Intramolecular triarylmethane-triarylmethylium complexes with a naphthalene-1,8-diyl skeleton: isolation, structure, and reactivities of the C--H-bridged carbocations

Isolation and low‐temperature X‐ray analyses of intramolecular triarylmethane–triarylmethylium complexes with a naphthalene‐1,8‐diyl‐type skeleton have been achieved. These bridged cations prefer a C? H localized structure both in solution and in the solid state. The bridging hydrogen undergoes a facile intramolecular 1,5‐hydride shift from one carbon to another in solution. The C? H delocalized geometry is suggested to be the transition‐state structure of the degenerate rearrangement. Charge‐transfer interaction from the triarylmethane to the triarylmethylium units is evident in the electronic spectra. This interaction stabilizes the present cations. Low reactivity toward Brønsted acids indicates that these species are not the reaction intermediates in the acid‐assisted long‐bond cleavage of 1,1,2,2‐tetraarylacenaphthene derivatives.     

Effect of temperature variation on the visible and near infrared spectra of wine and the consequences on the partial least square calibrations developed to measure chemical composition

Many studies have reported the use of near infrared (NIR) spectroscopy to characterize wines or to predict wine chemical composition. However, little is known about the effect of variation in temperature on the NIR spectrum of wine and the subsequent effect on the performance of calibrations used to measure chemical composition. Several parameters influence the spectra of organic molecules in the NIR region, with temperature being one of the most important factors affecting the vibration intensity and frequency of molecular bonds. Wine is a complex mixture of chemical components (e.g. water, sugars, organic acids, and ethanol), and a simple ethanol and water model solution cannot be used to study the possible effects of temperature variations in the NIR spectrum of wine. Ten red and 10 white wines were scanned in triplicate at six different temperatures (25 °C, 30 °C, 35 °C, 40 °C, 45 °C and 50 °C) in the visible (vis) and NIR regions (400-2500 nm) in a monochromator instrument in transmission mode (1 mm path length). Principal component analysis (PCA) and partial least squares (PLS) regression models were developed using full cross validation (leave-one-out). These models were used to interpret the spectra and to develop calibrations for alcohol, sugars (glucose + fructose) and pH at different temperatures. The results showed that differences in the spectra around 970 nm and 1400 nm, related to OH bonding were observed for both varieties. Additionally an effect of temperature on the vis region of red wine spectra was observed. The standard error of cross validation (SECV) achieved for the PLS calibration models tended to inverse as the temperature increased. The practical implication of this study it is recommended that the temperature of scanning for wine analysis using a 1 mm path length cuvette should be between 30 °C and 35 °C.     

Fingerprint developing of coffee flavor by gas chromatography-mass spectrometry and combined chemometrics methods

In this paper, chromatographic fingerprint was firstly used for quality control of tobacco flavors. Based on gas chromatography-mass spectrometry (GC-MS) and combined chemometrics methods, a simple, reliable and reproducible method for developing chromatographic fingerprint of coffee flavor, one of tobacco flavors, was described. Six coffee flavor samples obtained from different locations were used to establish the fingerprint. The qualitative and quantitative analysis of coffee flavor sample from Shenzhen was completed with the help of subwindow factor analysis (SFA). Fifty-two components of 68 separated constituents in coffee flavor sample from Shenzhen, accounting for 88.42% of the total content, were identified and quantified. Then, spectral correlative chromatography (SCC) was used to extract the common peaks from other five studied coffee flavor samples. Thirty-eight components were found to exist in all six samples. Finally, the method validation of fingerprint analysis was performed based on the relative retention time and the relative peak area of common peaks, sample stability and similarity analysis. The similarities of six coffee flavor samples were more than 0.9104 and showed that samples from different locations were consistent to some extent. The developed chromatographic fingerprint was successfully used to differentiate coffee flavor from coco flavor and some little difference sample prepared with coffee flavor and coco flavor by both similarity comparison and principal component projection analysis. The developed method can be used for quality control of coffee flavor.     

Quantum chemical and nuclear magnetic resonance spectral studies on molecular properties and electronic structure of berberine and berberrubine

The structural and electronic properties of berberine and berberrubine have been studied extensively using density functional theory (DFT) employing B3LYP exchange correlation. The geometries of these molecules have been fully optimized at the B3LYP/6-311G** level. The chemical shift of 1H and 13C resonances in NMR spectra of these molecules have been calculated using the gauge invariant atomic model (GIAO) method as implemented in Gaussian 98. One- and two-dimensional HSQC (1H-13C), HMBC (1H-13C) and ROESY (1H-1H) spectra were recorded at 500 MHz for the berberine molecule in D(2)O solution. All proton and carbon resonances were unambiguously assigned, and inter-proton distances obtained from ten observed NOE contacts. A restrained molecular dynamics (RMD) approach was used to get the optimized solution structure of berberine. The structure of berberine and berberrubine molecules was also obtained using the ROESY data available in literature. Comparison of the calculated NMR chemical shifts with the experimental values revealed that DFT methods produce very good results for both proton and carbon chemical shifts. The importance of the basis sets to the calculated NMR parameters is discussed. It has been found that calculated structure and chemical shifts in the gas phase predicted with B3LYP/6-311G** are in very good agreement with the present experimental data and the measured values reported earlier.     

Discrete Periodic Sampling with Jitter and Almost Periodically Correlated Processes

The zero-mean process is said to be almost periodically correlated whenever its shifted covariance kernel is almost periodic in t uniformly with respect to . Then it admits a Fourier–Bohr decomposition: . This paper deals with the estimation of the spectral covariance a(λ,τ) from a discrete time observation of the process , when jitter and delay phenomena are present in conjunction with periodic sampling. Under mixing conditions, we establish the consistency and the asymptotic normality of empirical estimators as the sampling time step tends to 0 and the sampling period tends to infinity.      

非线性光环境中引入的反向光相移的补偿

研究利用基于非线性光环境(NOLM)的波长变换器实现非归零(NRZ)码的波长变换,对基于NOLM的波长变换器进行理论分析,指出由于NOLM中引入的反向光相移的影响,无法实现NRZ码的波长变换,给出了对反向光相移进行补偿的方法,通过计算指出,补偿反向光相移后可以实现NRZ码的波长变换.     

阶跃光纤的偏振色散

利用全反射光在光纤包层中的横向偏移和渡越时间,导出了各向同性光纤的全反射偏振色散公式及双折射光纤偏振色散的修正公式,通过模拟计算分析了偏振色散随入射角的变化规律.     

LASING FROM A DYE-DOPED PENDANT DROP AND ITS PRECESSION

We have observed lasing from the rim of dye-doped ethylene glycol pendant drops. Spatial-resolved spectral measurements show that the lasing wavelength varies along a vertical rim of the drop. Time-resolved measurements indicate that lasing precession occurs within the drop. Various lasing patterns due to lasing precession are explained. The measured precession periods for different pumping points are in good agreement with the calculated values based on morphology-dependent resonance theory.     

Al-Li合金光谱标准样品制备和定值

本文叙述了Ａｌ－Ｌｉ合金光谱分析用标准样品的制备过程和定值结果。在制备过程中采用了先进的氩气保护、新型熔剂覆盖盖技术防止锂元素的烧损,首创作了“间歇式半连续铸造法 ”、“分步调整成分法”等先进的工艺,解决了Ａｌ－Ｌｉ标样铸锭不锡成形、成易偏析等技术难关;最后采用多家协作分析定值法和科学的数理统计方法对数据处理给出定值结果和不确定度。