新型连翘脂素-布洛芬酯合物的波谱学数据解析

以连翘脂素和布洛芬为原料,通过Schotten-Baumann酯化合成了酯合物——连翘脂素-布洛芬酯.对其紫外吸收光谱（UV）、红外吸收光谱（IR）、基质辅助激光解吸/电离飞行时间质谱（MALDI-TOF-MS）、1D和2D核磁共振（NMR）波谱（包括¹H NMR、¹³C NMR、DEPT、¹H-¹H COSY、¹H-¹H NOESY、¹H-¹³C HSQC和¹H-¹³C HMBC）进行了解析,对其¹H和¹³C NMR谱峰进行了全归属.     

新的4′-去甲表鬼臼衍生物的2D NMR研究

采用¹H-¹H COSY、NOESY、¹H-¹³C HMQC及HMBC二维NMR技术鉴定了2个新合成的4β-5- 氟尿嘧啶取代-4′-去甲表鬼臼毒衍生物, 并对它们的¹H和¹³C NMR 谱峰进行了全归属.     

N-异丁酰基-3'-O-(1-氟-1,1,3,3-四异丙基-1,3-二硅氧烷-3-基)-2'-苄氧羰基鸟苷的NMR研究

本文采用氢氟酸吡啶鎓在5′-位选择性断裂1,1,3,3-四异丙基二硅氧烷基保护基的方法得到了核苷衍生物N-异丁酰基-3′-O-（1-氟-1,1,3,3-四异丙基-1,3-二硅氧烷-3-基）-2′-苄氧羰基鸟苷（化合物1）,并应用液相色谱串联质谱（LC-MS）、气相色谱-高分辨质谱（GC-HRMS）、液体1D和2D NMR谱（包括¹H NMR、¹³C NMR、¹⁹F NMR、DEPT、¹H-¹H COSY、¹H-¹³C HSQC和¹H-¹³C HMBC）,对产物的¹H、¹³C和¹⁹F NMR信号进行了归属,确定了其结构．     

盐酸马尼地平的核磁共振数据解析

盐酸马尼地平是第三代合成降压新药．本文利用一维、二维核磁共振（NMR）技术,包括¹H NMR、¹³C NMR DEPT-135、¹H-¹H NOESY、¹H-¹H COSY、¹H-¹³C HSQC和¹H-¹³C HMBC,对其¹H和¹³C NMR信号进行了全归属,进一步确证了其分子结构．同时,对其¹H NMR和¹³C NMR谱中一些异常信号进行了讨论．     

白桦酯酸7',8'一二羟基肉桂酸脂的2D NMR研究

从产于甘肃的高山绣线菊植物中分离出一种新的化合物:白桦酯酸7',8'-二羟基肉桂酸脂.利用MS,IR,1D和2D NMR技术,其中包括¹H-¹H COSY,¹H-¹³C COSY,¹H-¹³C COLOC等对¹H和¹³C谱进行了归属.     

3'(,3")-(二)甲酰基(二)苯并冠醚的2D NMR研究

测定了3'(,3")-(二)甲酰基(二)苯并冠醚(1~7)的¹H、¹³C谱,首次结合¹H-¹H COSY、¹³C-¹H COSY、COLOC二维谱对这些化合物的¹H、¹³C化学位移进行了归属。用NOESY谱确定了合成产物冠4、冠5的结构,并对溶液中的构象异构体及其溶剂影响进行了初探。作者以冠1~8的¹H、¹³C谱的归属为参照,提出了正确归属冠醚醚环上次甲基¹H、¹³C化学位移的一般规则。     

基于咔唑-三嗪并吲哚的N-酰腙衍生物的NMR数据归属

N-酰腙类化合物在极性溶剂中存在着E/cis和E/trans两种异构体,本文利用元素分析、红外光谱、1D和2D核磁共振（NMR）波谱（包括¹H NMR、¹³C NMR、¹H-¹H COSY、¹H-¹³C HSQC、¹H-¹³C HMBC和NOESY）等技术,对基于咔唑-三嗪并吲哚的新型N-酰腙衍生物3,即2-（5H-[1,2,4]三嗪[5,6-b]吲哚-3-硫基）-N'-（9-乙基咔唑-3-亚甲基）乙酰肼的两种异构体（E/cis和E/trans）的¹H和¹³C NMR信号进行了全归属,测量了其偶合常数（J值）及两种异构体的含量,确定了其空间结构.     

南蛇藤中倍半萜生物碱的二维NMR研究

用DEPT和二维NMR技术包括:¹H-¹H COSY,¹H-¹³C COSY,NOESY,特别是¹H-¹³C COLOC对两个多酯基取代的倍半萜生物碱的化学及立体结构进行了研究,并对其¹H和¹³C NMR谱峰进行了归属。     

海博麦布结构确证

本文采用紫外吸收光谱、红外吸收光谱、质谱、核磁共振波谱(包含¹H NMR、¹³C NMR、DEPT、¹H-¹H COSY、¹H-¹H NOESY、¹H-¹³C HSQC和¹H-¹³C HMBC)以及单晶衍射等方法对海博麦布进行结构分析,对其所有的¹H NMR和¹³C NMR谱信号进行了归属,还通过差示扫描量热法、热重分析及粉末X-射线衍射分析对海博麦布晶型进行研究．     

1-(2-羧基苯基甲酰基)氨基硫脲及其Cu+配合物的NMR研究

利用¹H-¹H COSY,¹H-¹³C HMQC,HMBC等2D NMR技术对一种新的配体1-(2-羧基苯基甲酰基)氨基硫脲(H₃L)进行¹H、¹³C NMR谱数据分析与归属,对于它与Cu⁺离子配位的化合物[Cu₂(H₃L)₂Cl₂](H₂O)₃也作了¹H、¹³C NMR的测定,简单讨论了它的配位行为,粗略确定了它的结构.     

Measurement of one-bond heteronuclear dipolar coupling contributions for amine and diastereotopic methylene protons

One-bond heteronuclear and two-bond homonuclear residual dipolar couplings measured at methylene or amine sites can be utilized as long-range constraints in structure determination of molecules as well as to facilitate characterization of local conformation by stereospecific assignment of diastereotopic protons. We present two J-modulated HMQC type experiments to measure the one-bond heteronuclear dipolar coupling contributions of geminal protons individually. In addition two-bond homonuclear residual dipolar couplings between the diastereotopic protons are also obtained.     

Conformational Analysis of Longifolene

We describe the stable conformation of the tricyclic sesquiterpenoid, longifolene, by experimental NMR data and molecular mechanics calculations of the coupling constants. The flexible seven-membered ring of longifolene adopts a twist-chair conformation. Analysis of the coupling constants, particularly of the methylene protons in the cycloheptane ring moiety, agrees with this low-energy conformation. Low-temperature NMR experiments and nuclear Overhauser effect measurements indicate that there is a single exchange-averaged NMR spectrum that has the highest population of the most stable conformer.     

奥拉西坦的核磁共振波谱特征与构象研究

奥拉西坦是一种改善脑功能药物. 该文研究了该药的核磁共振波谱特征和构象. 吡咯环的各项异性效应使侧链亚甲基的质子的磁不等价. 由于吡咯环内酰胺键的部分双键性质,观测到了远程耦合现象. 信封式构象为吡咯环的优势构象. 同时研究了环外侧链上的酰胺键的受阻旋转.     

Structure and conformation of nitroxyl spin-label compounds in frozen solutions by electron nuclear double resonance spectroscopy

The structure and conformation of carboxylic acid, formyl, and propenoic acid derivatives of the nitroxyl spin-label 2,2,5,5-tetramethyl-1-oxypyrroline have been determined by electron nuclear double resonance (ENDOR) spectroscopy. From ENDOR spectra of the spin-label compounds in frozen solutions, we have assigned the resonance absorption features for each class of protons. The ENDOR spectra were analyzed on the basis of their dependence onH ₀. The maximum and minimum ENDOR shifts for each proton were shown to correspond to axially symmetric principal hyperfine coupling (hfc) components, from which the dipolar contributions were estimated to calculate electron-proton separations. Conformational analysis on the basis of torsion angle search calculations constrained by the ENDOR determined electron-proton distances revealed that in all three spin-label compounds the side chains are in a planar conformation with respect to the oxypyrrolinyl ring. In the carboxylic acid and formyl derivatives the C=O group is in as-trans conformation with respect to the vinyl group of the spin-label, while in the spin-labeled propenoic acid the conformation is found to be all planartrans-s-cis.     

核磁共振弛豫速率方法测定模拟正铁色素的结构

在生命体系内正铁色素具有摄铁和输铁的功能,人工合成的模拟化合物具备了正铁色素的主要功能基团和相近的性质.本工作利用铁(Ⅲ)离子的顺磁性质,测定不同铁(Ⅲ)离子浓度下模拟正铁色素的诱导弛豫时间,根据简化了的Solomon-Bloemoergen公式,计算出铁(Ⅲ)离子到所有被测质子(即氢原子)的相对距离,比较清楚地得到模拟正铁色素在溶液中的构象.     

In-situ analysis of the water distribution and protein structure of dough during ultrasonic-assisted freezing based on miniature Raman spectroscopy

The effect of ultrasonic-assisted freezing (UAF) on the water distribution of dough and molecular structure of gluten was in-situ monitored by low field nuclear magnetic resonance (LF-NMR) and micro-miniature Raman spectroscopy in this research. The results showed that UAF treatment increased the bound water content between 5 min and 30 min, and weakened the signal intensity of hydrogen protons due to the ultrasound enhanced heat and mass transfer during the freezing process. In-situ Raman spectra analysis indicated that UAF delayed the transition from embedded to exposure of tyrosine and tryptophan residues during the freezing process. Meanwhile, UAF reduced the number of hydrogen bonds, gauche-gauche-gauche (g-g-g) conformation breakage, the degree of α-helix to random coil conversion and damage to the gluten network during the freezing process. UAF treatment reduced the water mobility and breakage of non-covalent bonds, which prevented a dramatic shift in the protein advanced conformation during the freezing process, thereby improving the quality of frozen dough.     

利用二维接力相关谱和J分解谱对里杜霉素质子信号的归属

本文采用二维接力相关技术(单接力和三接力COSY)和J分解谱对氨基糖苷类化合物里杜霉素的全部质子信号进行了归属,为进一步测定里杜霉素的构型和构象打下了基础.     

利用二维接力相关谱和J分解谱对里杜霉素质子信号的归属

本文采用二维接力相关技术(单接力和三接力COSY)和J分解谱对氨基糖苷类化合物里杜霉素的全部质子信号进行了归属,为进一步测定里杜霉素的构型和构象打下了基础.     

Protonen-Dispersionskräfte und IR-Kontinuumsabsorption bei Säure- und Lauge-Lösungen

In the investigation of acid and alkali solutions a continuum absorption is observed in the IR spectrum, which is caused by protons or defect protons tunneling in hydrogen bridges. By means of a perturbation calculation it is shown that the variations of the electromagnetic fields caused by the tunneling of the protons give rise to coupling forces, which we term proton or defect-proton dispersion forces. These are dependent of the distance between the hydrogen bridges, of their orientation, and of the tunneling frequency. Since these quantities are statistically distributed and the forces are very considerable, the energy terms of the tunneling protons are spread out to broad energy bands.     

质子和中子在硅中位移损伤等效性计算

基于蒙特卡罗软件Geant4,探讨质子与硅的库仑散射和核反应及中子与硅的核反应产生反冲原子沉积非电离能量的过程,建立质子和中子在硅中的非电离能量阻止本领计算方法。在此方法中,描述了原子间库仑散射的物理过程,模拟带电粒子与晶格原子之间的屏蔽库仑散射。计算得到不同能量质子和中子在硅中因库仑散射和核反应产生反冲原子的非电离能量沉积及阻止本领的等效性,计算结果与中子ASTM标准及文献计算得到的质子数据符合很好。