核磁共振碳谱的研究:烷烃化学位移和CSS与分子距边矢量λ

系统研究了核磁共振碳谱及其化学位移规律性.提出了一种新的分子图论参数:分子距离一边数矢量(λ或MDE矢量),并发现它与烷烃的¹³C NMR有良好的相关性。     

Simulations of the chain length dependence of the melting mechanism in short-chain n-alkane monolayers on graphite

The melting transition in solid monolayers of a series of short-chained n-alkanes, n-octane (n-C₈H₁₈), n-decane (n-C₁₀H₂₂), and n-dodecane (n-C₁₂H₂₆) physisorbed onto the graphite basal plane are studied through use of molecular dynamics simulations. Utilizing previous experimental observations of the solid phase behavior of these monolayers, this study investigates the temperature dependence of the phases and phase transitions in these three monolayers during the solid-fluid phase transition, and compares the observed melting behavior to previous studies of hexane and butane monolayers. In particular, this study seems to indicate a greater dependence of the melting transition on the formation of gauche defects in the alkyl chains as the chain length is increased. In light of the previously proposed “footprint reduction” mechanism and variations where the formation of gauche defects are energetically negated, simulations seem to suggest that decane and dodecane monolayers are generally equally as dependent upon the formation of gauche defects for the melting transition to take place, whereas octane monolayers seem to have less dependence, but follow a trend that is established in previous studies of melting in butane and hexane monolayers. Also, the phase transition from a solid herringbone phase into an orientationally ordered “intermediate” phase is found to exhibit some differences as compared to a recent study of hexane monolayers, which may be interpreted as originating from the greater influence of gauche defects. Comparison to experimental melting temperatures is provided where possible, and applications involving thin film manipulation and lubrication is discussed.     

Composition as a method for data reduction: application to carbon-13 NMR chemical shifts

The concept of composition as the counterpart to partition is introduced and advocated for the discussion of molecular properties. In the partition approach an observable (experimental) quantity is fragmented into contributions which are non-observable but which hopefully maintain constancy for fragments (bonds) in similar environments and thus facilitate comparison of data. With the composition as an approach the role of fragments and whole are reversed: one starts with a collection of observable fragment properties (e.g., atomic chemical shifts of NMR spectra) and then constructs an abstract non-observable quantity representing the collection of fragments as a whole. If a so-derived quantity for different molecules shows some regularity, the initial loss of information in condensation of independent fragment data is compensated by insight into novel structural correlations. The approach is illustrated first by ordering isomers (e.g., nonanes C₉H₂₀) with respect to their content of special graph invariants p ₂ and p ₃ (numbers of paths of length two and length three, respectively) and then showing that the constructed global quantity derived from individual carbon-13 NMR chemical shifts shows a regular variation with p ₂ and p ₃, very similar to isomeric variations of numerous thermodynamic properties of nonanes. Subsequently it is outlined how the difference (p ₂ p ₃) leads to a correlation for mean carbon-13 chemical shifts in octanes and nonanes, taken as an illustration for the approach. It is expected that the outlined approach opens new avenues for data reduction and the search for structure-property correlations.Dedicated to Professor J. Koutecký on the occasion of his 65th birthdayOperated by Iowa State University for the US Department of Energy under Contract No. W-7405-ENG-82. This work was supported in part by the Office of the Director     

In situ XPS investigation of Pt(Sn)/Mg(Al)O catalysts during ethane dehydrogenation experiments

Calcined hydrotalcite with or without added metal (Mg(Al)O, Pt/Mg(Al)O and Pt,Sn/Mg(Al)O) have been investigated with in situ X-ray photoelectron spectroscopy (XPS) during ethane dehydrogenation experiments. The temperature in the analysis chamber was 450 °C and the gas pressure was in the range 0.3-1 mbar. Depth profiling of calcined hydrotalcite and platinum catalysts under reaction, oxidation and in hydrogen-water mixture was performed by varying the photon energy, covering an analysis depth of 10-21 Å. It was observed that the Mg/Al ratio in the Mg(Al)O crystallites does not vary significantly in the analysis depth range studied. This result indicates that Mg and Al are homogeneously distributed in the Mg(Al)O crystallites. Catalytic tests have shown that the initial activity of a Pt,Sn/Mg(Al)O catalyst increases during an activation period consisting of several cycles of reduction-dehydrogenation-oxidation. The Sn/Mg ratio in a Pt,Sn/Mg(Al)O catalyst was followed during several such cycles, and was found to increase during the activation period, probably due to a process where tin spreads over the carrier material and covers an increasing fraction of the Mg(Al)O surface. The results further indicate that spreading of tin occurs under reduction conditions.A PtSn₂ alloy was studied separately. The surface of the alloy was enriched in Sn during reduction and reaction conditions at 450 °C. Binding energies were determined and indicated that Sn on the particle surface is predominantly in an oxidised state under reaction conditions, while Pt and a fraction of Sn is present as a reduced Pt-Sn alloy.     

Superacid-Catalyzed Oxygenation of Alkanes. [New synthetic methods (26)]

Owing to the ready availability of the starting materials, the functionalization of saturated hydrocarbons for preparing chemical intermediates and products represents an attractive goal. The possibility of converting alkane in a controlled way into alcohols, ketones etc., i.e. to oxyfunctionalize them, is particularly challenging. After a short account of previous methods used for the oxidation of alkanes, particular emphasis will be given to recently developed reactions of alkanes with oxygenating agents in superacidic media.     

Can alkane isomers be separated? Adsorption equilibrium and kinetic data for hexane isomers and their binary mixtures on MFI

In this study we present a global overview of the adsorption behavior of hexane isomers on MFI. With an experimental approach that couples a manometric technique with Near Infrared (NIR) spectroscopy, which has been recently developed, we did address adsorption kinetic properties of n-hexane, 2-methylpentane, 2,2-dimethylbutane and 2,3-dimethylbutane, and their binary mixtures. The adsorption equilibrium properties of the binary mixtures were also assessed using the same technique. Whereas the adsorption isotherms and heats of adsorption for single components have been studied by a manometric technique coupled with a micro calorimeter. The differential heats of adsorption of n-hexane increase slightly with loading, on the other hand the heat of adsorption of branched hexanes exhibits a decrease with loading. The diffusion rates on MFI of n-hexane, 2-methylpentane and 2,3-dimethylbutane are in the same order of magnitude. However, the diffusion rate of 2,2-dimethylbutane is two orders of magnitude lower than rates of the other isomers. In the binary mixtures the components interact and the difference between the diffusion rates of the components decreases. The MFI zeolite presents equilibrium selectivity towards the less branched isomers. In conclusion, a separation process for linear/mono-branched alkanes + double-branched alkanes, has to be based on its equilibrium properties and not based on adsorption kinetics.     

Thermodynamic properties for binary liquid mixtures of 1-chlorobutane+n-alkanes

Isothermal compressibilities K and isobaric thermal expansion coefficients _p have been measured at 25 and 45°C for pure components and the following binary mixtures: 1-chlorobutane+normal alkanes (n-C_n) where n=6, 8, 10, 12, 14 and 16. With these results and other thermodynamic data from literature the next mixing quantities have also been reported: (V ^E/T)_P, – (V)^E/P)_T, K _S ^v , H ^E/P)_T, (_pVT and C_v. The obtained results have been compared at 25°C with the calculated values by using the Prigogine-Flory-Patterson theory of liquid mixtures. The theory predicts the excess volume V^E and V ^E/P)_T values rather well, the C _P ^E quite poorly, while for V ^E/T)_P and V ^E/P)_T it is only predicted the trend with the chain length of the n-alkane. The last two quantities show deviations between theoretical and experimental, slightly higher in systems with longer n-alkanes than for shorter ones. Our conclusion is that a nonrigid linear molecule, like 1-chlorobutane, has a low ability as a breaker of the pure n-C_n orientation correlations, in between that which we found for toluene and p-xylene and much smaller than for cyclohexane or benzene.     

Correlation between MO eigenvectors and enthalpies of formation for alkanes

A new model for the calculation of enthalpies of formation of alkanes (up to C₈) is presented. An additive bond energy scheme, using the experimental methane and diamond values for the CH and CC bond energies, respectively, is supplemented by correction for the CC π antibonding character of the highest occupied molecular orbitals (HOMOs), effectively adjusting the CC bond energies. The effect is calculated by the summation of products of appropriate eigenvectors from semiempirical PM3 or HF/STO-3G calculations, after orthogonal transformation. The enthalpy of formation can then be expressed in terms of only one adjustable parameter. With HF/STO-3G eigenvectors, the mean discrepancy between experimental and calculated enthalpies of formation, after a one-parameter correction for 1,4 steric interactions, is 2.2 kJ mol⁻¹, comparable with more highly parameterized models. The results using PM3 eigenvectors are less satisfactory, probably on account of the neglect of overlap in the semiempirical scheme.     

Polymerization of Langmuir–Blodgett films of diacetylenes

Monolayer and multilayer assemblies of Langmuir–Blodgett films of 10–12 pentacosadyinoic acid (12–8 diacetylene) were deposited on flat gold substrates. Micrometre-size features were patterned by polymerization of the films by using standard electron beam lithography. Polymerized areas on a monolayer and bilayer, as well as multilayer films, were examined by scanning electron microscopy, atomic force microscopy and resonant Raman spectroscopy. It was established that polymerized areas on a monolayer and bilayer LB film adhere onto the gold substrate after development. The exposure curve, sensitivity, contrast and resolution of the polymer have been determined by using atomic force microscopy and correlated with the deposition conditions and molecular parameters. Stresses induced in the organic film during polymerization lead to an in-plane buckling of the micrometre-size polymer structure. A simple self-consistent theory was developed to predict critical strain and critical length of buckling. The observed effect of buckling of polymers might open an avenue for a wide range of important practical applications in the area of nanomechanical engineering.     

应用分子子图指数估计与预测烷烃核磁共振碳谱位移和

系统地研究了核磁共振碳谱(¹³C NMR)与化学位移规律及其定量构谱关系(QSSR).本文研究了一组多元素分子子图指数矢量(VMSG),并发现它与烷烃化学位移和(CCSA)有很好线性相关性.采用多元线性回归(MVLR)进行准确估计与预测,结果良好.