氨基酸酯-烷基醚混合取代聚膦腈的合成与表征

聚膦腈高聚物,因其良好的生物相容性而用作生物医用材料。若在其侧链引入对热(如烷氧基醚)或对pH值敏感和可生物降解的基团(如氨基酸酯),则可得到具有环境敏感性和可生物降解性能的高聚物,这些高聚物可望作为药物载体,用于药物的控制释放。     

Structure elucidation and NMR spectral assignment of five new xanthones from the bark of Garcinia xanthochymus

Five new xanthones, namely Garcinexanthones A-E (1-5), were isolated from the barks of Garcinia xanthochymus. Their structures were elucidated by spectral analysis, primarily NMR, MS, and UV. The complete assignments of the (1)H NMR and (13)C NMR chemical shifts for the compounds were achieved by using 1D and 2D NMR techniques, including DEPT, HSQC, and HMBC NMR experiments.     

光谱法分析乙丙共聚物的序列结构及链节比

用FTIR, 1 H NMR和 13 C NMR分析乙丙共聚物的序列结构与链节比. 通过对乙丙共聚物 1 H NMR, 13 C NMR和 13 C-1 H二维核磁共振谱的综合分析, 提出了与前人不同的归属, 并提出了不同位置碳原子积分面积相关性分析方法, 该方法避免了烦琐的理论计算, 可简便地得到乙丙共聚物的主要序列结构. 通过比较 1 H NMR和 13 C NMR计算乙丙共聚物中乙烯、 丙烯链节比, 表明可以用 1 H NMR代替 13 C NMR完成对乙丙共聚物中乙烯、 丙烯链节比的定量计算.     

Investigation of structure, vibrational and NMR spectra of oxycodone and naltrexone: a combined experimental and theoretical study

In this work, two important opioid antagonists, naltrexone and oxycodone, were prepared from thebaine and were characterized by IR, (1)H NMR and (13)C NMR spectroscopy. Moreover, computational NMR and IR parameters were obtained using density functional theory (DFT) at B3LYP/6-311++G** level of theory. Complete NMR and vibrational assignment were carried out using the observed and calculated spectra. The IR frequencies and NMR chemical shifts, determined experimentally, were compared with those obtained theoretically from DFT calculations, showed good agreements. The RMS errors observed between experimental and calculated data for the IR absorptions are 85 and 105 cm(-1), for the (1)H NMR peaks are 0.87 and 0.17 ppm and for those of (13)C NMR are 5.6 and 5.3 ppm, respectively for naltrexone and oxycodone.     

Complete assignments of (1)H and (13)C NMR spectroscopic data for two new triterpenoid saponins from Ilex pernyi

Ilexpernoside A and ilexpernoside B, two new pentacyclic C(4)-nortriterpenoid saponins, were isolated from the leaves of Ilex pernyi Franch. Their chemical structures were determined by MS, NMR spectroscopy and chemical analysis. Complete assignments of the (1)H and (13)C NMR spectroscopic data were achieved by 1D and 2D NMR experiments (HSQC, HMBC, (1)H-(1)H COSY and NOESY).     

对甲苯烷酰胺基三苯基季膦盐的合成

以对甲苯胺为原料,氯烷酰氯为连接基团合成了4个含酰胺键的季膦盐,其结构经1H NMR,13C NMR,31P NMR,IR和MS表征。     

Solution structure of the palladium(II) complex of 1,4,7,10-tetrathiacyclododec-2-ene-2,3-dicarbonitrile

The solution structure of the Pd(II) complex of mn-12-S4 was studied in detail by NMR spectroscopy. The stoichiometry of the complex was determined by 1H NMR titration experiments. 3J(H,H) coupling constants were extracted from the 2D J-resolved NMR spectrum of the complex providing information concerning the S-C-C-S torsional angles. Further conclusions about the conformation of [Pd(mn-12-S4)](BF4)2 were drawn from experimental NOEs. The results of the NMR study were corroborated by molecular modelling.     

给药硝酸钕后大鼠完整肝组织及肝组织提取物的NMR代谢组学研究

通过分析不同给药剂量硝酸钕[Nd（NO3）3][2,10,50mg／kg（体重）]后,雄性Wistar大鼠完整肝组织的MAS1HNMR谱和肝组织提取物的^1H NMR谱,结合肝组织病理切片图,研究了稀土化合物Nd（NO3）3在大鼠体内的急性生物效应．利用模式识别方法对给药Nd（NO3）3组和对照组大鼠肝组织^1H NMR谱图数据进行了分析．结果表明,腹腔注射Nd（NO3）3后,大鼠肝脏中甘油三酯、亮氨酸（异亮氨酸）、乳酸、丙氨酸、丙酮酸、磷酸胆碱和葡萄糖含量升高,氮氧三甲胺含量降低．肝脏病理图显示,50mg／kg（体重）组大鼠肝细胞可见微小坏死灶和门管区炎细胞轻度增多．推测硝酸钕能影响大鼠肝脏中能量代谢（糖代谢和脂肪代谢）和氨基酸代谢,对大鼠肝脏造成损伤,且其损伤程度随剂量的增加有增强趋势．     

含二氮杂萘酮单元双官能团化合物结构的波谱表征

在成功地合成了11个用于制备聚芳酰胺类聚合物的含二氮杂萘酮单元的双官能团化合物基础上,本实验用核磁共振波谱确定了各化合物的结构。用二维同核位移相关谱(gCOSY)、异核^13C-^1H-键相关谱(gHSQC)和异核^13C-^1H远程相关谱(gHMBC)完成了全部^1H和^13C NMR谱带的归属;首次报道了该系列衍生物的氢和碳原子的化学位移值。对其系列化合物的核磁共振波谱及红外光谱的特征进行了讨论。     

Trachylobagibberellin类似物的化学合成研究（Ⅰ）──12．16R－环赤霉低酸甲酯的合成

Ｔｒａｃｈｙｌｏｂａｇｉｂｂｅｒｅｌｌｉｎ类似物的化学合成研究（Ⅰ）──１２．１６Ｒ－环赤霉低酸甲酯的合成谢文革，崔育新，马建泰，潘鑫复（兰州大学化学系，兰州大学应用有机化学国家重点实验室，兰州，７３００００）关键词Ｔｒａｃｈｙｌｏｂａｇｉｂｂｅｒｅ...     

Spectroscopic Characterization and Properties of Some Bioactive- Peroxovanadium Complexes in Aqueous Solution

1　ＩＮＴＲＯＤＵＣＴＩＯＮＰｅｒｏｘｏｖａｎａｄｉｕｍ ( ｐＶ )ｃｏｍｐｌｅｘｅｓａｒｅ ｐｏｔｅｎｔｐｒｏｔｅｉｎｔｙｒｏｓｉｎｅｐｈｏｓｐｈａｔａｓｅｉｎ ｈｉｂｉｔｏｒｓｗｉｔｈｉｎｓｕｌｉｎ ｍｉｍｅｓｉｓｐｒｏｐｅｒｔｉｅｓａｎｄｃｏｕｌｄｐｏｓｓｉｂｌｙｂｅｄｅｖｅｌｏｐｅｄｉｎｔｏａｎｅｗｋｉｎｄｏｆｏｒａｌｄｒｕｇｆｏｒｔｈｅｔｒｅａｔｍｅｎｔｏｆｄｉａｂｅｔｅｓ[1～ 3].Ｒｅｃｅｎｔｌｙ ,ｔｈｉｓｋｉｎｄｏｆｃｏｍｐｏｕｎｄｈａｓｒｅｃｅｉｖｅｄｃｏｎｓｉｄｅｒａｂｌｅａｔｔｅｎｔ…     

Characterization of dextrin hydrogels by FTIR spectroscopy and solid state NMR spectroscopy

Fourier transform infrared (FTIR) and ¹³C solid state nuclear magnetic resonance (NMR) spectroscopy were used to study dextrin structural changes occurring upon hydrogel formation by vinyl acrylate (VA) grafting and subsequent free radical polymerization. The degrees of VA substitution (DS) and polymerization (DP) were quantified up to 40%VA by FTIR intensity measurements and partial least squares (PLS)/FTIR, the latter being a faster and less error-prone method. Above 40%VA, both parameters are underestimated by FTIR. A spin counting NMR experiment showed high carbon observabilities for hydrogels and improved PLS/NMR models were achieved for DS and DP determination. Alternative NMR integration methods are hindered by the broad VA peaks and need for area correction, due to their CP dynamics. NMR changes in C1 profile showed that a single helical conformation predominates at lower %VA, being replaced by disordered conformations as %VA increases. Furthermore, a correlation FTIR/NMR study indicated that ring conformations are significantly affected in hydrogels, compared to unpolymerized dextrin.     

(s)-多沙唑嗪的核磁共振理论和实验研究

报道了(s)-多沙唑嗪的1H、13C、DEPT、1H-1H COSY等的NMR波谱数据, 并对1H、13C NMR信号进行了指认. (s)-多沙唑嗪分子中含有9个季碳原子, 其中绝大部分通过常规实验的方法难以指认. 应用量子化学规范不变原子轨道(GIAO)的Becke-3-Lee-Yang-Parr(B3LYP)和Hartree-Fock(HF)方法, 分别在6-21G基组下计算了标题化合物的13C NMR化学位移值. 计算结果表明, 理论计算数据与实验结果吻合较好, 可以帮助对(s)-多沙唑嗪季碳原子NMR位移信号进行指认.     

meso-四(烷氧基苯基)卟啉及其金属络合物的波谱研究

采用^1H NMR、MS、IR、UV、元素分析等分析测试表征手段确证了所合成的10个系列卟啉及其金属络合物的结构,研究了不同位置、不同链长烷氧基四苯基卟啉和不同金属离子卟啉络合物的结构与^1HNMR、IR和UV等波谱之间的关系,总结了卟啉配体及其金属络合物的^1H NMR、IR和UV判据,报道和解释了meso-四(烷氧基苯基)卟啉铜、锰络合物和meso-四(邻烷氧基苯基)卟啉钴络合物的^1H NMR研究结果,通过MS、^1H NMR、IR、UV、元素分析确证了我们所合成的铁卟啉为μ-氧桥联夹心二聚体结构,且存在两种典型构象,导致同系列络合物有四种类型^1H NMR谱图。     

两种立体构型的1,3,5,-三-α-萘基苯的合成

通过Adole反应和Grigard反应合成了相应的两种立体异构的1,3,5-三-α-萘基苯. 报道了它们的UV, IR, FD-MS和NMR . 论了两种异构体的^1H NMR 和^1^3C NMR的区别.     

Synthesis of N-Phosphoryl Branched Peptides

H-phosphonates were conveniently prepared by direct transesterification of diphenyl phosphite (DPP) with the corresponding alcohols, without further purification they were reacted with branched peptide methyl ester (L-Leu2-L-LysOMe) through Atherton-Todd method, a series of different substituted alkyloxy (N-phosphoryl-L-Leu)2-L-LysOMe were synthesized, and their stmctures were confirmed by ^31P NMR, ESI-MS, ^1H NMR, ^13C NMR, IR and elemental analysis. The approach possesses the advantages of easy operation, high yield and inexpensive phosphorylating reagent.     

Characterization of stationary phases for gas chromatography by 29Si nuclear magnetic resonance spectroscopy III. Carborane-siloxane copolymers

Five bis(dimethylsilyl)-m-carborane-siloxane polymers with methyl, phenyl, and 2-cyanoethyl ligands were characterized by (1)H, (11)B, (13)C, and (29)Si nuclear magnetic resonance (NMR) spectroscopy. All relevant chemical shifts are reported, whereas signal assignment was confirmed by 2D NMR spectroscopy. The chemical composition of the polymers was calculated from the (1)H and (29)Si NMR spectra. Only (29)Si NMR spectroscopy was able to quantify the methoxy end group, from which the average molecular weights were calculated. The copolymer Dexsil 300 turned out to have a regular microstructure, whilst the terpolymers Dexsil 400 and Dexsil 410 have only partly regular sequences. (11)B NMR spectroscopy confirmed the m-carborane structure and revealed some low molecular weight impurities.     

大位阻二胺基膦配体的合成

以取代苯胺为起始原料,依次经缩合反应和硼氢化钠还原制得1,2-二胺(4a,4b);4a和4b分别与苯基二氯化膦经亲核取代反应合成了两个新型的大位阻二氨基膦配体,其结构经~1H NMR,~(13)C NMR,31P NMR和HR-MS(ESI-TOF)表征。     

A comprehensive NMR methodology to assess the composition of biobased and biodegradable polymers in contact with food

A nuclear magnetic resonance (NMR) methodology was assessed regarding the identification and quantification of additives in three types of polylactide (PLA) intended as food contact materials. Additives were identified using the LNE/NMR database which clusters NMR datasets on more than 130 substances authorized by European Regulation No. 10/2011. Of the 12 additives spiked in the three types of PLA pellets, 10 were rapidly identified by the database and correlated with spectral comparison. The levels of the 12 additives were estimated using quantitative NMR combined with graphical computation. A comparison with chromatographic methods tended to prove the sensitivity of NMR by demonstrating an analytical difference of less than 15%. Our results therefore demonstrated the efficiency of the proposed NMR methodology for rapid assessment of the composition of PLA.     

手性镧系位移试剂核磁共振法测定芳氧丙酸酯类除草剂对映体纯度

以Eu(hfc)3和Pr(hfc)3为手性镧系位移试剂(CLSR),比较了两种CLSR对2,4-滴丙酸甲酯的1HNMR和13C NMR谱手性分离效果,结果表明:Pr(hfc)3比Eu(hfc)3对手性中心相连的甲基具有更好的手性分离效果。首次应用Pr(hfc)3测定了盖草能、稳杀得和喹禾灵3种手性芳氧丙酸酯类除草剂的1HNMR和13CNMR谱,其1HNMR谱分离度R约为1,盖草能和喹禾灵的13C NMR谱分离度R大于1.5,说明1H NMR和13CNMR谱手性分离效果适用于对映体纯度测定。与手性色谱法相比,CLSR-NMR法测定对映体纯度具有操作简便、分析速度快的显著优势。