31P核磁共振在肿瘤细胞代谢研究中的应用

综述31P NMR在肿瘤细胞代谢研究中的应用.通过细胞的灌流装置,用31P NMR测定细胞内含磷化合物、pH等的变化,对肿瘤细胞代谢进行分析.31PNMR能动态地一次同时监测活细胞内多种含磷代谢物及pH变化,较好地应用于肿瘤细胞的能量代谢和磷脂代谢等研究中.31P NMR具有无损伤性,克服了许多分析方法的提取分离步骤,具有独特的优点.     

用31P NMR研究硫代磷酸酯水解反应历程

磷酸酯的水解反应是一类较为重要的反应,了解这类反应历程及机理对研究农药的毒性、环境保护、及指导农药的生产与合成具有十分重要的意义。~(31)PNMR灵敏度高,化学位移范围宽,偶合常数大.~(31)P NMR的化学位移对于分子中磷原子的价态、与磷原子直接相连的原子或基团的类型、数量、性质及构型的变化十分敏感.是研究有关含磷化合物结构问题的有效手段之一,因此本文采用~(31)P NMR方法研究了疏代磷酸酯的水解反应历程。本文所研究的化合物是一种新合成的含七元环的二硫代磷酸酯。其结构式如下:     

有机磷化合物的研究 72.含磷非对映异构体^3^1P NMR 结构效应的分子力学研究

本文通过两组含磷非对映异构体~(31)p NMR化学位移的测定和分子力学计算,观察到非对映异构体之间,分子力学计算的磷原子局部Van der Waals相互作用能(E_(VDW-P))是影响其~(31)p NMR化学位移的主要因素,即E_(VDW-P)大的异构体,δ_(31P)在低场;E_(VDW-P)小的,δ_(31P)在高场。这一结果对利用非对映异构体中某核的NMR化学位移的实验测定,结合分子力学计算的该核的局部Van der Waals相互作用能。建立一种简便的确定非对映异构体中未知不对称中心的绝对构型的新方法,具有一定的理论意义和实用价值。     

新型大分子磷氮阻燃剂的合成及其在阻燃聚碳酸酯中的应用

以苯基膦酰二氯和哌嗪为原料合成了一种新型大分子含磷氮阻燃剂——聚苯基磷酰哌嗪(1),其结构经1H NMR,31P NMR和IR表征。对阻燃聚碳酸酯(2)的极限氧指数(LOI)测试结果表明:添加7%的1时,2的LOI值为34.8%。     

钒、铬、锰磷桥络合物中31P NMR化学位移的研究

ISSIe山和W6flSChllh山子1960年首次用pdCI。和二苯基磷合成出黄色的二聚络合物，后被H。yieY＊确认为具有pRZ的桥式结构．此后一系列该类结构的化合物被合成并引起了广泛的兴趣．磷可以和两个甚至多个金属原子络合构成多核金属络合物，在催化反应中有重要应用．磷原子存在多种电子态，其3d空轨道也能参与成键．P乃1的NMR谱是研究含磷化合物立体结构的有力工具．P－31与其它核素之间的耦合常数以及P－31的化学位移对阐明化合物的立体构象以及电子结构具有重要作用．近年来，West饲用计算机神经网络技术预测P－：if的化学位移，但仅…     

1-芳氧(α-取代)乙酰基-3-(取代)苯基-2-二乙氨基-2-硫(硒)代-1,3,2-二氮磷杂环戊-4-酮的合成及除草活性研究

利用P(NEt2)3与双官能基底物的环缩合反应合成了一系列新型五元磷杂环化合物. 化合物的结构经1H NMR, 31P NMR, MS和元素分析等手段证实. 对化合物Ⅱl作了X射线单晶衍射, 确定五元磷杂环为平面结构及P_N键具有dπ-pπ性质. 初步生物活性测定表明部分化合物具有较好的选择性除草活性.     

~(31)P核磁共振波谱表征高聚合度聚磷酸铵及其链结构

以液体定量~(31)P核磁共振波谱(~(31)P NMR)为主要表征手段,通过建立水中加盐促溶的高聚合度聚磷酸铵(APP)水溶液的制备方法,研究不同溶解温度、测试温度及NMR参数等对APP聚合度的影响,建立了~(31)P NMR准确表征APP的聚合度及其链结构的方法.研究结果表明,于36℃在水中加盐溶解APP,26℃下进行~(31)P NMR测试,既保证了APP溶液良好的溶解性,又在水溶液制备和~(31)P NMR测试过程中不引起APP降解,测得的APP聚合度稳定、准确.利用液体~(31)P NMR确定了不同温度下APP盐水溶液中端基磷和中间磷弛豫时间(T_1),发现T_1与温度呈线性关系,弛豫时间参数(D_1)的设置影响APP聚合度结果,D_1设置不满足磷所需的T_1时,APP的聚合度结果偏大.~(31)P NMR表征APP链结构结果显示,APP的端基磷存在3种化学环境,而溶液离子强度和温度会影响3种端基磷的化学位移;APP的中间磷中含有H~+.此外,提出了中国化工行业标准HG/T 2770-2008中APP高聚合度测定存在的问题.     

新型茚基膦金配合物的合成及其在炔烃水合反应中的催化作用研究

合成了四种新型茚基膦金配合物,其结构经1H NMR,31P NMR和元素分析表征,同时,两种配合物的结构通过X射线单晶衍射确证.化合物2能高效地催化炔烃水合反应,该催化反应具有反应条件温和、催化剂用量少、原子经济性好、对环境友好等优点.     

N-二异丙基磷酰化氨基酸-N-4-氨基吡啶衍生物的合成及对河豚毒素(TTX)解毒生物活性的研究

通过母体化合物4-氨基吡啶(4-AP)与N-二异丙基磷酰化氨基酸(DiPP-AA)在Ph3P和C2Cl6体系下的缩合反应,将具有生物活性的氨基吡啶环引入到磷酸化氨基酸结构中,设计、合成了5个N-二异丙基磷酰化氨基酸-N-4-氨基吡啶衍生物A1～A5.所有目标化合物均经IR,1H NMR,13C NMR,31P NMR,MS的表征.初步生物活性测试结果表明:目标化合物对河豚毒素(TTX)中毒的小鼠均有一定的解毒作用,并不同程度地延长了生存时间,而且毒性比母体化合物降低了.     

人宫颈癌细胞(Hela)内的31P核磁共振研究

建立了无损伤性³¹P NMR研究细胞内物质的实验方法, 并对人宫颈癌细胞(Hela)的³¹P NMR谱中含磷小分子代谢物的谱峰进行了分析; 细胞内无机磷(Pi)的化学位移对pH非常敏感, 通过测定其化学位移可间接确定细胞内的pH, Hela细胞内Pi峰的化学位移为5.88±0.01 (n＝3), 计算得到细胞内 pH值为7.05±0.01; 通过测量Hela细胞的³¹P NMR谱中ATP的α磷和β磷及γ磷的化学位移差值, 得出Hela细胞内Mg^2＋与ATP结合的复合物MgATP和整个ATP量的比值, 计算得到Hela细胞内游离Mg^2＋浓度为(253.3±0.13) mmol/L (n＝3), 与其它分析方法相比, ³¹P NMR测定细胞内游离Mg^2＋浓度具有对细胞样品无损伤的优点.     

31P NMR Study on Some Phosphorus-Containing Compounds

In view of the facts that the phenomena of aggregation are inseparably related to life processes and that phosphorus-containing compounds are one of the essential building blocks of life, we have studied the aggregation behavior of some phosphonates and phosphinates1. The application of NMR to the problems in chemistry has become rather popular. In phosphorus-containing compounds, phosphorus is a central or backbone atom in molecular structures. 31P NMR is of importance and special value in …     

Synthesis and Structure of Bis-phosphorylated 1,4:3,6-Dianhydro-D-mannitol Derivatives

A number of bis-phosphorylated 1,4:3,6-dianhydro-D-mannitol derivatives were synthesized. The increased steric loading of the phosphorus-containing residues in the compounds prepared gives rise to complicated ¹H and ³¹P NMR spectra and magnetic nonequivalence of structurally similar molecular fragments.     

Synthesis of phosphorus-containing polyoxamacrocycles with one to two reactive thiophosphoryl chloride groups

Novel phosphorus-containing polyoxamacrocycles with one to two reactive thiophosphoryl chloride groups 5, 6, 7, 8 were synthesized from bishydroxyl compounds 1, 2, 3, 4 and thiophosphoryl chloride respectively. Their structures were confirmed by ^ 1H NMR, ^13C NMR, ^31p NMR and elemental analysis.     

Phosphorus Derivatives of Natural Lactones. Synthesis of New Grosshemin Dialkylphosphonates

New phosphorus-containing derivatives of grosshemin were synthesized in 68-70% yield by reacting this guaianolide with dialkylphosphites. Their structures were established by IR, PMR, ¹³C NMR, and ³¹P NMR spectroscopies and two-dimensional ¹H-¹H NMR spectroscopy (COSY). The reaction of grosshemin with dialkylphosphites was found to be highly stereoselective.     

Synthesis of phosphorus-containing polyoxamacrocycles with one to two reactive thiophosphoryl chloride groups

Novel phosphorus-containing polyoxamacrocycles with one to two reactive thiophosphoryl chloride groups 5,6,7,8 were synthesized from bishydroxyl compounds 1,2,3,4 and thiophosphoryl chloride respectively.Their structures were confirmed by ~1H NMR,~(13)C NMR,~(31)p NMR and elemental analysis.     

Preparation, thermal properties, morphology, and microstructure of phosphorus-containing epoxy/SiO2 and polyimide/SiO2 nanocomposites

A phosphorus-containing tri-ethoxysilane (dopo-icteos) reacting from the nucleophilic addition reaction of 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide (dopo) and 3-(trieoxysilyl) isocyanate (icteos) was synthesized. The structure of dopo-icteos was confirmed by ¹H, ¹³C, ³¹P NMR and IR spectra. A triethylamine catalyzed mechanism for the dopo-icteos synthesis was proposed and verified by NMR spectra. The phosphorus-containing epoxy/SiO₂ and polyimide/SiO₂ nanocomposites were prepared from the in-situ curing of diglycidyl ether of bisphenol A (DGEBA)/4,4-diaminodiphenylmethane(DDM)/dopo-icteos, and imidization of poly(amic acid) of pyromellitic dianhydride (PMDA)/4,4′-oxydianiline (ODA)/dopo-icteos, respectively. The microstructure and morphology were investigated by ²⁹Si NMR, scanning electron microscope (SEM), EDS (Si and P mapping) analysis and atomic force microscope (AFM). The thermal properties, flame retardancy and dielectric properties of the organic-inorganic hybrids were investigated by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), limiting oxygen index (LOI), thermal gravimetric analysis (TGA) and dielectric analyzer (DEA).     

Solid-state NMR and EXAFS spectroscopic characterization of polycrystalline copper(I) O,O'-dialkyldithiophosphate cluster compounds: Formation of copper(I) O,O'-diisobutyldithiophosphate compounds on the surface of synthetic chalcocite

A number of polycrystalline copper(I) O,O'-dialkyldithiophosphate cluster compounds with Cu4, Cu6, and Cu8 cores were synthesized and characterized by using extended X-ray absorption fine-structure (EXAFS) spectroscopy. The structural relationship of these compounds is discussed. The polycrystalline copper(I) O,O'-diisobutyldithiophosphate cluster compounds, [Cu8{S2P(OiBu)2}6(S)] and [Cu6{S2P(OiBu)2}6], were also characterized by using 31P CP/MAS NMR (CP = cross polarization, MAS = magic-angle spinning) and static 65Cu NMR spectroscopies (at different magnetic fields) and powder X-ray diffraction (XRD) analysis. Comparative analyses of the 31P chemical-shift tensor, and the 65Cu chemical shift and quadrupolar-splitting parameters, estimated from the experimental NMR spectra of the polycrystalline copper(I) cluster compounds, are presented. The adsorption mechanism of the potassium O,O'-diisobutyldithiophosphate collector, K[S2P(OiBu)2], at the surface of synthetic chalcocite (Cu2S) was studied by means of solid-state 31P CP/MAS NMR spectroscopy and scanning electron microscopy (SEM). 31P NMR resonance lines from collector-treated chalcocite surfaces were assigned to a mixture of [Cu8{S2P(OiBu)2}6(S)] and [Cu6{S2P(OiBu)2}6] compounds.     

A high-resolution phosphorus-31 nuclear magnetic resonance (NMR) spectroscopic method for the non-phosphorus markers of chemical warfare agents

A high-resolution phosphorus-31 nuclear magnetic resonance (NMR) spectroscopic method has been developed for detection, identification and quantification of non-phosphorus markers of toxic nerve agents (soman and V-class), vesicants (HD, HN-2, HN-3), and incapacitating agent (Bz). These analytes were converted to phosphorus-containing derivatives via phosphitylation reaction of their hydroxyl and sulfhydryl functions (using 2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane). This was followed by ³¹P{¹H} and ³¹P NMR analysis of these derivatives. The chemical shifts (δ) and coupling constants (³ J _P–H) of derivatives were used for their specific detection and identification. The method allowed clear distinction between the alcohols and thiols. The lower limits of detection of these analytes were found to be between 12 and 28 μg obtained from 128 transients of ³¹P{¹H} quantitative NMR experiments. Utility of the method was ensured by the detection and identification of triethanolamine present (at an original concentration of 5 μg/mL) in an aqueous sample from 28th OPCW Official Proficiency Tests.     

Reaction of rhodium trichloride with P-functionalized calix[4]resorcinols in various media

The features of the reaction of rhodium trichloride with calix[4]resorcinols modified with various types of phosphorus-containing groups in ethanol, ethanol-formate medium and acetone under an inert atmosphere were studied. Neutral complexes were isolated in the solid form, the solvent molecules were shown to be actively involved into the formation of the final reaction products. The compounds were characterized by IR, Raman, ³¹P NMR, ESR, X-ray photoelectron and electronic spectroscopy, and electric conductivity. The composition was confirmed by the data of elemental analysis, X-ray fluorescence analysis, and derivatography. Based on the analysis of the ESR spectrum, the electronic and geometric structures of the paramagnetic product isolated from the acetone medium was determined.     

含咔唑生色团的三聚磷腈分子玻璃的合成

含咔唑生色团的三聚磷腈分子玻璃的合成;三聚磷腈;后重氮偶合;咔唑;光折变分子玻璃