Assignment of absolute configuration of cyclic secondary amines by NMR techniques using Mosher's method: a general procedure exemplified with (-)-isoanabasine

A general procedure to determine the absolute configuration of cyclic secondary amines with Mosher's NMR method is demonstrated, with assignment of absolute configuration of isoanabasine as an example. Each Mosher amide can adopt two stable conformations (named rotamers) caused by hindered rotation around amide C-N bond. Via a three-step structural analysis of four rotamers, the absolute configuration of (-)-isoanabasine is deduced to be (R) on the basis of Newman projections, which makes it easy to understand and clarify the application of Mosher's method to cyclic secondary amines. Furthermore, it was observed that there was an unexpected ratio of rotamers of Mosher amide derived from (R)-isoanabasine and (R)-Mosher acid. This phenomenon implied that it is necessary to distinguish the predominant rotamer from the minor one prior to determining the absolute configuration while using this technique.

Compositional differences of propylene-ethylene block copolymers manufactured by degradation and hydrogenation techniques

The purpose of the present work is to investigate the compositional difference of polypropylene-polyethylene block copolymers (PP-b-PE) manufactured industrially by the process of degradation and hydrogenation, respectively. Each of the PP-b-PE copolymers was fractionated into three fractions with heptane and chloroform. The compositions of the three fractions were characterized by C-13 nuclear magnetic resonance (NMR) and Fourier transform infrared (FTIR) spectroscopy, as well as differential scanning calorimetry (DSC) and thermal fractionation. The results showed that the Chloroform-soluble fraction was amorphous ethylene-propylene rubber, and the content of the rubber in PP-b-PE manufactured by hydrogenation was less than that by degradation. The degree of crystallinity of the chloroform-insoluble fraction of the PP-b-PE manufactured by hydrogenation is higher than that of by degradation.

Comparison of biochemical effects induced by Changle between male and female rats using NMR and ICP-MS techniques

Metabolic profiles caused by rare earth complex were investigated using NMR and ICP-MS techniques. Male and female Wistar rats were treated orally with Changle (A kind of rare earth complex applied in agriculture to raise the production of crops) at dose of 2, 5 and 20 mg (.) kg(-1) body weight/day respectively for 90 d. Urine and serum samples are collected on 90 d. The relative concentrations of important endogenous metabolites in urine and serum are determined from H-1 NMR spectra and the contents of the four rare earth elements ( La, Ce, Pr and Nd) constituting Changle in the serum samples are measured by ICP-MS technique. Changle-induced renal and liver damage in rats is found based on the increase in the amounts of the amino acids, trimethylamine N-oxide, N, N-dimethyglycine, dimethylamine, succinate, aketoglutarate and ethanol as well as rare earth concentrations. The similarities and differentiations are found in the alteration patterns of metabolites and rare earth concentrations in serum.

Investigating mechanical response of single chain polystyrene particles by scanning probe techniques

Single chain polystyrene particles were obtained by dilute solution casting method. The sample with both single chain polystyrene particles and multi-chain (more than 1000 molecular chains) polystyrene particles was obtained by a little more concentrate solution. Force modulation technique showed that single chain polystyrene particles were softer than multichain polystyrene particles. On the other hand, nanoindentation experiments on multi-chain particles and bulk polystyrene manifested that the elastic modulus of multi-chain polystyrene particles was very close to that of bulk polystyrene. Therefore, it was concluded that single chain polystyrene particles were softer than bulk polystyrene,which indicated that the density of intrachain entanglement points in the single chain polystyrene particles was not as large as that of the interchain entanglement points in the bulk state.

Recent development of tip modification techniques in chemical force microscope

A review is given on the recent development of scanning probe microscope (SPM) tip modification techniques for chemical force microscope, including the preparation and application of SPM tip modified by self-assembled monolayer, atomic force microscope (AFM) tip modified by biological molecule, scanning tunneling microscope tip modified by electrochemical method, AFM tip modified by carbon nanotube.

Characterization of the structural and functional changes of hemoglobin in dimethyl sulfoxide by spectroscopic techniques

Circular dichroism (CD), fourier transform infrared (FTIR), and fluorescence spectroscopy were used to explore the effect of dimethyl sulfoxide (DMSO) on the structure and function of hemoglobin (Hb). The native tertiary structure was disrupted completely when the concentration of DMSO reached 50% (v/v), which was determined by loss of the characteristic Soret CD spectrum. Loss of the native tertiary structure could be mainly caused by breaking the hydrogen bonds, between the heme propionate groups and nearby surface amino acid residues, and by disorganizing the hydrophobic interior of this protein. Upon exposure of Hb to 52% DMSO for ca. 12 h in a D2O medium no significant change in 1652 cm(-1) band of the FTIR spectrum was produced, which demonstrated that alpha-helical structure predominated. When the concentration of DMSO increased to 57%: (1) the band at 1652 cm(-1) disappeared with the appearance of two new bands located at 1661 and 1648 cm(-1); (2) another new band at 1623 cm(-1) was attributed to the formation of intermolecular beta-sheet or aggregation, which was the direct consequence of breaking of the polypeptide chain by the competition of S=O groups in DMSO with C=O groups in amide bonds. Further increasing the DMSO concentration to 80%, the intensity at 1623 cm(-1) increased, and the bands at 1684, 1661 and 1648 cm(-1) shifted to 1688, 1664 and 1644 cm(-1), respectively. These changes showed that the native secondary structure of Hb was last and led to further aggregation and increase of the content of 'free' amide C=O groups. In pure DMSO solvent, the major band at 1664 cm(-1) indicated that almost all of both the intermolecular beta-sheet and any residual secondary structure were completely disrupted. The red shift of the fluorescence emission maxima showed that the tryptophan residues were exposed to a greater hydrophilic environment as the DMSO content increased. GO-binding experiment suggested that the biological function of Hb was disrupted seriously even if the content of DMSO was 20%. (C) 1998 Elsevier Science B.V. All rights reserved.

Study of cupric hexacyanoferrate-modified platinum electrodes using probe beam deflection and electrochemical quartz crystal microbalance techniques

The ion exchange mechanism accompanying the oxidation/reduction processes of cupric hexacyanoferrate-modified platinum electrodes in different aqueous electrolyte solutions has been studied by means of in situ probe beam deflection and the electrochemical quartz crystal microbalance technique. The results demonstrate that the charge neutrality of the film during the reoxidation/reduction process is accomplished predominantly by the movement of cations, but anions and/or solvent are also participator(s). Moreover, in KHC8H4O4 (potassium biphthalate) solution, the EQCM data obtained from chronoamperometry experiment are more complicated than those in KCl and K2SO4 solutions. (C) 1997 Elsevier Science Ltd.

COMPARATIVE-STUDY OF KALMAN FILTERING, SYNCHRONOUS EXCITATION AND NUMERICAL DERIVATIVE TECHNIQUES IN FLUOROMETRY

The performance of Kalman filtering, synchronous excitation and numerical derivative techniques for the resolution of overlapping emission spectra in spectrofluorimetry was studied. The extent of spectrum overlap was quantitatively described by the separation degree D(s), defined as the ratio of the peak separation to the full width at half-maximum of the emission spectrum of the interferent. For the system of Rhodamine B and Rhodamine 6G with a large D(s) of about 0.4, both Kalman filtering and synchronous techniques are able to resolve the overlapping spectra well and to give satisfactory results while the derivative spectra are still overlapped with each other. Moreover, the sensitivities are greatly decreased in derivative techniques. For more closely spaced spectra emitted by the complexes of Al and Zn with 7-iodo-8-hydroxyquinoline-5-sulphonic acid (Ferron)-hexadecyltrimethylammonium bromide, the synchronous excitation technique cannot completely separate the overlapping peaks, although it increases the separation degree from 0.25 in the conventional spectra to 0.37 in the synchronous spectra. On the other hand, Kalman filtering is capable of resolving this system. When the Al/Zn intensity ratio at the central wavelength of Al was > 1, however, the accuracy and precision of the estimates for Zn concentration produced by the Kalman filter became worse. In this event, the combination of synchronous excitation and Kalman filtering can much improve the analytical results.

ON THE SIGNIFICANCE OF WAVELENGTH POSITIONING ACCURACY IN MULTICOMPONENT ANALYSIS TECHNIQUES FOR THE CORRECTION OF LINE INTERFERENCES IN INDUCTIVELY COUPLED PLASMA ATOMIC EMISSION-SPECTROMETRY

The present paper reports some definite evidence for the significance of wavelength positioning accuracy in multicomponent analysis techniques for the correction of line interferences in inductively coupled plasma atomic emission spectrometry (ICP-AES). Using scanning spectrometers commercially available today, a large relative error, DELTA(A) may occur in the estimated analyte concentration, owing to wavelength positioning errors, unless a procedure for data processing can eliminate the problem of optical instability. The emphasis is on the effect of the positioning error (deltalambda) in a model scan, which is evaluated theoretically and determined experimentally. A quantitative relation between DELTA(A) and deltalambda, the peak distance, and the effective widths of the analysis and interfering lines is established under the assumption of Gaussian line profiles. The agreement between calculated and experimental DELTA(A) is also illustrated. The DELTA(A) originating from deltalambda is independent of the net analyte/interferent signal ratio; this contrasts with the situation for the positioning error (dlambda) in a sample scan, where DELTA(A) decreases with an increase in the ratio. Compared with dlambda, the effect of deltalambda is generally less significant.

WAVELENGTH POSITIONING ERRORS AND TRUE DETECTION LIMIT IN RELATION TO MULTICOMPONENT ANALYSIS TECHNIQUES FOR THE CORRECTION OF LINE INTERFERENCES IN INDUCTIVELY COUPLED PLASMA ATOMIC EMISSION-SPECTROMETRY

The present paper deals with the evaluation of the relative error (DELTA(A)) in estimated analyte concentrations originating from the wavelength positioning error in a sample scan when multicomponent analysis (MCA) techniques are used for correcting line interferences in inductively coupled plasma atomic emission spectrometry. In the theoretical part, a quantitative relation of DELTA(A) with the extent of line overlap, bandwidth and the magnitude of the positioning error is developed under the assumption of Gaussian line profiles. The measurements of eleven samples covering various typical line interferences showed that the calculated DELTA(A) generally agrees well with the experimental one. An expression of the true detection limit associated with MCA techniques was thus formulated. With MCA techniques, the determination of the analyte and interferent concentrations depend on each other while with conventional correction techniques, such as the three-point method, the estimate of interfering signals is independent of the analyte signals. Therefore. a given positioning error results in a larger DELTA(A) and hence a higher true detection limit in the case of MCA techniques than that in the case of conventional correction methods. although the latter could be a reasonable approximation of the former when the peak distance expressed in the effective width of the interfering line is larger than 0.4. In the light of the effect of wavelength positioning errors, MCA techniques have no advantages over conventional correction methods unless the former can bring an essential reduction ot the positioning error.

IMPROVEMENT OF SELECTIVITY WITH NUMERICAL DERIVATIVE TECHNIQUES IN INDUCTIVELY COUPLED PLASMA ATOMIC EMISSION-SPECTROMETRY

One of the most attractive features of derivative spectrometry is its higher resolving power. In the present power, numerical derivative techniques are evaluated from the viewpoint of increase in selectivity, the latter being expressed in terms of the interferent equivalent concentration (IEC). Typical spectral interferences are covered, including flat background, sloped background, simple curved background and various types of line overlap with different overlapping degrees, which were defined as the ratio of the net interfering signal at the analysis wavelength to the peak signal of the interfering line. the IECs in the derivative spectra are decreased by one to two order of magnitudes compared to those in the original spectra, and in the most cases, assume values below the conventional detection limits. The overlapping degree is the dominant factor that determines whether an analysis line can be resolved from an interfering line with the derivative techniques. Generally, the second derivative technique is effective only for line overlap with an overlapping degree of less than 0.8. The effects of other factors such as line shape, data smoothing, step size and the intensity ratio of analyte to interferent on the performance of the derivative techniques are also discussed. All results are illustrated with practical examples.

基于GIS的黄河三角洲地面沉降研究及相关分析

黄河三角洲存在着不可忽视的地面沉降现象，并在一定程度上阻碍着三角洲的快速发展。对黄河三角洲地面沉降的研究在黄河三角洲防灾减灾、土地利用、河口河道治理等方面具有理论与实践指导意义。 本文收集了黄河三角洲地区1956年、1967年、1980年和1995年四个时期的1：5万地形图，提取高程信息，应用地理信息系统（GIS）软件生成数字高程模型并展开了相应的空间分析，得到各个时间段内黄河三角洲的地面沉降速率图，通过对各沉降速率图的统计分析得出了三角洲地区地面沉降的时空变化规律。文章继而分析了引发黄河三角洲地面沉降的三个主要诱导因子、它们在影响范围、作用时间、作用强度等方面的特点，以及在不同时间段内各诱导因子在引发地面沉降方面所发挥作用的主次。随后，在列举地面沉降对黄河三角洲产生的影响之后，归纳总结了防治地面沉降及其引发灾害的对策。最后，基于采用常规水准测量方法进行地面沉降监测费时费力，提出利用InSAR技术对黄河三角洲地面沉降进行监测的设想，并简要分析了其可行性。

基于GIS探讨人类活动和坡度对藏羚生境的影响

以3S技术为手段，研究了藏羚在青海最主要分布区曲麻莱、治多和可可西里境内藏羚生境状况及其坡度、道路、和居民点对藏羚生境的影响。通过野外考察基本掌握了藏羚的生境的基本特征，取得了考察路线附近区域内藏羚分布的GPS数据及其具有对应的数量、地形地貌、生境类型、人类活动状况等属性数据的藏羚分布点图层。对研究地区LANDSAT TM / ETM+ 5（红）、4（绿）、3（蓝）波段组合影像进行非监督分类，共分出水体和裸岩、沼泽地、沙地、砾石地、低草地、中草地和高草地7种生境类型，将藏羚生境适宜等级划分为不适宜、较差、适宜和非常适宜，其中适宜等级和非常适宜等级的生境类型为藏羚适宜的生境。 首先，将藏羚分布点图层分别和遥感影像假彩色合成图像、坡度图层、道路图层、居民点图层进行叠加分析、距离查询等分析了遥感影像非监督分类的判图依据，设立了坡度、道路、居民点对藏羚生境影响强度的评价原则。然后，通过对研究地区遥感影像进行非监督分类分析研究了藏羚不同适宜程度的生境面积。通过坡度分析和地图查询分析研究了坡度对藏羚生境的影响。通过缓冲区分析研究了道路和居民点对藏羚生境的影响。最后将坡度、道路和居民点三个因素结合起来通过地图综合查询分析研究了这三个因素对藏羚生境的综合影响，并给出了研究地区藏羚不同适宜等级的生境面积。 主要的研究结果和结论如下： 1、从不同类型生境在研究地区中所占比例的趋势上看，治多地区和曲麻莱地区的植被要明显优于可可西里地区，这与整个研究地区从西北到东南地势逐渐降低、水热条件逐渐变好的趋势相一致，至少可以说，从食物条件来看，治多地区和曲麻莱地区比可可西里地区更适于藏羚的栖息。 在曲麻莱地区藏羚的潜在生境面积共26861 km2，占该地区总面积的69%；在治多地区藏羚的潜在生境面积共21617 km2，占该地区总面积的68%；在可可西里地区藏羚的潜在生境面积共26398 km2，占该地区总面积的54%。 2、根据藏羚分布点图层与坡度分析图层的地图查询分析，把藏羚的生境按坡度分为2类，坡度小于等于30度时为适宜生境，坡度大于30度时为不适宜生境。将研究地区坡度栅格图像（grid文件）和非监督分类结果栅格图像（grid文件）进行地图查询分析，结果表明，在整个研究地区坡度大于30度的生境面积所占的比例不到总面积的3%，坡度影响下研究地区藏羚适宜栖息的生境面积变化不大。考虑到坡度的影响，曲麻莱、治多和可可西里适合藏羚栖息的面积分别为26663 km2（68%）、21187 km2（66%）和26350 km2（54%）。 3、根据最近原则连接藏羚分布点图层与道路图层空间数据，通过Distance综合查询分析，把道路对藏羚的影响程度划分为4个等级：距离道路0－1000m，强烈影响；距离道路1000－2000m，中度影响；距离道路2000－3000m，轻度影响；距离道3000m以外，无影响。然后在ArcView GIS 3.2a软件环境的支持下对研究地区的道路图层分别做距离道路为1000m、2000m和3000m的缓冲区分析研究，则曲麻莱、治多和可可西里地区藏羚生境受道路累计影响的面积及其分别占各研究地区总面积的比例分别为20215 km2（51.80%）、19480 km2（61%）和4437 km2（9 %）。考虑道路对藏羚生境的影响，在治多和曲麻莱地区，由于道路的影响将使得藏羚生境大面积丧失，生境高度破碎化。 4、根据最近原则连接藏羚分布点图层与居民点图层空间数据，通过Distance综合查询分析，把居民点对藏羚的影响程度划分为4个等级：距离居民点0－3000m，强烈影响；距离居民点3000－6000m，中度影响；距离居民点6000－9000m，轻度影响；距离居民点9000m以外，无影响。然后在ArcView GIS 3.2a软件环境的支持下对研究地区的居民点图层分别做距离居民点距离为3000m、6000m和9000m的缓冲区分析。曲麻莱、治多和可可西里地区藏羚生境受居民点影响的面积及其分别占总面积的比例分别为11282 km2（29%）、15258 km2（48%）和3846 km2（8%）。从居民点对藏羚生境的影响看，由于居民点的影响使得治多和曲麻莱地区，尤其是治多地区，藏羚生境大面积丧失，生境高度破碎化。 5、人类活动（主要是道路和居民点）对藏羚生境适宜生境面积的影响是研究中主要的内容，鉴于道路和居民点对藏羚生境影响的评价原则分类方法一致，我们把道路和居民点对藏羚的影响程度合并为4个等级（距离道路0－1000m内或距离居民点0－3000m内，强烈影响；距离道路1000－2000m内或距离居民点3000－6000m内，中度影响；距离道路2000－3000m内或距离居民点6000－9000m内，轻度影响；距离道路3000m以外或距离居民点9000m以外，无影响，对道路和居民点相应距离的缓冲区分析图层进行合并等操作，测定曲麻莱、治多和可可西里地区藏羚生境受人类活动影响的面积及其占总面积的比例分别为21595 km2（55%）、22271 km2（70%）和4775 km2（10%）。 在治多和曲麻莱地区，由于人类活动的影响使得藏羚生境大面积丧失，生境高度破碎化，尤其是治多地区，影响面积达将近70%。在可可西里地区，10%的影响面积虽然不是太大，但是近几年来由于各种形式的旅游日趋升温，尤其是青藏铁路建设开通，将增加道路对藏羚生境的影响程度。人类活动影响在研究地区分布极不平均，在曲麻莱的中东部、治多的东部以及可可西里的109国道附近人类活动影响的强度较大，在这些地区藏羚的生存条件恶劣，甚至部分地区已经不适合藏羚栖息了。 6、最后，基于研究地区的坡度grid图层、非监督分类grid图层以及不同程度人类活动影响的grid图层，对不同坡度、道路和居民影响的生境面积进行综合查询分析。把人类活动对藏羚生境的影响强度重新划分为如下3个等级，A、短距离影响，距离道路1000m或距离居民点3000m范围内的影响，也就是人类活动的强烈影响；B、中距离影响，距离道路2000m或距离居民点6000m范围内的影响，也就是人类活动的强烈影响和中度影响之和；C、长距离影响，距离道路3000m或距离居民点9000m范围内的影响，也就是人类活动的强烈影响、中度影响和轻度影响的总和。曲麻莱、治多和可可西里研究地区中坡度小于等于30度并且人类活动长距离范围影响下藏羚适合栖息的生境面积及占相应研究地区总面积的比例为12597 km2（32%）、6117km2（19%）和23564km2（48%）。 在研究地区，治多地区人类活动对藏羚生境适宜性的影响最为严重，其次为曲麻莱地区，而可可西里地区的人类活动影响较小。尤其是治多地区和曲麻莱地区，当人类活动的影响最大距离时，治多地区藏羚适宜生境面积竟然不到总面积的1/5，曲麻莱地区不到1/3。这两地区人类活动主要集中在东部，导致治多东部地区和曲麻莱中东部地区几乎没有藏羚分布。于是，由于人类活动的影响，使得拥有良好生境条件的治多和曲麻莱地区适合藏羚栖息的生境却较少，而生境条件相对较差的可可西里地区反而拥有相对较多的适合藏羚栖息的生境。