核磁共振波谱法测定液体乳中的1,2-丙二醇

采用核磁共振氢谱(~1H NMR)、选择性一维全相关谱(1D-TOCSY)及定量核磁共振法(qNMR)对液态乳中的1,2-丙二醇进行了快速筛查及含量测定,并与气相色谱法的测定结果进行了比较。~1H NMR法以液态乳基质中1,2-丙二醇的甲基质子信号特征为初步定性标准,选择性一维全相关谱法以1,2-丙二醇的亚甲基和次甲基质子信号特征为精确定性标准。在定性检测基础上,采用定量核磁共振法以1,2-丙二醇δ 1.15处的质子峰为定量峰,3-(三甲基硅基)氘代丙酸钠(TMSP)δ 0.00处的峰为内标峰,测定了液体乳中1,2-丙二醇的绝对含量。方法的检出限为0.002 mg/mL,定量下限为0.006 mg/mL。实际样品测定结果显示,NMR法与气相色谱法的检测结果一致,且NMR法前处理简单,操作方便,专属性高,在提高检测效率的同时能够避免假阳性结果出现,非常适合实际检测中液体乳中1,2-丙二醇的批量、快速检测。     

核磁共振技术在保健食品非目标成分分析中的应用

采用二维扩散排序谱(2D-DOSY)和脉冲宽度(PULCON)定量等多种核磁共振(NMR)技术,对具有减肥功效的保健食品中主要成分进行了定性、定量研究。采用布鲁克AvanceⅢ600 MHz超导核磁共振波谱仪,以氘代丙酮为溶剂,对待测物进行了核磁检测。2D-DOSY表明该保健食品中含有3种主要化学成分,结合多种NMR技术对3个化合物进行了结构解析,归属了其所有的NMR谱信号,确定样品的主要成分为邻苯二甲酸二乙酯、褪黑素和奥美拉唑。最后采用PULCON定量技术测得3种成分的绝对含量分别为16.65、5.38、46.35 mg/g。测定结果与HPLC定量结果的对比表明,核磁共振方法能够在无对照品作参比,无需分离的条件下,直接、快速、准确分析保健食品中非目标成分的物质组成和绝对含量。     

核磁共振定量法测定利培酮含量

采用氢核磁共振定量法和氟核磁共振定量法测定利培酮含量。氢核磁共振定量法以利培酮δ7.29~7.35处质子峰为定量峰,马来酸δ6.02处为内标峰,在恒温300 K,采样时间4.0 s,弛豫延迟时间15 s,扫描次数为32次条件下采集氢谱。氟核磁共振定量法以4-溴-2-氟-乙酰苯胺为内标,在恒温300 K,谱宽12 500.0 Hz,中心频率-43 662.7 Hz下采集氟谱。测试结果显示,利培酮氢核磁共振定量法和氟核磁共振定量法的含量测定结果基本与质量平衡法的结果一致。因此,核磁共振法可用于利培酮绝对含量的测定,具有快速、简单、准确的优势。     

量子化学计算在有机化合物核磁共振教学中的应用

用量子化学方法计算化合物的核磁共振数据并与实验数据进行比较已经广泛应用于复杂天然产物构型的确定。以核磁共振教学为例,介绍量子化学计算在有机化合物波谱解析教学中的具体应用。通过计算核磁共振氢谱和碳谱的化学位移值,辅助解析分子结构,帮助学生对电子的分布、原子核的化学环境等有更直观的认识,有利于学生理解核磁共振的本质,有效提高学生的学习兴趣和积极性。同时,让学生了解量子化学计算在核磁共振中的应用,了解化学研究的前沿手段,开阔学生视野,培养学生解决实际问题的能力。     

水峰调制下的3,4-Seco-olean-11,13-dien-4,15α,22β,24-tetraol-3-oic Acid的NMR结构解析

对海南半红树植物黄槿(Hibiscus tiliaceus)内生菌中提取的一个新化合物进行核磁共振结构解析的研究. 在核磁共振测试时发现水峰信号与部分样品信号发生了重叠, 直接影响了该化合物谱图数据的分析. 本工作通过实验确证了在氘代二甲亚砜(DMSO-d₆)溶剂中水峰化学位移与含水量之间的变化规律. 依据该规律, 利用定量加入纯水的方法对实际样品中的水峰信号进行了调制, 解决了水峰信号与样品信号的重叠问题, 得到了较理想的¹H NMR, ¹³C NMR一维谱和COSY, HMQC, HMBC等二维谱. 利用核磁共振提供的信息完成了对新化合物结构的解析, 确定该化合物为齐墩果烷三萜类化合物3,4-seco-olean-11,13-dien-4,15α,22β,24-tetraol-3-oic acid.     

氟苯尼考胶体金免疫层析定量检测方法的建立

建立了定量检测氟苯尼考的胶体金免疫层析方法.对胶体金标记抗体时溶液pH和抗体浓度、金标抗体用量、检测线上抗原浓度以及检测时间进行了优化.采用胶体金试纸条读取仪测定试纸条检测线和质控线的信号强度,以标准品的浓度为横坐标,阳性样本和阴性样本的检测线/质控线的信号比值(Bx/B0)为纵坐标建立标准曲线.结果表明,胶体金免疫层析试纸定量检测氟苯尼考的线性范围为0.1~1.5 ng/mL,检出限为0.08 ng/mL,检测时间为15 min.本方法具有简便、快速和可定量等特点,适于大批量样品的现场筛查.     

肌酐纯度标准物质的定值方法及其不确定度评定研究

通过定性及定量分析,研究了肌酐纯度标准物质的定值方法,并进行了定值分析的不确定度评定。首先使用三重四极杆质谱仪及核磁共振谱仪(氢谱)对肌酐样品进行定性分析,然后采用质量平衡法(包括液相色谱法、水分、灰分、挥发性物质和无机元素分析)与定量核磁共振法共同对肌酐纯度标准物质进行准确定值,最后对定值结果进行不确定度评定。肌酐的定值结果为99.7%,扩展不确定度为0.4%。该研究对于实际检测中肌酐的准确测定及临床上相关疾病的正确诊断治疗具有重要意义,且经过定值的肌酐纯品还可做定量核磁共振法的定量内标使用。定量分析后的肌酐经过均匀性检验和稳定性考察后可申报为国家标准物质。     

定量核磁共振氢谱法测定枸橼酸托法替布片的有效含量

建立了枸橼酸托法替布片中有效含量的定量核磁共振氢谱测定方法。以托法替布化学位移δ 7.13为定量峰,3,5-二甲基吡唑化学位移δ 5.73为内标峰,氘代二甲亚砜（DMSO-D6）为溶剂,使用核磁共振谱仪采集混合物的氢谱,对枸橼酸托法替布片中的有效成分进行定量测定。该方法专一性强,在0.793～7.925 mg/mL范围内呈现良好的线性关系（r2=0.998 4）。精密度、重复性和稳定性的相对标准偏差（RSD）分别为0.82%、1.7%和0.67%。该方法测得的枸橼酸托法替布片中托法替布的质量分数为2.25%,其结果与高效液相色谱法基本一致。定量核磁共振氢谱法具有操作方便简单,可同时进行定性与定量,检测时间短,无需对照品等优势,可用于枸橼酸托法替布片有效含量的测定。     

利用核磁共振氢谱分析异构化产物

核磁共振是解析有机化合物结构的一种常用的方法，也是有机波谱分析课程教学中的重点内容之一。本文结合三个实例介绍了核磁共振氢谱解析思路，理论与科研实际相结合，利用核磁共振氢谱判断产物中异构体的结构，通过峰组的积分面积确定异构体的比例，以便培养学生的科学素养，激发学生的学习兴趣，提高谱图的解析能力。     

^(1)H和^(19)F核磁共振定量法测定诺氟沙星标准品的绝对含量EI北大核心CSCD

采用^(1)H和^(19)F核磁共振定量法测定诺氟沙星标准品的绝对含量。^(1)H核磁共振定量法以DMSO-d6为溶剂,诺氟沙星峰(δ7.9)为定量峰,马来酸峰(δ6.3)为内标峰。在脉冲程序zg30,采样时间4.09 s,延迟时间20 s,扫描次数为16的条件下采集氢谱。^(19)F核磁共振定量法以利培酮为内标物,诺氟沙星峰(δ-121.3)为定量峰,利培酮峰(δ-109.9)为内标峰。在脉冲程序zgfhigqn.2,延迟时间7 s,扫描次数为16的条件下采集氟谱。^(1)H和^(19)F核磁共振定量法测定结果接近,且与质量平衡法测定结果一致。核磁共振定量法可用来测定诺氟沙星绝对含量,快速、简单高效、且不需要对照品。     

A carbanion induced synthesis of highly congested pyrazole and imidazole containing heterocycles

An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

Selective synthesis of 4,5-dihydroimidazo- and imidazo[1,5-a]quinoxalines via modified Pictet–Spengler reaction

An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Understanding the Diels-Alder reactivity of 1,2-azaborine analogues

The Diels-Alder reactivity of 1,2-heteroborines (H₄C₄B(H)X, X?=?NH, PH, AsH; O, S, Se) has been computationally explored by means of Density Functional Theory (DFT) calculations. The influence of the HB?=?X fragment on the reactivity of the system has been quantitatively analyzed in detail by means of the so-called Activation Strain Model (ASM) of reactivity. It is found that the interaction between these species and the dienophile is significantly stronger than that computed for their all-carbon isoelectronic counterpart, benzene. In addition, the strain energy plays a key role in the observed reactivity trends. The role of the aromaticity strength of these heteroarenes on the reactivity is also assessed.     

Synthesis of N-substituted carbazolones from α-iodo enaminones via Pd(0)-catalyzed intramolecular coupling under microwave irradiation

A variety of N-aryl and N-alkyl carbazolones were conveniently achieved in good to high yields via Pd₂(dba)₃-mediated intramolecular coupling of N-substituted α-iodo enaminones under microwave irradiation. The Pd(0)-catalyzed cyclization was found to proceed favorably with the more electron-deficient phenyl ring during the reactions involving unsymmetrical N,N-diaryl α-iodo enaminones. This unique property enables the construction of carbazolone skeleton containing nitro substituted benzenoid ring.     

Synthesis of substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles by intramolecular nitrilimine cycloaddition

Both substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles have been synthesized by the 3+2 intramolecular dipolar cycloaddition of nitrilimines to alkynes. This cyclization has been extended to more versatile 3-bromo derivatives by the use of alkynylbromides as dipolarophiles.     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.