and chloroform and by using the extrapolation method developed recently. We first studied correlation time scales of the two amide I vibrational frequency fluctuations, cross correlation between the two fluctuating local mode frequencies, ensemble averaged conformations of the acetylproline molecule in liquids water and chloroform. The corresponding conformations of the acetylproline in liquids water and chloroform are close to the ideal 3(10) helix and the C(7) structure, respectively. A few methods proposed to determine the angle between the two transition dipoles associated with the amide I vibrations were tested and their limitations are discussed.  相似文献   
82.
The ring-opening polymerization of an unsaturated bicyclic lactam, 2-azabicyclo-[2,2,1]-hept-5-en-3-one (ABHEO), was carried out using metathesis catalysts under various reaction conditions. It is observed that the best results (34% conversion and ηinh: 0.18 dL/g) were obtained when the mole ratios of ABHEO to WCl6 as a catalyst and WCl6 to AlEt3 as a cocatalyst were 200 and 4, respectively. The infrared (IR) and nuclear magnetic resonance (1H- and 13C-NMR) spectra of the polymer obtained indicated that the ABHEO was transformed to the ring-opened polymer, poly(2-pyrrolidone-3,5-diylvinylene) [poly(ABHEO)]. The resulting polymer was amorphous as determined by DSC analysis, which showed only secondary transition at 100°C.  相似文献   
83.
Laser-ablated W atoms react with CH4 in excess argon to form the CH3-WH, CH2=WH2, and CH[triple bond]WH3 molecules with increasing yield in this order of product stability. These molecules are identified from matrix infrared spectra by isotopic substitution. Tungsten methylidene and methylidyne hydride molecules are reversibly interconverted by alpha-H transfers upon visible and ultraviolet irradiations. Matrix infrared spectra and DFT/B3LYP calculations show that CH[triple bond]WH3 is a stable molecule with C3v symmetry, but other levels of theory were required to describe agostic distortion for CH2=WH2. Analogous reactions with Cr gave only CH3-CrH, which is calculated to be by far the most stable product.  相似文献   
84.
The structures of hydrated 1-hydroxyanthraquinone complexes (1-HAQ), 1-HAQ(H2O)n=1,2, with intramolecular and intermolecular hydrogen bonding interactions were studied using laser spectroscopic methods such as laser induced fluorescence, fluorescence-detected infrared, infrared-visible hole burning, and visible-visible hole burning spectroscopy. In the 1:1 complex 1-HAQ(H2O)1, the water binds to the free carbonyl group of 1-HAQ not associated with intramolecular hydrogen bond. The second water in the 1:2 complex, 1-HAQ(H2O)2, binds to the first water of the 1:1 complex rather than other hydrogen bonding sites of 1-HAQ. A pair of two geometric isomers was produced in a supersonic jet for each of the 1:1 and 1:2 complexes. Both isomers of each complex have the same vibrational spectra in the region of the OH stretching vibration of water, but have different energies for the 0-0 band of vibronic transition due to the asymmetry of the two phenyl rings in 1-HAQ. The 0-0 bands for all four species of 1-HAQ(H2O)n=1,2 were unambiguously assigned by comparing with the results of ab initio calculations, which yielded the structures, vibrational frequencies, and relative energies of the frontier molecular orbitals.  相似文献   
85.
A simple method of synthesizing a large quantity of TiO(2) nanorods was developed. A nonhydrolytic sol-gel reaction between titanium(IV) isopropoxide and oleic acid at 270 degrees C generated 3.4 nm (diameter) x 38 nm (length) sized TiO(2) nanocrystals. The transmission electron microscopic image showed that the particles have a uniform diameter distribution. X-ray diffraction and selected-area electron diffraction patterns combined with high-resolution transmission electron microscopic image showed that the TiO(2) nanorods are highly crystalline anatase crystal structure grown along the [001] direction. The diameters of the TiO(2) nanorods were controlled by adding 1-hexadecylamine to the reaction mixture as a cosurfactant. TiO(2) nanorods with average sizes of 2.7 nm x 28 nm, 2.2 nm x 32 nm, and 2.0 nm x 39 nm were obtained using 1, 5, and 10 mmol of 1-hexadecylamine, respectively. The optical absorption spectrum of the TiO(2) nanorods exhibited that the band gap of the nanorods was 3.33 eV at room temperature, which is 130 meV larger than that of bulk anatase (3.2 eV), demonstrating the quantum confinement effect. Oleic acid coordinated on the nanorod surface was removed by the reduction of the carboxyl group of oleic acid, and the Brunauer-Emmett-Teller surface area of the resulting naked TiO(2) nanorods was 198 m(2)/g. The naked TiO(2) nanorods exhibited higher photocatalytic activity than the P-25 photocatalyst for the photocatalytic inactivation of E. coli.  相似文献   
86.
The copper(II) ion in the synanti carboxyl­ate‐bridged one‐dimensional zigzag chain title complex, {[Cu(C16H18N3O2)]ClO4}n, exhibits a distorted trigonal–bipyramidal environment. Two N atoms and one carboxyl­ate O atom of the ligand form the basal plane, while the axial positions are filled by an N atom of the ligand and one O atom belonging to the carboxyl­ate group of an adjacent mol­ecule. The crystal packing is enhanced by C—H⋯O(perchlorate) hydrogen bonds.  相似文献   
87.
In this study, the thermal properties of bio-flour-filled, polypropylene (PP) bio-composites with different pozzolan contents were investigated. With increasing pozzolan content, the thermal stability, 5% mass loss temperature and derivative thermogravimetric curve (DTGmax) temperatures of the bio-composites slightly increased. The coefficient of thermal expansion (CTE) and thermal expansion of the bio-composites decreased as the pozzolan content increased. The glass transition temperature (T g), melting temperature (T m) and percentage of crystallinity (X c) of the bio-composites were not significantly changed. The thermal stability, thermal expansion and X c of the maleic anhydride-grafted PP (MAPP)-treated bio-composites were much higher than those of non-treated bio-composites at 1% pozzolan content due to enhanced interfacial adhesion. X-ray diffraction (XRD) analysis confirmed the crystallinity of pozzolan-added bio-composites. From these results, we concluded that the addition of pozzolan in the bio-composites was an effective method for enhancing the thermal stability and thermal expansion.  相似文献   
88.
Electronically coupled porphyrin arrays are suitable for artificial light harvesting antenna in light of a large absorption cross-section and fast excitation energy transfer (EET). Along this line, an artificial energy transfer model system has been synthesized, comprising of an energy donating meso-meso linked Zn(II) porphyrin array and an energy accepting 5,15-bisphenylethynylated Zn(II) porphyrin linked via a 1,4-phenylene spacer. This includes an increasing number of porphyrins in the meso-meso linked Zn(II) porphyrin array, 1, 2, 3, 6, 12, and 24 (Z1A, Z2A, Z3A, Z6A, Z12A, and Z24A). The intramolecular singlet-singlet EET processes have been examined by means of the steady-state and time-resolved spectroscopic techniques. The steady-state fluorescence comes only from the acceptor moiety in Z1A-Z12A, indicating nearly the quantitative EET. In Z24A that has a molecular length of ca. 217 A, the fluorescence comes largely from the acceptor moiety but partly from the long donor array, indicating that the intramolecular EET is not quantitative. The transient absorption spectroscopy has provided the EET rates in real time scale: (2.5 ps)(-1) for Z1A, (3.3 ps)(-1) for Z2A, (5.5 ps)(-1) for Z3A, (21 ps)(-1) for Z6A, (63 ps)(-1) for Z12A, and (108 ps)(-1) for Z24A. These results have been well explained by a revised F?rster equation (Sumi formula), which takes into account an exciton extending coherently over several porphyrin pigments in the donor array, whose length is not much shorter than the average donor-acceptor distance. Advantages of such strongly coupled porphyrin arrays in light harvesting and transmission are emphasized in terms of fast EET and a large absorption cross-section for incident light.  相似文献   
89.
Using first-principles density-functional calculations we predict a self-directed growth of benzonitrile molecular line on a H-terminated Si(001) surface. The C[triple bond]N bond of benzonitrile reacts with a single Si dangling bond which can be generated by the removal of a H atom, forming one Si-N bond and one C radical. Subsequently, the produced C radical can be stabilized by abstracting a H atom from a neighboring Si dimer, creating another H-empty site. This H-abstraction process whose activation barrier is 0.65 eV sets off a chain reaction to grow one-dimensional benzonitrile line along the Si dimer row. Our calculated energy profile for formation of the benzonitrile line shows its relatively easier formation compared with previously reported styrene and vinylferrocene lines.  相似文献   
90.
Abstract— C4--Photocycloaddition of 5,7-dimethoxycoumarin (DMC) to thymine (λ≥ 300 nm) was studied in dioxane-water solution, in aqueous frozen state, and solid film state. The major product was isolated and characterized by physical methods. Elemental analysis data, spectral analyses, and photo-splitting of the product indicate the product to be a 1:l C4--cycloadduct of DMC and thymine.  相似文献   
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