1H and 13C NMR assignments of abietane diterpenes from Aegiphila lhotzkyana

An NMR study of one new and several known abietane diterpenes isolated from the roots of Aegiphila lhotzkyana is described. In addition to 1D NMR, several 2D shift‐correlated NMR pulse sequences (¹H–¹H‐COSY, NOESY, HMQC and HMBC) were used to establish all the structures, and unambiguously perform the ¹H and ¹³C chemical shift assignments of the new natural diterpene and three derivatives, the NMR data for which have not been reported previously. Revision of current data assignment for teuvincenone H is also suggested. Copyright © 2003 John Wiley & Sons, Ltd.     

Possible spectroscopic manifestation of the angular group induced bond alteration (AGIBA) effect in toluene

The most obvious consequence of the concept of aromaticity is the common confidence that in aromatic compounds, bond lengths do not alternate and are between typical to the single and double ones. However, in 1994, performing crystal structure investigations of substituted pyridines and their salts, Krygowski and co‐workers have discovered a very surprising angular group induced bond alteration (AGIBA) effect: It appears that some angular substituents, like methoxy or nitrozo groups, can induce bond alternation in aromatic rings. Crystal studies do not allow one to operate with liquids that are more common in organic chemistry. This paper presents the first possible evidence of spectroscopic manifestations of the AGIBA effect. Raman spectra of the liquid toluene are analyzed. It is found that instead of being single, the line corresponding to the ring breathing vibrations is clearly split by 1.0–1.4 cm^?1, thus indicating the presence of two (cis‐ and trans‐) AGIBA isomers. The energy difference between these isomers estimated in temperature dependent Raman studies is found equal to 6.68 kJ mol^?1. The low‐wavenumber line therefore corresponds to the cis‐AGIBA isomer and the high‐wavenumber line to the trans‐AGIBA isomer stabilized by the AGIBA effect. Copyright © 2007 John Wiley & Sons, Ltd.     

On‐line Determination of Particle Size Distributions in Flowing Dispersions

Emulsions are of great importance to industry. They are involved in many engineering operations, including chemical reactions, extraction, emulsification and suspension polymerization, etc. However, an important problem for these processes is how to control the size distribution of the dispersed phase. Indeed, off‐line analysis of the emulsion may generate uncertainties due to sampling and dilution of the product, which are likely to change the dispersion state and physico‐chemical properties. In this work, an on‐line optical method is proposed to characterize dispersed media in real flowing conditions. This method is based on the time‐analysis of back‐scattered light fluctuations. The present paper deals with the development of this method and its application to dispersions of alumina in water. The results obtained with the on‐line optical method are compared with those acquired by classical laser light scattering and microscopy.     

Fluorescence line narrowed spectra of Zn and metal-free cytochrome c

Fluorescence line narrowing (FLN) spectroscopy was used to study the role of the polypeptide chain in influencing the spectrum of Zn-substituted cytochrome c (Zn cyt c) and metal-free cyt c (porphyrin cyt c). For both derivatives the spectra show characteristics of relaxed fluorescence from an inhomogeneously broadened sample. Zero phonon lines and phonon wings can be clearly distinguished, and vibrational frequencies of the ground and excited states were identified. The inhomogeneous distribution width for porphyrin cyt c is slightly wider than that of Zn cyt c and a second population of molecules was apparent in the porphyrin cyt c. The phonon coupling was greater for Zn cyt c than for porphyrin cyt c, which may be due to the extra coupling to the polypeptide chain by metal ligation.This work has been done in partial fulfillment of the requirements for the Doctor of Philosophy degree.     

Magnetic resonance imaging and pulsed Doppler sonography of poststenotic jets: Correlation between signal void and flow velocity distribution

To correlate the appearance of poststenotic jets on gradient echo images with features of localized Doppler spectra of the jets, we studied an in vitro model of steady flow-through stenoses of 86, 96, and 99% area reduction. As fluids, water and a 40% glycerol solution in water were used. MRI was performed with a 1.5 T whole body imager and gradient echo images were obtained in planes parallel to the direction of flow. Doppler spectra were acquired separately from the MR measurements at 1 cm intervals for a distance of 10 cm downstream from the stenosis. Poststenotic signal void was observed for water and for the 40% glycerol solution only if the mean velocity within the stenosis exceeded a limit of 50–60 cm/sec. On the MR images, the jets could be divided into two segments: A proximal jet segment of uniform width equal to the diameter of the stenosis, followed by a distal jet segment which was characterized by broadening and then dissipating signal void. Except for the 99% stenosis, a high signal intensity core was present within the proximal jet segment. In the proximal jet segment, the Doppler measurements showed a low temporal fluctuation of the maximal flow velocity and only little flow opposite to the main flow direction. In the distal jet segment, the velocity fluctuation and the intensity of reverse flow increased sharply. The high signal intensity core of the jet was associated with a poststenotic zone of constant maximal flow velocity. The results demonstrate a close relationship between characteristic features of poststenotic jets in MRI and pulsed Doppler sonography.     

高频单线圈双调谐NMR单晶探头的研制

本文报道了一种测角单晶NMR探头。该探头采用单线圃双调谐电路,工作频率在90MHz-110 MHz连续可调,可进行交叉极化大功率去耦实验。文中提出了一种简单而有效的测角装置,可使单晶绕三个互相垂直轴转动实现单晶的NMR测量。作为典型的应用例子,本文利用该探头实现了单晶DGO(2NH₂CH₂COOH·H₂C₂O₄)屏蔽张量的测量。     

How should one define a (weak) crystal?

We compare two proposals for the study of positional long-range order: one in terms of the spectrum of the translation operator, the other in terms of the Fourier spectrum. We point out that only the first one allows for the consideration of molecular, as opposed to atomic, (weakly) periodic structures. We illustrate this point on the Thue-Morse system.     

Regularization of singular systems of linear algebraic equations by shifts

Regularization of singular systems of linear algebraic equations by shifts is examined. New equivalent conditions for the shift regularizability of such systems are derived.     

激光标线的原理和实验

根据几何光学知识分析了激光标线原理.理论和实验表明:激光标线长度与激光光束形状、光学元件形状及材料折射率有关.并讨论了激光标线向两侧扩展的原因.     

R~(2,1)中线性Weingarten曲面的Bcklund变换(英文)

本文对三维Minkowski空间R~(2,1)中具有性质K-2mH+m~2-l~2=0或H=constant的类时曲面定义了一个Darboux线汇,同时得到了相应的Bcklund变换。