人淋巴瘤白血病细胞系Molt-4的31P核磁共振研究

用³¹P核磁共振(NMR)观察了人淋巴瘤白血病细胞系Molt-4的³¹P谱.NMR测试温度为37℃、20℃和4℃时,随着测试时间增长,细胞³¹P谱中ATP峰降低,无机磷峰升高,细胞³¹P谱的变化随测试温度降低依次减缓.实验温度为4℃,从收集细胞至开始NMR累加在30min内,NMR累加在60min内,获得活细胞的稳定的³¹P谱.根据细胞内无机磷的化学位移数值,对细胞内pH值进行了测定.     

31P-spectroscopy of head and neck tumors--surface coil technique

Comparative phosphorus-31 magnetic resonance spectroscopy (MRS) and magnetic resonance imaging (MRI) of 15 patients with superficial masses such as sarcoma, carcinoma, lymphoma, adenoma, and tuberculosis revealed significant increased concentrations of phosphomonoester, phosphodiester, and inorganic phosphorus in the lesion, whereas the concentration of the phosphocreatine was lower in comparison to muscle tissue. In nearly all masses, pH showed a slight alkaline shift. Existence of necrotic regions detected by MRI was marked by an increase of inorganic phosphorous in the spectra. Tumor growth was characterized by raised concentrations of phosphomonoester. Follow-up studies in a case of lymphoma showed a six-fold decrease of the tumor, while the spectra indicated a gradual transition of tumor values to muscle values. A follow-up study during irradiation of a squamous cell carcinoma revealed a considerable decrease of inorganic phosphate and a subsequent increase of phosphodiester.     

利用实验I(L)/I(K)比值改进薄膜无标样定量分析

利用透射扫描电子显微镜和X射线能谱仪,在入射电压V₀为40,80,100,120,160和200kV下,测定了从Ge到Sn八种元素薄膜的标识X射线强度比值I(L)/I(K),并结合Cliff-Lorimerk_XSi因子和它的内插值,扩充了目前仅有的少数几个L系的Cliff-Lorimer因子。为了确定哪个电离截面Q公式最好,比较了利用九种不同Q公式计算出的I(L)/I(K)和我们的实验值I(L)/I(K)。发现两者之间存在着很大的差别。进一步考虑计算强度公式中各物理参量引起的误差后,我们认为上述差别主要来源于不准确的Q公式,而且和实验值符合最好的Fabredela Ripelle的电离截面也需要进行修正。利用我们修正后的Q公式,在V₀为100和200kV下,分析了几种已知成分的样品并和EDAX的分析结果进行了比较。结果表明:在不同电压下,利用不同线系K—K,K—L,我们分析结果的误差有显著的降低。 关键词：     

Anoxia followed by hyperoxia: In vivo 31-P NMR of cat brain

In vivo ³¹P NMR spectroscopy was performed on a cat brain subjected to an extended period of anoxia followed by restoration of oxygen. High energy phosphate spectra were continuously obtained and pH measured. Following the onset of anoxia, phosphocreatine and ATP peaks decreased with a concomitant increase in inorganic phosphate. Following 34 min ventilation on 100% N₂, the animal was ventilated on 100% O₂. The spectral content progressively changed, inorganic phosphate decreased and ATP increased with the spectrum closely resembling that of control. Our results suggest that the absence of NMR detectable ATP signal cannot be interpreted as an irreversable change in cellular metabolic function.     

天然产物喹啉生物碱13C NMR谱的经验计算

本文基于化学位移加和性理论,建立了一个经验公式,利用所得公式计算了9个化合物的δ_C值,计算值与文献值符合良好,并对32个化合物的¹³C NMR化学位移进行了预测。     

Observations of energy metabolism in neuroectodermal tumors using in vivo 31P-NMR

The energy metabolism of living tumors in rats and hamsters were investigated by obtaining in vivo 31P-NMR spectra, and the effects of chemotherapy on tumors were evaluated by observing the changes of these spectra. Tumor cells of rat glioma, human glioblastoma and human neuroblastoma were inoculated subcutaneously in the lumbar region of the animals. After the tumor grew to over 1.5 cm in diameter, in vivo 31P-NMR spectrum data was obtained selectively from the tumor with a TMR-32 spectrometer (Oxford Research Systems, U.K.). Several peaks (ATP, inorganic phosphate (Pi), phosphodiesters and phosphomonoesters (PME) were observed in the tumors. The heights of these peaks varied widely corresponding to the tumor growth. However, the spectrum pattern of each tumor in an active stage was found to be essentially the same regardless of histological type or tumor origin. The phosphocreatine (PCr) peak was small, ATP and PME peaks were large and tissue pH calculated from the chemical shift of Pi was low in each tumor group. After intravenous injection of a large dose of a chemotherapeutic agent, ATP peaks decreased and the Pi peak increased gradually, resulting in a dominant Pi peak pattern after several hours in all groups. With lower drug doses, spectrum changes were temporarily seen in the tumors. These findings indicated that drugs with a high dose have a selective and a direct action on the energy metabolism of tumor tissues. In vivo 31P-NMR spectra measurement is very valuable not only to investigate the energy metabolism in tumor tissue but also to evaluate the effects of chemotherapy on the tumor.     

Syntheses and pH sensing applications of imine-coupled phenol and polyphenol species derived from 2-amino-4-nitrophenol

Developing of new generation optical polymeric pH sensors has increasing importance due to their stable structures. Available polymeric sensors for different pH ranges are already needed. In the present study new kinds of monomeric and polymeric absorption pH sensors (HBANP and PHBANP) derived from 2-amino-4-nitrophenol were prepared. The novel sensors were investigated in various pH values using spectrophotometric, spectrofluorometric, and electrochemical techniques. The sensors showed sigmoidal correlations vs. pH range in optical measurements. These correlations were improved as mathematical formula to obtain the solution pH. HBANP and PHBANP differed from each other by response fields. HBANP had a sharp absorption increase between the pH of 6.5→7.5 while PHBANP spectrophotometrically responded at lower pHs. HBANP was colorless in acidic pHs, yellow-colored in neutral media and red-colored in alkaline pHs. With its colorimetric responses in various pHs HBANP can be used to develop color-tunable pH sensors. Electrochemical oxidation peak potentials and currents also particularly changed in various pHs.     

迭代法计算多元酸碱滴定的pH

介绍了迭代法计算多元弱酸碱滴定pH计算原理,使用一个公式,用Excel计算多元酸碱滴定过程中溶液pH值,列举了H3PO4和Na2CO3滴定的pH值计算方法.     

Diffraction transfer function and its calculation of classic diffraction formula

In scalar diffraction theory, Kirchhoff formula, Rayleigh–Sommerfeld formula, and angular spectrum transmission formula are classic formulas that express diffraction correctly. But as complex calculation, Fresnel diffraction integral, which is the paraxial approximate solution to these formulas, is used widely. This paper presents diffraction transfer function corresponding to each classic diffraction formula, gives discussion on methods when using fast Fourier transform to calculate these formulas, derives conditions each formula must meet when it is calculated correctly based on sampling theorem, and finally real examples are finished to certify the results.     

High-energy phosphate metabolism during incremental calf exercise in humans measured by 31 phosphorus magnetic resonance spectroscopy (31P MRS)

Several previous 31 phosphorus magnetic resonance spectroscopy ((31)P MRS) studies performing incremental or progressive muscle exercises have observed that a decrease in pH is accompanied with an acceleration in phosphocreatine (PCr) hydrolysis. The purpose of this study was to investigate the relationship between PCr breakdown and pH during isotonic, exhaustive, incremental plantar flexion exercises. We included eight healthy, male volunteers into this study. Using a 1.5 Tesla MR scanner and a self-built exercise bench, we performed serial free induction decay (FID) (31)P MRS measurements with a time resolution of 1 min at rest, isotonic calf muscle exercise, and recovery. The exercise protocol consisted of 5-min intervals with 4.5, 6, 7.5, and 9 W workload followed by 9-min recovery. Changes in PCr and inorganic phosphate (Pi) were determined as percent changes in comparison to the baseline. In addition, pH values were calculated. This study obtained significant decreases in PCr corresponding to the gradual increases in workload. In each workload level that was succeeded by all volunteers, PCr hydrolysis passed into a steady state. After an early biphasic response, we detected a significant decrease in pH from the first to the second minute of the 6-W workload level followed by a further continuous decrease in pH up to the second minute of the recovery phase. The decrease in pH was not accompanied by acceleration in PCr hydrolysis. In conclusion, this study shows that PCr hydrolysis during incremental plantar flexion exercises passes into a steady state at different workload levels. The observed decrease in pH does not result in acceleration of PCr hydrolysis.     

Considerations for brain pH assessment by 31P NMR

Recently in vivo NMR spectroscopy has been used to measure brain pH non-invasively. Both the inorganic orthophosphate (Pi) chemical shift (delta) and the difference between the chemical shifts of phosphocreatine (PCr) and Pi(delta delta PCr-Pi) have been proposed as indicators of brain pH. However, the precise delta of Pi may be difficult to determine under normoxic conditions as is the delta of PCr under hypoxic/ischemic conditions. Ideally one needs a NMR delta parameter that: (1) linearly changes between pH 6.0-8.0, (2) is either relatively unaffected or predictably affected by cations (e.g., Mg2+) other than H+, and that (3) comes from readily observable 31P NMR resonances whose delta's can be accurately assessed under all physiological conditions. Therefore, we undertook a systematic 31P NMR study of the pH and Mg2+ titration curves for 16 phosphorus-containing metabolites observed in brain by 31P NMR. On the basis of the titration curves, the delta delta's for PCr-Pi, phosphoethanolamine (PE)-Pi, and PCr-PE fulfill criteria (1) and (2), but not criterion (3). However, the delta delta of ATP gamma-alpha fulfills all three criteria and potentially provides information on the intracellular Mg2+ concentration.     

The 13C chemical shift tensor principal values and orientations in dialkyl carbonates and trithiocarbonates

The 13C chemical shift tensor principal values for the trigonal carbonate and thiocarbonate carbon atoms in the dialkyl carbonates, dimethyl carbonate, ethylene carbonate, and diphenyl carbonate, and in the trithiocarbonates, ethylene trithiocarbonate and dimethyl trithiocarbonate, respectively, were measured in various solid-state one-dimensional and two-dimensional nuclear magnetic resonance experiments. Furthermore, the chemical shift tensor principal values and orientations were calculated for the corresponding isolated molecules with quantum mechanically fully optimized geometries. Proton-optimized X-ray geometries of ethylene carbonate, ethylene trithiocarbonate, and diphenyl carbonate were used in embedded ion method (EIM) calculations and in calculations on the isolated molecules to obtain the theoretical principal values and to assign the chemical shift tensor orientations in these three compounds. Considerable improvement in the correlation between the experimental and calculated principal values is obtained when the electrostatic crystal potentials are included in EIM calculations. The chemical shift tensor orientations and principal values obtained for the dialkyl compounds in this study complement the previous data on a series of ionic potassium carbonates and thiocarbonates.     

The C Chemical Shift Tensor Principal Values and Orientations in Dialkyl Carbonates and Trithiocarbonates

The ¹³C chemical shift tensor principal values for the trigonal carbonate and thiocarbonate carbon atoms in the dialkyl carbonates, dimethyl carbonate, ethylene carbonate, and diphenyl carbonate, and in the trithiocarbonates, ethylene trithiocarbonate and dimethyl trithiocarbonate, respectively, were measured in various solid-state one-dimensional and two-dimensional nuclear magnetic resonance experiments. Furthermore, the chemical shift tensor principal values and orientations were calculated for the corresponding isolated molecules with quantum mechanically fully optimized geometries. Proton-optimized X-ray geometries of ethylene carbonate, ethylene trithiocarbonate, and diphenyl carbonate were used in embedded ion method (EIM) calculations and in calculations on the isolated molecules to obtain the theoretical principal values and to assign the chemical shift tensor orientations in these three compounds. Considerable improvement in the correlation between the experimental and calculated principal values is obtained when the electrostatic crystal potentials are included in EIM calculations. The chemical shift tensor orientations and principal values obtained for the dialkyl compounds in this study complement the previous data on a series of ionic potassium carbonates and thiocarbonates.     

丝氨酸及其La~(3+)配合物的~1H核磁共振谱参数的pH依赖性

本文测得不同pH值下丝氨酸及其La~(3+)配合物的~1H谱,用PANIC程序对谱图进行模拟,获得化学位移和偶合常数,考察了~1H核磁共振谱参数的pH依赖性,从理论上进行了解释,并由得到的偶合常数计算出丝氨酸及其La~(3+)配合物的三种构象的比例,讨论了它们在不同pH条件下的变化,这些结果为下一步的生物大分子的研究提供了有用的信息。     

Band head spin assignment of superdeformed bands in Hg isotopes through power index formula

The power index formula has been used to obtain the band head spin(I_0) of all the superdeformed(SD) bands in Hg isotopes. A least squares fitting approach is used. The root mean square deviations between the determined and the observed transition energies are calculated by extracting the model parameters using the power index formula. Whenever definite spins are available, the determined and the observed transition energies are in accordance with each other. The computed values of dynamic moment of inertia J~((2)) obtained by using the power index formula and its deviation with the rotational frequency is also studied. Excellent agreement is shown between the calculated and the experimental results for J~((2)) versus the rotational frequency. Hence, the power index formula works very well for all the SD bands in Hg isotopes expect for ~(195)Hg(2, 3, 4).     

Integrals in the theory of four-particle atomic-molecular systems

Explicit expressions for four-particle Coulomb interaction integrals and overlap integrals for exponential basis functions dependent on five interparticle distances have been obtained. These formulas significantly simplify calculations in comparison with the general algorithm and are free from uncertainties arising in its application. The values of the integrals under consideration are calculated for a number of points forbidden in the general algorithm. The results obtained are applicable to analysis of four-particle integrals of the general form and calculation of four-particle atomic-molecular systems with partial allowance for the correlation of particle motion.     

Low-temperature thermoluminescence study of GaSe:Mn layered single crystals

Mangan doped GaSe single crystals have been studied by thermoluminescence measurements performed with various heating rates between 0.4 and 1.0 K/s in the temperature range of 10?300 K. Thermoluminescence spectra exhibited four distinguishable peaks having maximum temperatures at 47, 102, 139 and 191 K revealing the existence of trapping levels in the crystals. Curve fitting and initial rise methods were applied to observed peaks to determine the activation energies of four trapping levels. Capture cross-sections of each level were also evaluated using the obtained energy values. Moreover, heating rate dependencies of the obtained peaks were investigated. It was shown that increase in the heating rate resulted in the decrease in thermoluminescence intensity and shift of the peak maximum temperatures to higher values. Discrete, single trap behaviour was established for acceptor level related with the peak at 191 K by analysing the sequentially obtained peaks with different stopping temperatures between 15 and 65 K.     

Analysis of NMR shifts of high-spin cobalt(II) pyrazolylborate complexes

We present a detailed study on the correlation of the nuclear magnetic resonance (NMR) parameters with the results of density functional theory (DFT) calculations performed for paramagnetic high-spin cobalt(II) complexes with trispyrazolylborate ligands. This work is a first attempt to calculate dipolar and contact shifts in high-spin cobalt(II) pyrazolylborate systems. The calculation results show frontier orbitals that may be responsible for the contact shift. The contact shift values are compared with the dipolar shift ones. The latter shift values were both obtained from experimental data and calculated using DFT methods. We attempt to explain the dipolar effect, which may have a great share in NMR chemical shift of paramagnetic compounds.     

19F NMR化学位移经验公式的影响因素

化学位移是核磁共振技术的重要参数,目前对¹H NMR、¹³C NMR已提出一系列估算化学位移的经验公式,但¹⁹F NMR化学位移规律研究报道则较少,以δ=B+∑△i+C化学位移通式为基础,分析屏蔽常数对化学位移的作用,并针对¹⁹F原子,分析了氟的电子云密度、立体效应、溶剂效应、氢键、标准、浓度和温度等影响因素,对¹⁹F NMR化学位移经验公式的提出提供理论依据。     

圆介质参考波导特征方程的近似式及其应用

本文将作为参考波导的圆介质波导模式的特征方程进行了有效的近似简化,使之成为独立的四个简单特征方程组。利用这些方程组作为参考波导的特征方程来计算各种复杂波导的传输参数时,能够大大简化计算工作。