The reaction of 2,5-dimethylfuran with hydrogen atoms – An experimental and theoretical study

The kinetics of the reaction of hydrogen atoms with 2,5-dimethylfuran (25DMF), a promising liquid transport biofuel, was experimentally studied in a shock tube at temperatures between 970 and 1240 K and pressures of 1.6 and 4.8 bar. The hydrogen atoms were produced by pyrolysis of ethyl iodide and monitored by atom resonance absorption spectrometry. From the hydrogen atom concentration–time profiles, overall rate coefficients for the reaction H + 25DMF → products (R1) were inferred. The results can be expressed by the Arrhenius equation k₁ = 4.4 × 10^?11 exp(?1180 K/T) cm^?3 s^?1 with an estimated uncertainty of ±30%. A significant pressure dependence was not observed. The results were analyzed in terms of statistical rate theory with molecular and transition state data from quantum chemical calculations. Three different compound methods were used to characterize the potential energy surface: CBS-QB3, CBS-APNO, and G3. It is found that reaction (R1) mainly (>75%) proceeds via an addition–elimination mechanism to yield 2-methylfuran + CH₃. Kinetic parameters for the most important competing channels of the net reaction (R1) were calculated.     

Formation mechanism of hydroxyacetone in glucose pyrolysis: A combined experimental and theoretical study

During fast pyrolysis of biomass, hydroxyacetone (HA, also known as 1-hydroxy-2-propanone) is a vital linear ketone product from fragmentation (ring scission) of cellulose. In this study, density functional theory (DFT) calculations are employed to reveal the HA formation mechanisms and pathways from fast pyrolysis of glucose that is the cellulose-based monosaccharide. Moreover, isotopic labeling fast pyrolysis experiments were conducted to confirm the theoretical calculation results from glucose. The results indicate that during glucose pyrolysis, HA is mainly derived from C1–C2–C3 and C4–C5–C6 segments, with C1 or C6 in the methyl group of HA. The HA from C1–C2–C3 is mainly generated via the 3-ketohexose intermediate, while the formation of the HA from C4–C5–C6 mainly involves the d-fructose intermediate. In addition, the formation of HA is parallel and competitive with the formation of levoglucosan (LG, the most important pyrolytic product of glucose), and the secondary decomposition of LG will result in trace of the HA from C4–C5–C6.     

Recent theoretical and experimental development of Mössbauer effect with synchrotron radiation

The elements of a dedicated beam line are introduced. Computer simulations of the nuclear monochromator response to an incident broad band of radiation show the special features of the new source-speed up, dynamical beats, quantum beats and polarization mixing. Experiments with YIG and FeBO₃ confirm the theoritical picture. It is shown that time differential measurements have the potential of greatly improving the accuracy of future experiments. New fields of investigations will be broadband spectroscopy in the eV range and -optics.Dedicated to Ulrich Bonse on the occasion of his 60th birthday     

Rate coefficients for the gas-phase reaction of OH radical with α-pinene: an experimental and computational study

The rate coefficient for the gas-phase reaction of OH radical with α-pinene was measured at 298 K using relative rate methods, with propylene as a reference compound. The ratio of the rate coefficient for the reaction of OH radicals with α-pinene to that of with OH radicals with propylene was measured to be 1.77 ± 0.21. Considering the absolute value of the rate coefficient of the reaction of OH radicals with propylene as (3.01 ± 0.42)×10^?11 cm³ molecule^?1 s^?1, the rate coefficient for the reaction of OH radicals with α-pinene was determined to be (5.33 ± 0.79)×10^?11 cm³ molecule^?1 s^?1. To gain a deeper insight into the reaction mechanism, theoretical calculations were also carried out on this reaction. The rate coefficient of OH radical with α-pinene was calculated using canonical variational transition state theory with small-curvature tunnelling. The kinetics data obtained over the temperature range of 200–400 K were used to derive the Arrhenius expression: k(T) = 3.8×10^?28 T^5.2 exp[2897/T] cm³ molecule^?1 s^?1. The OH-driven atmospheric lifetime (τ) and ozone formation potential of α-pinene were calculated and reported in this work.     

Experimental and theoretical study on the β-FeOOH nanorods: growth and conversion

This study presents an experimental and theoretical study on the growth of monodispersed akaganéite (β-FeOOH) nanorods with tunable aspect ratios (longitudinal to transversal) under mild conditions (80 °C, aqueous solution). The synthesis of β-FeOOH nanorods is highly influenced by the presence of salt ions, and thus, the effect of various anions (e.g., NO₃ ⁻, SO₄ ²⁻, F⁻, Cl⁻, and Br⁻) were investigated on the microstructure, morphology, and size of the nanoparticles. It was found that these anions could interact strongly or weakly with the FeO₆ octahedral unit in the ferric oxyhydroxides, hence greatly affect the morphology, crystallization, and structure of the iron oxide/oxyhydroxide nanoparticles under the reported conditions. Moreover, these nanorods could be converted into magnetite (Fe₃O₄) through the reduction of hydrazine, which provides a new template approach to prepare magnetite nanorods with shape and size control at ambient conditions. The microstructure, composition, and structural transformation of the as-synthesized nanoparticles were characterized by various techniques, such as transmission electron microscopy (TEM and HRTEM), X-ray diffraction (XRD), and energy dispersive spectroscopy (EDS). The possible formation and growth mechanism of akaganéite nanorods were discussed. Finally, the influence of anions on the β-FeOOH(100), (110), and (001) surfaces was further understood by theoretical simulations (e.g., molecular dynamics method).     

Theoretical and experimental study of the intensity distribution in biological tissues

Based on the diffusion approximate theory （DA）, a theoretical model about the distribution of the intensity of a narrow collimation beam illuminating on a semi-lnfinite biological tissue is developed. In order to verify the correctness of the model, a novel method of measuring the distributions of the intensity of light in Intralipid-10% suspension at 650 nm is presented and ts of the distributions of the distance-dependent intensity of scattering light in different directions are made. The investigations show that the results from our diffusion model are in good agreement with the experimental results beyond and in the areas around the light source, and the distance-dependent intensity in the incident direction attenuates approximately in the exponential form. Furthermore, our theoretic results indicate the anisotropic characteristics of the intensity in different directions of scattering light inside the biological tissue.     

Mechanism and kinetics of the atmospheric degradation of 2-formylcinnamaldehyde with O3 and hydroxyl OH radicals – a theoretical study

In the present investigation, the reaction mechanism and kinetics of 2-formylcinnamaldehyde (2-FC) with O₃ and hydroxyl OH radicals were studied. The reaction of 2-FC with O₃ radical are initiated by the formation of primary ozonide, whereas the reaction of 2-FC with the hydroxyl OH radical are initiated by two different ways: (1). H-atom abstraction by hydroxyl OH radical from the –CHO and –CH = CHCHO group of 2-FC (2). Hydroxyl OH addition to the –CH = CHCHO group to the ring-opened 2-FC. These reactions lead to the formation of an alkyl radical. The reaction pathways corresponding to the reactions between 2-FC with O₃ and hydroxyl OH radicals have been analysed using density functionals of B3LYP and M06-2X level of methods with the 6-31+G(d,p) basis set. Single-point energy calculations for the most favourable reactive species are determined by B3LYP/6-311++G(d,p) and CCSD(T)/6-31+G(d,p) levels of theory. From the obtained results, the hydroxyl OH addition at C8 position of 2-FC are most favourable than the C9 position of 2-FC. The subsequent reactions of the alkyl radicals, formed from the hydroxyl OH addition at C8 position, are analysed in detail. The individual and overall rate constant for the most favourable reactions are calculated by canonical variational transition theory with small-curvature tunnelling corrections over the temperature range of 278–350 K. The calculated theoretical rate constants are in good agreement with the available experimental data. The Arrhenius plot of the rate constants with the temperature are fitted and the atmospheric lifetimes of the 2-FC with hydroxyl OH radical reaction in the troposphere calculate for the first time, which can be applied to the study on the atmospheric implications. The condensed Fukui function has been verified for the most favourable reaction sites. This study can be regarded as an attempt to investigate the O₃-initiated and hydroxyl OH-initiated reaction mechanisms of 2-FC in the atmosphere.     

Drug–DNA interaction: A theoretical study on the binding of thionine with DNAs of varying base composition

The recent studies carried out on the binding of small molecule to deoxyribonucleic acids suggested that the intercalation of a tricyclic heteroaromatic molecule, thionine, with natural DNAs provided thermal stabilization to the DNA complex. In the present study, we reported theoretical analysis of thionine binding with natural DNAs of varying base composition by using an amended Zimm and Bragg theory, to explain the melting behaviour and heat capacity of DNAs with and without thionine binding. We used experimental models of Paul et al. for implementing this study (Paul et al., 2010). The sharpness of transition has been examined in terms of half width and sensitivity parameter (ΔH/σ). The results of theoretical analysis concluded that the various parameters such as heat capacity curve, transition profile, half widths and sharpness of the transition are in good agreement with the experimental measurements for binding of thionine determined through DSC. The theoretical analysis proposed in this study, therefore, may be useful to understand interaction of small molecules with deoxyribonucleic acids. This approach may also be applied to design DNA binding therapeutic molecules and in the process of drug formulation and development.     

Experimental and theoretical study of linearly polarized Lorentz–Gauss beams with heterogeneous distribution

The unevenly distributed Lorentz–Gaussian beams are difficult to reproduce in practice, because they require modulation in both amplitude and phase terms. Here, a new linearly polarized Lorentz–Gauss beam modulated by a helical axicon(LGB-HA)is calculated, and the two various experimental generation methods of this beam, Fourier transform method(FTM) and complex-amplitude modulation(CAM) method, are depicted. Compared with the FTM, the CAM method can modulate the phase and amplitude simultaneously by only one reflection-type phase-only liquid crystal spatial light modulator.Both of the methods are coincident with the numerical results. Yet CAM is simpler, efficient, and has a higher degree of conformance through data comparison. In addition, considering some barriers exist in shaping and reappearing the complicated Lorentz–Gauss beam with heterogeneous distribution, the evolution regularities of the beams with different parameters(axial parameter, topological charge, and phase factor) were also implemented.     

The focus of light – theoretical calculation and experimental tomographic reconstruction

We present numerical calculations on the field distribution in the focus of an optical system with high numerical aperture. The diffraction integrals which are based on the Debye approximation are derived and evaluated for a radially polarized input field with a doughnut-shaped intensity distribution. It is shown that this mode focusses down to a spot size significantly smaller as compared to the case of linear polarization. An experimental setup to measure the three-dimensional intensity distribution in the focal region is presented, which is based on the knife-edge method and on tomographic reconstruction. Received: 14 July 2000 / Published online: 30 November 2000     

Ab initio study of synergetic effects of two strong interactions of cation–π interaction and lithium bond in M+ ··· phenyl lithium ··· N (M = Li,Na, K; N = H2O and NH3) complex

Quantum chemical calculations have been performed to investigate the interplay between the cation–π interaction and lithium bonding in the M⁺?···?phenyl lithium?···?OH₂ and M⁺?···?phenyl lithium?···?NH₃ (M?=?Li, Na, K) complexes. The cation–π interaction and lithium bonding in the trimers become stronger relative to the dimers. The interaction energy of cation–π interaction is increased by about 4.4–6.3%, while that of lithium bonding is increased by about 5.2–15.9%. The cooperative energy becomes larger for the stronger cation–π interaction and lithium bond. The F atom and methyl group in the phenyl ring impose a reverse effect on the cation–π interaction and lithium bond. The interaction mechanism in the complexes has been understood with the many-body interaction analysis, electrostatic potentials, and energy decomposition.     

Vibrational Spectroscopic and Theoretical Studies of Urea Derivatives with Biochemical Interest: N,N′-Dimethylurea,N,N,N′,N′-Tetramethylurea,and N,N′-Dimethylpropyleneurea

Abstract

Mid-infrared, far-infrared, and Raman vibrational spectroscopic studies were combined with density functional theory (DFT) calculations and normal coordinate force field analyses for N,N′-dimethylurea (DMU), N,N,N′,N′-tetramethylurea (TMU), and N,N′-dimethylpropyleneurea (DMPU: IUPAC name 1,3-dimethyltetrahydropyrimidin-2(1H)-one). The equilibrium molecular geometry of DMU (all three conformers), TMU, and DMPU and the frequencies, intensities, and depolarization ratios of their fundamental infrared (IR) and Raman vibrational transitions were obtained by DFT calculations. The vibrational spectra were fully analyzed by normal coordinate methods as well. A starting force field for DMPU was obtained by adapting corresponding force constants for DMU and TMU, resulting after refinements in the stretching force constants C=O (7.69, 7.30, 7.68 N·cm^?1), C–N (5.16, 5.55, 5.05 N·cm^?1), and C-Me (5.93, 4.00, 4.22 N·cm^?1) for DMU, TMU, and DMPU, respectively. The dominating conformer of liquid DMU was identified as trans-trans, strong intermolecular hydrogen bonding was verified in solid DMU, and weak dipole–dipole association was found in liquid TMU and in DMPU. Special attention was paid to analyzing the methyl group frequencies, which revealed deviations from local C_3v symmetry. A linear correlation was found between the CH stretching force constants and the inverse of the CH bond lengths (1/r ²). The averaged NH stretching frequencies of gaseous, dissolved, and solid urea and of DMU, with variations for hydrogen bonding of different strength, are linearly correlated to the NH stretching force constants. Characteristic skeletal vibrations were assigned for a broad variety of urea derivatives and also for pyrimidine derivatives, which all contain the N₂C=O entity. The very strong IR bands of C=O stretching (1,676 ± 40 cm^?1) and asymmetric CN₂ stretching (1,478 ± 60 cm^?1), and the very intense Raman feature of symmetric CN₂ stretching or ring breathing (757 ± 80 cm^?1), can be recognized as fingerprint bands also for the pyrimidine derivatives cytosine, thymine, and uracil, which all are nucleobases in DNA and RNA nucleotides.     

A theoretical study of N–H ··· π H-bond interaction of pyrrole: from clusters to the liquid

The N–H?···?π H-bond interactions of clusters and liquid formed by pyrrole molecules were investigated by Quantum Mechanics (QM) and classical Molecular Dynamics (MD), respectively. Based on the optimized geometry at the B97-D/aug-cc-pVTZ level of theory including dispersion correction, the nature and the origin of N–H?···?π H-bond interactions were unveiled by atoms in molecules (AIM), natural bond orbital (NBO), and energy decomposition analysis (EDA). Among them, the AIM analysis gives evidence to the presence of N–H?···?π H-bond interactions, the NBO examination reveals that π?→?σ* donor-acceptor orbital interaction is of great importance. EDA study indicates that N–H?···?π interactions are governed by the electrostatic and dispersion term. Meanwhile, MD simulation with OPLS-AA (optimized potentials for liquid simulations all-atom) was applied to study the pure liquid pyrrole at different temperature. The results confirm the existence of the N–H?···?π H-bond in the pure liquid pyrrole, and further characterized the structures of this H-bond which is somewhat different to the clusters.     

Optical characterization of photopolymers materials: theoretical and experimental examination of primary radical generation

Several studies of the time varying photon absorption effects, which occur during the photo-initiation process in photopolymer materials, have been presented. Three primary mechanisms have been identified: (i) the dye absorption, (ii) recovery, and (iii) bleaching. Based on an analysis of these mechanisms, the production of primary radicals can be physically described and modelled. In free radical photo-polymerization systems, the excited dye molecules induce the production of the primary radicals, R ^?, which is a key factor in determining how much monomer is polymerized. This, in turn, is closely related to the refractive index modulation formed during holographic recording. In this article, by modifying the composition of a polyvinylalcohol/acrylamide based photopolymer material, i.e. excluding any co-initiator, the photo-kinetic behaviour of the material is greatly simplified. In this way, the rate constant of intersystem crossing, k _st, in going from the excited singlet state dye to the excited triple state dye can be determined. k _st is then available to be applied in a full model of the photo-initiation process making it possible to accurately predict the time varying concentration of primary radicals generated during exposure.     

Some theoretical and experimental aspects of three-grating Mach–Zehnder atom interferometers

In this contribution, we present some recent theoretical results concerning the fringe contrast in Mach–Zehnder atom interferometers and the use of Bloch states to describe atomic diffraction. We also describe the observation of diffraction of lithium at thermal energy by a quasi-resonant laser standing wave.     

An experimental study on the sound scattering of the ship's wakes

lIntroductionWaks,asaldndofacousticaltarget,haveveryimportantIIillitaresense,becausetrackingwithwakstorpedohasbeenoneoftheefficientweaPontoattaCklargeseasurfacetarget-CowtrlesallovertheworldmakegreateffortstodevelopwaktraCkingtorpedo.Moreandmoreattelltionistobepaidtothestudyofsoundscatteringcharacteristicsofshipwakes.ThewdssofshiPareconsistedofalotofbubblesrollingallthetimebecauseofpropellerturbulence-Moreover,somebubblesa-redissolvedinthewaterandsomegoneup.TheascendingspeedofdiIfrelltsize…     

A theoretical and experimental evaluation of Ⅲ–nitride solar-blind UV photocathode

We have developed a superior solar-blind ultraviolet(UV) photocathode with an Al_xGa_(1-x)N photocathode(x ～ 0.45)in semi-transparent mode, and assessed spectra radiant sensitivity related to practical use. Before being grown over a basal plane sapphire substrate by low-pressure metal organic chemical vapor deposition(MOCVD), a reasonable design was made to the photocathode epitaxy structure, focusing on the Al_xGa_(1-x)N: Mg active layer, then followed by a comprehensive analysis of the structural and optical characterization. The spectra radiant sensitivity is peaked of 41.395 mA/W at wavelength 257 nm and then decreases by about 3 to 4 decades at 400 nm demonstrating the ability of this photocathode for solar-blind application prospects.