Millimeter-Wave Spectroscopy of Methylfuran Isomers: Local vs. Global Treatments of the Internal Rotation

Methylfurans are methylated aromatic heterocyclic volatile organic compounds and primary or secondary pollutants in the atmosphere due to their capability to form secondary organic aerosols in presence of atmospheric oxidants. There is therefore a significant interest to monitor these molecules in the gas phase. High resolution spectroscopic studies of methylated furan compounds are generally limited to pure rotational spectroscopy in the vibrational ground state. This lack of results might be explained by the difficulties arisen from the internal rotation of the methyl group inducing non-trivial patterns in the rotational spectra. In this study, we discuss the benefits to assign the mm-wave rotational-torsional spectra of methylfuran with the global approach of the BELGI-Cs code compared to local approaches such as XIAM and ERHAM. The global approach reproduces the observed rotational lines of 2-methylfuran and 3-methylfuran in the mm-wave region at the experimental accuracy for the ground vt=0 and the first torsional vt=1 states with a unique set of molecular parameters. In addition, the V3 and V6 parameters describing the internal rotation potential barrier may be determined with a high degree of accuracy with the global approach. Finally, a discussion with other heterocyclic compounds enables the study of the influence of the electronic environment on the hindered rotation of the methyl group.     

A comparison of quantitative nuclear magnetic resonance methods: internal,external, and electronic referencing

The performance of three quantitative NMR methods was compared in terms of short‐term and long‐term precision and accuracy, robustness, linear range, and general applicability. The Internal Reference method employs a reference material co‐dissolved with sample; the External Reference method employs a reference material contained in a separate solution; and the third method, known as Electronic REference To access In vivo Concentrations (ERETIC), employs an externally calibrated digital reference peak. The Internal Reference method results were the most precise and remained stable within 0.1% for at least 4 weeks. The results from the External Reference and ERETIC methods were practically equivalent to each other during this time. These methods exhibited small differences relative to the standard set by the Internal Reference method and slightly lower precision, establishing them as practical alternatives to the Internal Reference method. In contrast to the Internal Reference method, the External Reference and ERETIC methods possess several advantages that address peak overlap, flexibility of calibration, and duration of applicability. The study was designed such that each spectrum contained the information needed to compare the three methods while all other variables were kept constant. Applicability of pulse width compensation is addressed. ERETIC software compensation and minor adjustments to 90° pulse width were concluded to be unnecessary for this system. Although each of the methods was applied here to specifically calculate and compare chemical purity values, this evaluation applies generally to absolute quantitation by NMR. Copyright © 2013 John Wiley & Sons, Ltd.     

Frequency‐dependent NMR relaxation of liquids confined inside porous media containing an increased amount of magnetic impurities

Frequency‐dependent NMR relaxation studies have been carried out on water (polar) and cyclohexane (nonpolar) molecules confined inside porous ceramics containing variable amounts of iron oxide (III). The porous ceramics were prepared by compression of powders mixed with iron oxide followed by thermal treatment. The pore size distribution was estimated using a technique based on diffusion in internal fields that exposed a narrow distribution of macropore sizes with an average pore dimension independent of iron oxide content. The relaxation dispersion curves were obtained at room temperature using a fast field cycling NMR instrument. They display an increase of the relaxation rate proportional to the iron oxide concentration. This behavior is more prominent at low Larmor frequencies and is independent of the polar character of the confined molecules. The results reported here can be fitted well with a relaxation model considering exchange between molecules in the close vicinity of the paramagnetic centers located in the surface and bulk‐like molecules inside the pores. This model allows the extraction of the transverse diffusional correlation time that can be related to the polar character of the confined molecules. Copyright © 2013 John Wiley & Sons, Ltd.     

电阻抗图像重建中Jacobi矩阵的快速算法

Jacobi矩阵是电阻抗图像重建中计算量最大的部份。利用摄动法导出该矩阵的快速算法,可以大幅度地减少计算量。算例表明,这种方法是有效的。     

Optical inspection by internal reflection and spatial filtering

Some optical techniques for surface inspection applications are described. Paper texture is analyzed by a frustrated-total-internal-reflection method followed by spatial filtering of the diffracted pattern. Fibre-optics and micro-lenses are used to obtain a rugged and flexible sensor. Similar sensors are used for defect monitoring of roughly-polished surfaces. The practical aspects of sensor manufacture, speckle and vignetting considerations are discussed.     

半线性椭圆方程的正解

本文用特征理论及上下解方法,证明了一类半线性椭圆方程边值问题的正解的存在性,同时给出了解的估计.     

Existence of solutions for integral inclusions of Urysohn type with nonconvex-valued orientor field

In this paper, we prove the existence of solutions for an integral inclusion of Urysohn type with nonconvex orientor field and with delay. We make standard boundedness and continuity assumptions on the data, and we assume that the orientor field is l.s.c. in the state variable. Using a selection theorem of Fryszkowski, we are able to prove the existence of solutions, extending an earlier result of Angell.This research was supported by NSF Grant No. DMS-86-02313.     

New general guidance method in constrained optimal control,part 2: Application to space shuttle guidance

The application and the performance of the neighboring optimal feedback scheme presented in Part 1 of this paper is demonstrated for the heating-constrained cross-range maximization problem of a space-shuttle-orbiter-type vehicle. This problem contains five state variables, two control variables, and a state variable inequality constraint of order zero.This research was supported in part by the Deutsche Forschungsgemeinschaft under the Schwerpunktprogramm Anwendungsbezogene Optimierung und Steuerung.The authors wish to express their sincere and grateful appreciation to Professor Roland Bulirsch who encouraged this work.     

Service stage Petri net models with product form solution

A class of service stage Petri net models whose equilibrium probabilities satisfy local balance equations is presented. Examples of their applicability include bus oriented multiprocessor interconnections, the classical dining philosophers problem and the alternating bit protocol. The natural topological space for embedding the state transition lattice for this class of SSPN is shown to be a multidimensional toroidal manifold.     

含内裂纹的有限圆盘的平面问题

本文用弹性理论复变函数方法讨论了在内部任意位置含直线裂纹的有限圆盘在一般载荷作用下的平面问题,得到了复应力函数和应力强度因子用级数表示的一般表达式,并对此问题讨论了三种特殊情形,即裂纹受均布压应力,均布剪应力和圆盘匀速旋转的情形,其中还给出了计算应力强度因子的近似式.计算结果表明,对位于圆盘内部且不靠近外边界的中、小裂纹,这些近似式给出好的或较好的近似.