Structural and dynamical properties of methane clathrate hydrates

Equilibrium molecular dynamics (MD) simulations have been performed in both the NVT and NPT ensembles to study the structural and dynamical properties of fully occupied methane clathrate hydrates at 50, 125, and 200 K. Five atomistic potential models were used for water, ranging from fully flexible to rigid polarizable and nonpolarizable. A flexible and a rigid model were utilized for methane. The phonon densities of states were evaluated and the localized rattling modes for the methane molecules were found to couple to the acoustic phonons of the host lattice. The calculated methane density of states was found to be in reasonable agreement with available experimental data.     

Multiple steady states in a CSTR with total condenser: Comparison of equilibrium and nonequilibrium models

Comparison of equilibrium and nonequilibrium models of a CSTR with total condenser focused on the multiple steady states and dynamic behaviour was carried out. The steady-state behaviour of the model system, MTBE synthesis from methanol and isobutene in a reactive distillation column, was studied in terms of the input parameters, i. e. feed flow rate of methanol or butenes, reflux ratio, and mass of catalyst. The dynamic behaviour of the system during the start-up was investigated and perturbations of manipulated variables were found to cause transitions between the parallel steady states. Presented at the 33rd International Conference of the Slovak Society of Chemical Engineering, Tatranské Matliare, 22–26 May 2006.     

New Experimental Insight into the Nature of Metal−Metal Bonds in Digallium Compounds: J Coupling between Quadrupolar Nuclei

Multiple bonding between atoms is of ongoing fundamental and applied interest. Here, we report a multinuclear (¹H, ¹³C, and ⁷¹Ga) solid‐state magnetic resonance spectroscopic study of digallium compounds which have been proposed, albeit somewhat controversially, to contain single, double, and triple Ga?Ga bonds. Of particular relevance to the nature of these bonds, we have carried out two‐dimensional ⁷¹Ga J/D‐resolved NMR experiments which provide a direct measurement of J(⁷¹Ga,⁷¹Ga) spin–spin coupling constants across the gallium?gallium bonds. When placed in the context of clear‐cut experimental data for analogous singly, doubly, and triply bonded carbon spin pairs or boron spin pairs, the ⁷¹Ga NMR data clearly support the notion of a different bonding paradigm in the gallium systems. Our findings are consistent with an increasing role across the purported gallane–gallene–gallyne series for classical and/or slipped π‐type bonding orbitals.     

Fast analysis of triterpenoids in Ganoderma lucidum spores by ultra‐performance liquid chromatography coupled with triple quadrupole mass spectrometry

A rapid and reliable method was established for simultaneous determination of main triterpenoids in Ganoderma lucidum spores using ultra‐high‐performance liquid chromatography coupled with triple quadrupole mass spectrometry (UPLC‐TQ‐MS). The established method was validated in terms of linearity, sensitivity, precision, accuracy and stability, and was successfully applied to determine the contents of 10 main triterpenoids in different batches of G. lucidum spores. The analysis results showed that moderate levels of triterpenoids were found in G. lucidum spores. In addition, a MS full scan with a daughter ion scan experiment was performed to identify the potential derivatives of triterpenoids present in G. lucidum spores. As a result, a total of 22 triterpenoids from different G. lucidum spores were unequivocally or tentatively identified via comparisons with authentic standards and literatures. This method provides both qualitative and quantitative results without the need for repetitive UPLC‐MS analyses, thereby increasing efficiency and productivity, making it suitable for high‐throughput applications. Copyright © 2013 John Wiley & Sons, Ltd.     

Time-delay effects on dynamics of a two-actor conflict model

We present a study of time-delay effects on a two-actor conflict model based on nonlinear differential equations. The state of each actor depends on its own state in isolation, its previous state, its inertia to change, the positive or negative feedback and a time delay in the state of the other actor. We use both theoretical and numerical approaches to characterize the evolution of the system for several values of time delays. We find that, under particular conditions, a time delay leads to the appearance of oscillations in the states of the actors. Besides, phase portraits for the trajectories are presented to illustrate the evolution of the system for different time delays. Finally, we discuss our results in the context of social conflict models.     

Base‐Stabilized Phosphinidene Boranes by Silylium‐Ion Abstraction

We report the preparation of N‐heterocyclic carbene (NHC)‐stabilized compounds containing P=B double bonds. The reaction of the highly functionalized phosphinoborane Mes*(SiMe₃)P?B(Cl)Cp* with Lewis bases allows access to base‐stabilized phosphinidene boranes Mes*P=B(L)Cp* (L=4‐dimethylaminopyridine (DMAP), NHC) by Me₃SiCl elimination. The formation of these species is shown to proceed through transient borylphosphide anions generated by Me₃Si abstraction.     

层叠Blumlein线多开关导通时间分散性

高介电常数陶瓷储能脉冲形成线需要用到多开关触发的层叠Blumlein线结构。从形成线波过程理论出发，分析了多开关导通时间分散性对层叠Blumlein线及其输出波形的影响。主要包括两方面影响:其一是造成输出方波脉冲的前沿和后沿均出现阶梯形畸变；其二是使得各延迟导通的平行平板Blumlein线承受过电压，容易引起陶瓷储能介质的电击穿。在不单独考虑开关电感的理想情况下，利用PSpice电路程序模拟了开关导通时间分散性对四级层叠Blumlein线的影响，模拟结果与波过程理论分析一致。为减弱这些影响，提出了可行的解决方案。     

Minireview: Advances in Germanium Isotope Analysis by Multiple Collector–Inductively Coupled Plasma–Mass Spectrometry

The advent of multiple collector–inductively coupled plasma–mass spectrometry (MC-ICP-MS) has made the high-precision determination of Ge isotopes possible, which leads to the widespread application of Ge isotopes in earth, ocean, and cosmochemistry fields. This paper reviews the history of Ge isotope analysis, chemical dissolution and purification, and mass spectrometry measurements. Concentrated HNO₃ is sufficient to dissolve nearly all types of samples and HF is also involved for Si-rich samples. Low-temperature ashing prior to dissolution is an alternative way to preconcentrate Ge in organic-rich samples. For different matrices, Ge isotopes can be determined by MC-ICP-MS coupled with a traditional nebulizer system or hydride generation system after two-step separation, one step cation/anion-exchange separation, or Mg/Fe co-precipitation protocols. Ion-exchange column methods are suitable for samples with elevated matrix and Ge content such as sulfides, iron oxides, silicate rocks, and coals, whereas Mg or Fe coprecipitation methods are particularly suitable for all kinds of water. Hydride generation systems are improved over traditional nebulizer system due to the smaller sample quantity and fewer matrix-related interferences. Sample-standard bracketing, double spike, and external Ga isotope normalization are used to mass bias correction and yield consistent results. Analytical methods involving Ge-poor samples and Ge isotope analyses based on different Ge species or specific Ge compound in natural environment will be important prospects in the further study. For further applications of Ge isotopes in mineral deposits such as sulfide and iron oxide deposits, sulfides, and iron oxides reference materials should be developed in the future.     

The role of delay times in subcycle-resolved probe retardation measurements

The delay in the nonlinear response of matter to intense laser pulses has been studied since a long time regarding its nuclear contribution. In contrast, the electronic part of the nonlinear response in wide-band-gap dielectrics, which is usually dominant, is not well explored regarding its delay, and previous studies have revealed that the timescale is below 1 fs. Here, the influence of delay times on the recently introduced method of subcycle-resolved probe retardation measurements is investigated using a simulation. In the model assumed, the electronic nonlinearity is divided into the third order Kerr effect and the plasma contribution due to conduction band population in the strong laser field. In the regime of close-to-collinear pump-probe geometries, the probe retardation shows both π- and 2π-oscillations in the pump-probe delay. Sub-femtosecond delay times influence the phase of the oscillations significantly, but it remains difficult to distinguish the influence of the Kerr response from the plasma contribution.