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.     

离体心脏的31P NMR谱

³¹P NMR谱自70年代后期开始被用于离体心脏中含磷化合物代谢的动态研究.^3lP NMR谱不仅可以鉴定心肌组织中浓度较高的含磷化合物,即ATP、磷酸肌酸和无机磷酸盐,而且可提供有关这些化合物化学环境(包括pH和Mg²⁺)和细胞内分布的信息.利用这一非损伤性的定量分析方法,可连续观测心肌的代谢并可同时测定离体心脏的机械功能.利用饱和转移技术还能对完整心脏中肌酸激酶和腺苷酸激酶反应的速率加一测定.本文综述介绍了近年来进行离体灌流心脏^3lP NMR谱测定的实验方法以及这一技术所提供的各种信息.     

二嗪磷的NMR研究

通过¹H , ¹³C及DQF-COSY,¹³C-¹H CO SY, COLOC等NMR技术对作为中等毒性农药二嗪磷的¹H,¹³C NMR谱峰归属作了详尽的研究，以杂化轨道理论阐明了二嗪磷结构中两个乙氧基的化学环境差异及谱峰特征, 并讨论了³¹P对二嗪磷中¹H 及¹³C NMR的影响.     

三稠环系三唑磷茂啉的化学IV.系列化合物Ⅱ和Ⅲ的31P和13C NMR研究

本文通过对两个新的三稠环系三唑磷茂啉系列化合物Ⅰ和Ⅱ的¹³C NMR谱的解析,初步指定了谱线的归属。同时,发现了系列化合物Ⅱ中³¹P NMR化学移值与Ar基上取代基的Hammett σ常数呈线性关系。     

Langendorff灌流心脏的31P NMR谱测定

测定了Langendorff灌流大鼠和兔心脏的³¹P NMR谱.观测到PCr、ATP、SP、P_i以及PME和GPC等含磷代谢物的共振峰,各谱峰之间实现了很好的分辨.在3~5min的累加时间内测得的图谱具有较好的S/N,可用于以上含磷代谢物的定量测定,以高能含磷化合物ATP和PCr相对峰强度以及冠脉流量的变化对灌流大鼠心脏代谢的稳定性进行了考察,结果表明,在本实验条件下大鼠心脏的能量储存至少可稳定2h,用所建方法以3min的时间间隔对同一大鼠心脏缺血21min及再灌注12min过程中心脏的³¹P NMR谱进行了连续跟踪测定,并初步观测了缺血及再灌注过程中心肌细胞内ATP、PCr与P_i之间的消长关系.     

双环磷酸酯类化合物NMR结构效应研究

用现有理论说明不了双环磷酸酯类化合物³¹P NMR化学位移的变化。本文在我们提出的核外电子云球对称效应原理基础上,用量子化学和分子力学计算的参数,表达了这类化合物³¹P化学位移变化的规律,同时还研究了它们的¹³C NMR化学位移和偶合常数的取代基效应。     

体内31P NMR表面线圈探头的研制

报道一种为进行活体小动物核磁共振实验而研制的体内³¹P NMK表面线圈探头.该探头工作频率为161.83MHz,无载Q值为300,可无损伤地研究生命体内各部位的性质.本文给出了用该探头所测得的小鼠体内肝脏、大腿肌肉、大脑以及大脑缺氧状态下³¹P NMR谱图实例.     

活体动物代谢过程的31P NMR研究——方法与初步结果

利用表面线圈探头测得了小鼠大脑,大腿肌肉和肝脏的体内³¹P NMR谱图。观察到PCr,ATP,PME,PDE,P_i等化合物的共振峰,并确定了各谱峰的化学位移。由大脑的P_i化学位移计算得到其细胞内pH值为7.15.用差谱方法解决了因定位不准而造成的肝脏谱图不纯。观察了小鼠大脑在缺氧状态下的代谢变化过程。当O₂浓度降至2%时,PCr开始下降,降到1%时,P_i明显升高。从空气变化到1%的O₂含量,致使小鼠死亡,小鼠大脑的pH值从7.16降到6.46。     

离子性指数、立体效应参数与膦类化合物31P NMR δP的关系

利用离子性指数(INI)和立体效应参数（α、β、γ）对100个膦化合物中磷原子进行结构表征，并与其核磁共振磷谱(³¹P NMR)建立了优良的定量构谱相关(QSSR)模型：δ_P=-163.695 3-1.003 1INI+34.632 7α+13.892 9β-3.331 7γ. 建模的计算值、留一法(Leave-One-Out, LOO)交互校验(Cross-Validation, CV)预测值的复相关系数(R)分别为0.976 5和0.973 9. 所建模型不仅在一定程度上阐明了膦类化合物³¹P NMR谱化学位移与其分子结构信息之间的关系，同时也提供了一种从理论上计算膦类化合物³¹P NMR谱化学位移的新方法，并对深入了解膦类化合物结构与性能的关系及解析、预测其³¹P NMR谱提供了一定的理论依据.     

应用E.COSY型的13C-1H相关谱准确测定果糖-1,6-二磷酸根离子中异核31P-1H和31P-13C偶合常数

建议了一种E.COSY型的¹³C-¹H相关实验.在相应的¹³C-¹H相关谱中,³¹P核对¹³C,¹H核的被动偶合给出E.COSY型的谱峰裂分,可用于准确测定含磷化合物中的³¹P-¹H和³¹P-¹³C偶合常数及其相对符号.测定了果糖-1,6-二磷酸根离子的³¹P-¹H和³¹P-¹³C偶合常数。     

O-(α-氰基-间-苯氧基苄基)硫代磷酸酯和磷酰胺的NMR研究

本文合成了20个题示的化合物,研究了它们的¹H和³¹P谱,找出了δ_P与取代基关系的一些规律,观察到了手性中心对δ_H的影响、及一个手性中心对另一个手性中心R、S体不等价的诱导位移,并观察了产物中R、S体的不同含量比例。     

杂多阴离子的NMR和ESR研究——P-V-W Keggin阴离子的31P、51V、17O-NMR谱

本文合成了六种含有P-V-W和V-V-W Keggin结构的杂多阴离子,并研究了它们的³¹P、⁵¹V、¹⁷O-NMR谱,对于PV_xW_12-xO₄₀^(x+3)-(x=1~4)阴离子,当x=1时,³¹P和⁵¹V-NMR谱只有一条线,并且此线化学位移和pH无关。当x ≥ 2时,谱线数目随着x迅速增加,其原因是几何异构体的数目和类型迅速增加。它们的化学位移δ_p,和δ_v。依赖于溶液的酸性和x,即δ_p,随pH值和x增加而减少,而δ_v,却随pH和x的增加而增加。最后简短讨论了桥氧上质子化的影响。     

Residual 31P, 35,37Cl dipolar coupling in 31P MAS spectra of chlorocyclophosphazenes

In ³¹P MAS NMR spectra of chlorocyclophosphazenes, characteristic splittings have been observed for PCl or PCl₂ groups. At different applied magnetic fields, the fine structure and total width of the patterns change in a characteristic way, demonstrating that the splittings are due to indirect spin–spin and residual dipolar interactions with the chlorine nuclei directly bonded to phosphorus. For trans-nongeminal N₃P₃Cl₃(NMe₂)₃ and N₃P₃Cl₆ as examples, the spectra have been analyzed to obtain information on chlorine nuclear quadrupole coupling constants and ^35,37Cl, ³¹P indirect spin–spin coupling constants. Neglect of these interactions may result in misinterpretations of the multiplicity in ³¹P MAS spectra of chlorophosphazenes.     

NMR-spectroscopic study of Pb in pure and barium diluted lead phosphate

³¹P and ²⁰⁷Pb MAS and static ²⁰⁷Pb NMR spectra of Pb₃(PO₄)₂ and (Pb_1−xBa_x)₃(PO₄)₂ (x=0.08, 0.12) are analysed. The resonances stemming from different cation sites are correlated with the corresponding local symmetry and their oxygen neighbours. The coordination sphere of Pb(1) consists of 12 oxygen atoms and shows characteristics of a near-axial arrangement with a comparatively low anisotropy. The tenfold coordinated Pb(2) atoms are located in a more anisotropically-coordinated site. In Pb-diluted lead phosphate crystals the Pb(2) positions appear to be preferentially substituted by barium. There are indications that the cation distributions in the diluted samples are inhomogeneous. Furthermore, ³¹P MAS NMR experiments indicate a single phosphorus position.     

金属核的磁共振研究*Ⅱ含磷配体铂(Ⅱ)络合物的195Pt和31P-NMR谱

本文测定了12个含苯基环戊基磷、亚磷酸、卤素等配体的铂(Ⅱ)络合物的¹⁹⁵Pt、³¹P-NMR谱,考察了溶剂、浓度、温度对¹⁹⁵Pt谱的影响,研究了¹⁹⁵Pt、³¹P化学位移、偶合常数与络合物几何构型的关系及对卤素的依赖关系。讨论1,2-丙二胺溶液中络合物³¹P谱的变化,以及各种含亚磷酸配体的铂络合物¹⁹⁵Pt和³¹P谱的变化。     

Solid-state 29Si, 113Cd, 119Sn, and 31P NMR studies of II-IV-P2 semiconductors

Solid-state ²⁹Si, ¹¹³Cd, ¹¹⁹Sn, and ³¹P MAS NMR spectra are reported on a series of II-IV-P₂ compounds. In favorable cases (e.g., high degree of crystallinity, low concentration of unpaired electrons), well-defined spectra, with sharp lines for each specific nearest-neighbor configuration, are observed; in such cases, expected J coupling patterns are also seen. High-resolution solid-state NMR studies of this type provide useful information on structure (disorder), doping, and electron-mediated coupling in semiconductor systems.     

In vivo 31P MRS of human brain at high/ultrahigh fields: a quantitative comparison of NMR detection sensitivity and spectral resolution between 4 T and 7 T

The primary goal of this study was to establish a rigorous approach for determining and comparing the NMR detection sensitivity of in vivo ³¹P MRS at different field strengths (B₀). This was done by calculating the signal-to-noise ratio (SNR) achieved within a unit sampling time at a given field strength. In vivo ³¹P spectra of human occipital lobe were acquired at 4 and 7 T under similar experimental conditions. They were used to measure the improvement of the human brain ³¹P MRS when the field strength increases from 4 to 7 T. The relaxation times and line widths of the phosphocreatine (PCr) resonance peak and the RF coil quality factors (Q) were also measured at these two field strengths. Their relative contributions to SNR at a given field strength were analyzed and discussed. The results show that in vivo ³¹P sensitivity was significantly improved at 7 T as compared with 4 T. Moreover, the line-width of the PCr resonance peak showed less than a linear increase with increased B₀, which leads to a significant improvement in ³¹P spectral resolution. These findings indicate the advantage of high-field strength to improve in vivo ³¹P MRS quality in both sensitivity and spectral resolution. This advantage should improve the reliability and applicability of in vivo ³¹P MRS in studying high-energy phosphate metabolism, phospholipid metabolism and cerebral biogenetics in the human at both normal and diseased states noninvasively. Finally, the approach used in this study for calculating in vivo ³¹P MRS sensitivity provides a general tool in estimating the relative NMR detection sensitivity for any nuclear spin at a given field strength.     

P and N solid-state nuclear magnetic resonance spectroscopic study of some monophospha-λ-azenes

³¹P Cross-polarization magic-angle spinning nuclear magnetic resonance (CP-MAS NMR) spectra of eight monophospha-λ⁵-azenes were measured at room temperature. Three of these compounds, with 2-OH substituents, are in principle capable of taking part in the equilibrium process. However, only the open form, tautomer A, is found in the present study. ¹⁵N CP-MAS NMR spectra support the results. The most shielded component of the ³¹P chemical shift tensor lies in the direction of the P=N bond.