毛冬青甲素的核磁共振法分析

采用^1H、^13C、DEPT(无畸变极化转移增益法)、^1H-^1 COSY(氢-氢化学位移相关谱)、HMQC(异核多量子相关谱)、HMBC(异核多键相关谱)、NOESY(二维核欧沃豪斯效应谱)等多种NMR分析方法,对毛冬青甲素的^1H和^13C NMR谱信号进行了归属;并对生产过程常同时存在的丁二酸二钠也进行了谱线归属,提出通过^1H NMR法对产品中的丁二酸二钠进行定量测定。为其结构鉴定和生产过程中的质量控制提供了重要依据。     

加速溶剂萃取/HPLC-MS对毛冬青药材中Ilexgenin A与Ilexsaponin A1含量的测定

建立了加速溶剂萃取/高效液相色谱-质谱法(ASE/HPLC-MS)测定毛冬青药材中活性成分ilexgenin A和ilexsaponin A1含量的方法.采用ASE萃取毛冬青药材中的活性成分ilexgenin A和ilexsaponin A1,萃取溶剂为甲醇,萃取温度100 ℃,压力1.0×107 Pa,静态萃取模式,循环3次,每次萃取10 min.采用HPLC-MS对萃取液中ilexgenin A和ilexsaponin A1进行定量分析,色谱柱选用Dikma Diamonsil C18(4.6 mm×250 mm,5 μm),以水和乙腈为流动相进行梯度洗脱,大气压化学电离源(APCI),定量离子m/z 485.ilexgenin A和ilexsaponin A1的线性范围为1.0 ～200.0 mg/L,对毛冬青试样的定量下限分别为19.5和35.0 μg/g,RSD分别为6.7%和7.8%,回收率分别为87% ～96%和93% ～102%.将建立的方法用于分析11个不同产地的毛冬青药材,ilexgenin A含量为0.42 ～6.3 mg/g,ilexsaponin A1含量为0.80 ～8.9 mg/g.     

高效液相色谱-质谱法快速鉴定复方毛冬青冲剂中三萜皂苷活性成分

建立了高效液相色谱-质谱法(HPLC-MS)快速鉴定复方毛冬青冲剂中三萜皂苷活性成分的方法.以甲醇为萃取剂超声萃取复方毛冬青冲剂30 min.采用高效液相色谱-离子阱质谱(HPLC-IT-MS)和高效液相色谱-飞行时间质谱(HPLC-TOF-MS)对萃取液进行分析,选用Agilent Zorbax Eclipse XDB C18色谱柱(250 mm×4.6 mm, 5 μm),以水(含0.1 %甲酸)-乙腈为流动相进行梯度洗脱,柱后流出液采用电喷雾离子阱质谱(ESI-IT-MS)和电喷雾飞行时间质谱(ESI-TOF-MS)的正、负离子模式进行检测.检测结果经离子阱一级质谱(IT-MS1)、离子阱二级质谱(IT-MS2)和分析时间质谱(TOF-MS)信息分析,并与相关文献报道进行比较,鉴定出1种三萜酸和8种三萜皂苷成分,并推测了其它3种可能的三萜皂苷化学成分,通过对照品对比分析,三萜酸确证为Ilexgenin A,其中一种三萜皂苷确证为Ilexsaponin A1.本方法无需对照品即可快速有效地鉴定出复方毛冬青冲剂中的三萜皂苷活性成分,为建立冲剂的质量标准提供了依据.     

毛冬青总皂苷对AHNP诱导肝损伤大鼠骨中7种微量元素的影响

目的探讨了毛冬青总皂苷对AHNP诱导肝损伤大鼠骨中微量元素的影响。方法应用逆行胰胆管术注射牛磺胆酸钠（TAC）复制急性出血坏死性胰腺炎（AHNP）大鼠实验动物模型,进行了毛冬青总皂苷（高、低剂量）的治疗。观察了5组（假手术对照组、AHNP模型组、毛冬青总皂苷高剂量组、毛冬青总皂苷低剂量组、尼尔雌醇组、）大鼠股骨中Cu、Mn、Fe、Zn、Pb、Mg和ca等微量元素的变化。结果统计学结果显示与AHNP模型组比较,毛冬青总皂苷能提高AHNP大鼠骨质中cu、Fe、Mn、Mg、Ca等元素的含量,尼尔雌醇组中的zn含量提高,毛冬青总皂苷组中的zn含量反而下降;尼尔雌醇组与毛冬青总皂苷组中Pb含量下降明显。结论说明毛冬青总皂苷的治疗作用并不是单一的,可以认为中药毛冬青总皂苷是通过发挥对人体整体的调节作用来调节骨骼中微量元素的变化,改变骨质的代谢情况,促进骨密度的提高。     

毛冬青化学成分的研究II: 毛冬青皂苷甲的化学结构

从毛冬青的根皮中分得一种新的三萜皂苷,命名为毛冬青皂苷甲,经^1H NMR、^1^3C NMR、MS、IR、UV和化学转化产物的研究,推定它为3β,19α-二羟基-乌索-12-烯-24,28-二羧酸-28-β-D-葡萄吡喃糖基酯.     

毛冬青总皂苷对大鼠脑缺血再灌注损伤的保护作用及血液微量元素影响

目的研究毛冬青总皂苷对脑缺血再灌注损伤的保护作用,并初步探讨其血液微量元素的影响。方法动物随机分为假手术组、模型组、毛冬青总皂苷(高、中、低)剂量组及阳性药物对照组,运用大鼠大脑中动脉栓塞,制作脑缺血再灌注损伤模型,缺血10 min后,给药组及阳性药物组于舌下静脉给予高、中、低剂量的毛冬青总皂苷及假手术组、模型组给予等体积的溶剂。缺血60 min再灌注24 h后,每组取8只大鼠断头取脑,TTC染色,测定脑梗死体积;取血,测定血液中3种微量元素Ca、Zn、Cu的含量。结果毛冬青总皂苷组与模型组相比,毛冬青总皂苷治疗组脑梗死体积减小,病理变化较轻;模型组与假手术组比较血液中Ca、Cu含量增加明显有统计学意义,Zn含量明显降低与假手术组比较有统计学意义(P0.05),毛冬青高、中、低剂量组与模型组比较Ca、Cu含量明显降低,Zn含量明显升高,而且呈明显的量效关系,与模型组比较有统计学意义(P0.05)。结论毛冬青总皂苷对脑缺血再灌注损伤具有一定的保护作用,其保护机制与毛冬青总皂苷抗氧化作用及增强氧自由基的清除有关。     

In（Ⅲ）－和Y（Ⅲ）－1，2－PDTA配合物的动态核磁共振研究

研究了Ｉｎ（Ⅲ）和Ｙ（Ⅲ）－１，２－丙二胺四乙酸配合物￣１ＨＮＭＲ谱的温度依赖性，其结果显示出８个乙酸质子处于不同的磁环境中，分４组ＡＢ谱。ＡＢ谱交换现象由氮原子翻转引起，通过全线型分析求得了速率常数及相关热大学参数。对不对称的氮原子，其翻转速率不同，靠近ＣＨ＿３─基团的氮原子翻转速率要比远离ＣＨ＿３─的小．活化能与金属离子的离子势呈线性关系。     

4-羟基-2(1H)-吡啶酮-3-甲酰胺类冬青生菌素类似物的合成与生物活性

以反式-4-羟基肉桂酸为起始原料,经乙酰化、酰基叠氮、curtius重排、加成和环合等6步反应合成了4-羟基-2(1 H)-吡啶酮-3-甲酰胺类冬青生菌素类似物,总收率17%.随后用滤纸片扩散法对该化合物的抑菌性能进行了初步研究.实验表明,该化合物对于白色念珠菌具有较好的抑制作用,对于酵母菌抑制作用较弱,对大肠杆菌和金黄色葡萄球菌基本无抑制作用.     

Y2O3包覆LiCo1/3Ni1/3Mn1/3O2的电化学性能

通过在硝酸钇水溶液浸渍并焙烧的简单工艺, 在LiCo1/3Ni1/3Mn1/3O2材料表面包覆了一层Y2O3. 采用X射线衍射(XRD), 扫描电子显微镜(SEM), 透射电子显微镜(TEM), 循环伏安(CV)和恒流充放电对包覆和未包覆的LiCo1/3Ni1/3Mn1/3O2进行了测试分析. 结果表明, Y2O3包覆并没有改变LiCo1/3Ni1/3Mn1/3O2的晶体结构, 只存在于LiCo1/3Ni1/3Mn1/3O2的表面; 与未包覆的材料相比, Y2O3包覆后的材料在高电位下具有更好的容量保持率和放电容量. CV测试表明, 包覆层的存在有效抑制了材料层状结构的转变及电极与电解液的负反应.     

CH2(～X3B1)与NO的基元化学反应研究

The reaction of methylene radicals in their 3B1 electronic ground state with molecular NO was studied. Pure CH2(～X3B1) radicals were produced by UV photolysis of ketene at 351 nm. The products were measured by Time-Resolved Fourier Transform Infrared (TR-FTIR) spectrometer. CO、OH、NH2 and HOCN or its isomer HNCO were found as primary products and several possible channels of this reaction were suggested.     

一种新的六氢嘧啶并嘧啶二酮衍生物的核磁共振分析

采用氢谱(1H NMR)、碳谱(13C NMR)、梯度场氢氢化学位移相关谱(1H-1H COSY)、梯度场质子检测异核单量子化学位移相关谱(HSQC)、梯度场质子检测异核多重键化学位移相关谱(HMBC)等多种NMR分析方法,确证了8a-对甲氧苯基-4,5-双(对氯苯基)六氢嘧啶[4,5-d]并嘧啶-2,7(1H,3H)-二酮的结构,对它的1H和13C NMR谱信号进行了归属,为其结构鉴定提供了重要依据。     

Structural determination of atricins A and B, new triterpenes from Perovskia atriplicifolia, by 1D and 2D NMR spectroscopy

Atricins A (1) and B (2), two new oleanane-type triterpenes have been isolated from the chloroform-soluble fractions of Perovskia atriplicifolia and their structures assigned from (1)H and (13)C-NMR spectra, Distortion Enhancement by Polarization Trasfer (DEPT) and by 2D-COSY, HMQC, Nuclear Overhauser Enhancement Spectroscopy (NOESY) and Hetronuclear mutiple-bond correlation (HMBC) experiments.     

Structural determination of diterpenes from Daphne genkwa by NMR spectroscopy

Five daphnane type diterpenes have been isolated from the chloroform soluble fraction of Daphne genkwa. The structure of the new compound (1) was assigned as 5beta-hydroxyresiniferonol-6alpha,7alpha-epoxy-12beta-acetoxy-9,13,14-ortho-2E-decenoate by extensive NMR studies.     

Structural determination of abutilins A and B,new flavonoids from Abutilon pakistanicum,by 1D and 2D NMR spectroscopy

Two new flavonoids, abutilin A and B, were isolated from the chloroform soluble fraction of Abutilon pakistanicum and their structures assigned from ¹H and ¹³C NMR spectra, DEPT and by 2D COSY, HMQC and HMBC experiments. Ferulic acid (3), (E)‐cinnamic acid (4), 5‐hydroxy‐4′,6,7,8‐tetramethoxyflavone (5), kaempferol (6), luteolin (7) and luteolin 7‐O‐β‐D ‐glucopyranoside (8) have also been reported from this species. Copyright © 2009 John Wiley & Sons, Ltd.     

Structural determination of silymins A and B, new pentacyclic triterpenes from Silybum marianum, by 1D and 2D NMR spectroscopy

Silymins A (1) and B (2), the new pentacyclic triterpenes, have been isolated from ethyl acetate fraction of Silybum marianum and their structures assigned from 1H and 13C NMR spectra, DEPT and by 2D COSY, NOE and HMBC experiments.     

Structural determination of salsolins A and B, new antioxidant polyoxygenated triterpenes from Salsola baryosma, by 1D and 2D NMR spectroscopy

Salsolins A (1) and B (2), the new triterpenes, have been isolated from the chloroform soluble fraction of Salsola baryosma along with 2alpha,3beta,23,24-tetrahydroxyurs-12-en-28-oic acid (3) reported for the first time from this species. Their structures have been assigned from 1H and 13C NMR spectra, DEPT and by 2D COSY, NOESY, HMQC and HMBC experiments. The compounds 1-3 showed significant antioxidant activity.     

Structural determination of prunusins A and B,new C‐alkylated flavonoids from Prunus domestica,by 1D and 2D NMR spectroscopy

Prunusins A (1) and B (2), the new C‐alkylated flavonoids, have been isolated from the seed kernels of Prunus domestica. Their structures were assigned from ¹H and ¹³C nuclear magnetic resonating spectra, DEPT and by correlation spectroscopy, HMQC and HMBC experiments. 3, 5, 7, 4′‐Tetrahydroxyflavone (3) and 3, 5, 7‐trihydroxy‐8, 4′‐dimethoxyflavone (4) have also been reported from this species. Both compounds (1) and (2) showed significant antifungal activity against pathogenic fungus Trichophyton simmi. Copyright © 2009 John Wiley & Sons, Ltd.     

维生素B2的NMR含量测定

建立了维生素B2片剂中维生素B2含量的核磁共振测定方法。核磁共振的测定条件:脉冲程序为cpmgpr1d,氢谱宽度为6 009 Hz,脉冲宽度为11.95μs,延迟时间为6.50μs,采样温度为27℃,采样次数为32次。以参比物质3-(三甲基硅基)氘代丙酸钠(TSP)为内标,将不同浓度标准品与内标的NMR峰面积比对维生素B2浓度绘制标准曲线,结果显示,维生素B2在1.25~10 mg/mL范围内呈良好线性,其线性方程为:y=2.989 4 x+0.185 5,r2=0.999 2。方法的加标回收率为83.2%。该方法灵敏度高、重现性好、操作简便,可用于维生素B2片剂中维生素B2含量的测定。     

Structural determination of seven new triterpenoids from Kadsura heteroclita by NMR techniques

Seven new triterpenoids, namely heteroclitalactones G-M (1-7), were isolated from the ethanol extract of the stems of Kadsura heteroclita. Structures of these compounds were characterized by extensive 1D and 2D NMR spectroscopic analyses.     

Structural determination of kochiosides A-C, new steroidal glucosides from Kochia prostrata, by 1D and 2D NMR spectroscopy

Kochiosides A-C, three new steroidal glucosides, have been isolated from the ethyl acetate fraction of Kochia prostrata and their structures assigned from its (1)H and (13)C NMR spectra, DEPT and by 2D COSY, NOESY, HMQC and HMBC experiments.