We describe the design and execution of a novel synthetic route to the tricyclic core of haliclonin A,a tetracyclic marine natural product.The approach features Bachi＇s thiol-medicated free radical cyclization of alk...We describe the design and execution of a novel synthetic route to the tricyclic core of haliclonin A,a tetracyclic marine natural product.The approach features Bachi＇s thiol-medicated free radical cyclization of alkenyl isocyanide to build the bridged ring system,and ring-closing metathesis（RCM） reaction to form the macrocycle.Execution of the synthetic plan ultimately resulted in a diazatricyclic compound.By means of 2D NMR techniques,the structure of this compound was revealed to an unexpected product 8.Analysis of the synthetic pathways allowed concluding that the unexpected product is a result of an ＂unexpected＂ migration of olefinic bond during dioxolanation of the 2-cyclohexenone derivative 7.This investigation also resulted in a concise construction of the functionalized hexahydro-1H-isoindole-1,5（4H）-dione 12 and the macrocyclic tricyclic ring system 8.展开更多
The 2D NMR(T_(1)-T_(2))mapping technique,which can be used to separate different proton populations from various sources(hydroxyls,solid organic matter,free water,and free HC)has gained attention in petroleum industry...The 2D NMR(T_(1)-T_(2))mapping technique,which can be used to separate different proton populations from various sources(hydroxyls,solid organic matter,free water,and free HC)has gained attention in petroleum industry.To separate proton contributions,a fixed straight line is commonly employed to separate different regions representing proton sources on the map.However,some of these regions(Region 1 and 2)might overlap which makes extracting the NMR signal amplitude from these regions inaccurate.In order to solve this issue,in this study,we applied the Gaussian distribution deconvolution method to separate the T_(1)and T_(2)relaxation distributions and then derived the signal amplitude of each region instead of following the common fixed line approach.Next,we employed this method to analyze several shale samples from the literature and compared the results following both methods to verify our methodology.Finally,samples from the Bakken Shale were studied to separate signals from Region 1 and Region 2 and corelated the results with geochemical properties that were obtained from programmed(Rock Eval)pyrolysis.Results demonstrated an improvement in their relation when our approach is employed compared to the fixed line technique to differentiate signal from overlapping regions.This means the Gaussian distribution deconvolution method can be used with confidence to provide us with more accurate petrophysical and geochemical understanding of complex formations.展开更多
The Oxytropis, legume genus, is native in the northwest of China, and some of its members have been reported to be toxic to grazing livestock. In the course of studying toxic reason of this legume, a toxic alkaloid wa...The Oxytropis, legume genus, is native in the northwest of China, and some of its members have been reported to be toxic to grazing livestock. In the course of studying toxic reason of this legume, a toxic alkaloid was isolated from Oxytropis glabra D C. grown in the Inner Mongolian Autonomous Region. The LD+（50） of （—）-thermopsine（Ⅰ） was shown to be 89.98 mg/kg（in mice）. This paper reports an approach to the structure elucidation of（-）-thermopsine by combining 2D NMR[;H-;H and;H-;C （one-bond and long-range） COSY] and other physicochemical methods. The stereochemistry of compound Ⅰ is also discussed.展开更多
Nuclear magnetic resonance(NMR)spectroscopy is a powerful tool for analyzing molecular structure and composition.However,traditional NMR experiments suffer from long acquisition times,especially in multidimensional NM...Nuclear magnetic resonance(NMR)spectroscopy is a powerful tool for analyzing molecular structure and composition.However,traditional NMR experiments suffer from long acquisition times,especially in multidimensional NMR spectroscopy.This problem,to some extent,limits broader applications of NMR techniques.Various methods have been proposed to accelerate sampling,including non-uniform sampling(NUS),multi-FID acquisition(MFA),Hadamard encoding,Fourier encoding,spatial encoding Ultrafast 2D NMR(UF2DNMR),and so on.The review focuses on rapid sampling methods developed in contemporary China,introducing their fundamental principles and applications while discussing their respective advantages and disadvantages.展开更多
Employing triflic anhydride/2-fluoropyridine as an activation system, the coupling reactions of secondary N-aryl amides with terminal alkynes yielded substituted quinolines in moderate to excellent yields. The reactio...Employing triflic anhydride/2-fluoropyridine as an activation system, the coupling reactions of secondary N-aryl amides with terminal alkynes yielded substituted quinolines in moderate to excellent yields. The reaction tolerated both electron-donating and electron-withdrawing groups at the benzamide moiety. Electron-rich aryl acetylenes served as excellent coupling partners, and aliphatic terminal alkynes such as cyclopropyl and conjugate vinyl acetylenes could also be used as reaction partners. By means of 2 D NMR techniques(heteronuclear multiple bond correlation(HMBC), heteronuclear single quantum correlation(HSQC)),nitrilium ions were probed as reactive intermediates which are in contrast with that suggested by Movassaghi on the basis of in situ IR monitoring experiments. On the basis of these results, a plausible mechanism for the formation of quinolines was suggested.展开更多
We present here the application of one-dimensional and two-dimensional NMR techniques to characterize the structure of methoxyl end-functionalized polystyrenes （PS）. The peaks in 1H-NMR spectra corresponding to main...We present here the application of one-dimensional and two-dimensional NMR techniques to characterize the structure of methoxyl end-functionalized polystyrenes （PS）. The peaks in 1H-NMR spectra corresponding to main-chain, side-chain and chain-end groups are assigned by 1H-1H gCOSY, 1H-13C gHSQC and gHMBC spectra. For the first time, the spin-lattice relaxation time （T1） of protons of the chain-ends is revealed to be affected more by polymer molecular weight （MW） than by the protons of the main-chains and the side-chains （almost independent from MW）. As a result, a much higher delay time （dl） for chain-ends （d1〉 20T1） is needed for quantitative NMR measurement when using end-group estimation method to obtain the MW of PS, which is in accordance with the value estimated by GPC. An improved method for the polymer MW determination is established, by combination of different NMR techniques to distinguish the peaks, and a large dl setting to achieve quantitative NMR analysis.展开更多
Structural elucidation (automatic determination of the structure of amolecule from its spectra) is frequently hampered by combinatorial explosion when trying to assemblethe identified substructures. We devised a new m...Structural elucidation (automatic determination of the structure of amolecule from its spectra) is frequently hampered by combinatorial explosion when trying to assemblethe identified substructures. We devised a new method which can avoid this pitfall by a systematicexamination of allowed ^(13)C chemical shifts ranges for all substructures chemically possible andcombined with a progressive pruning thanks to neighbouring relationships appearing from 2D NMR. Thismethod is explained by a detailed example.展开更多
Bile acids are the main body of enterohepatic circulation in vivo.They have essential functions such as emulsifying fat,bacteriostasis and regulating multiple metabolic pathways as signal molecules.However,the assignm...Bile acids are the main body of enterohepatic circulation in vivo.They have essential functions such as emulsifying fat,bacteriostasis and regulating multiple metabolic pathways as signal molecules.However,the assignments of NMR signals for some lowconcentration bile acids are still needed.This study combined 1D nuclear magnetic resonance(NMR)and 2D NMR techniques including 1He1H correlation spectroscopy(COSY),1He1H total correlation spectroscopy(TOCSY),1H J-resolved spectroscopy(J-Res),1He13C heteronuclear single quantum coherence spectroscopy(HSQC),and 1He13C heteronuclear multiple bond correlation spectroscopy(HMBC)to assign the 1H and 13C signals of six bile acids in aqueous solution at physiological pH(~7.4)and nine bile acids in methanol.These data are of importance to the NMR-based studies on lipid digestion,absorption,and metabolism.展开更多
Two-dimensional(2D)nuclear magnetic resonance(NMR)inversion operates with massive echo train data and is an ill-posed problem.It is very important to select a suitable inversion method for the 2D NMR data processing.I...Two-dimensional(2D)nuclear magnetic resonance(NMR)inversion operates with massive echo train data and is an ill-posed problem.It is very important to select a suitable inversion method for the 2D NMR data processing.In this study,we propose a fast,robust,and effective method for 2D NMR inversion that improves the computational efficiency of the inversion process by avoiding estimation of some unneeded regularization parameters.Firstly,a method that combines window averaging(WA)and singular value decomposition(SVD)is used to compress the echo train data and obtain the singular values of the kernel matrix.Subsequently,an optimum regularization parameter in a fast manner using the signal-to-noise ratio(SNR)of the echo train data and the maximum singular value of the kernel matrix are determined.Finally,we use the Butler-Reeds-Dawson(BRD)method and the selected optimum regularization parameter to invert the compressed data to achieve a fast 2D NMR inversion.The numerical simulation results indicate that the proposed method not only achieves satisfactory 2D NMR spectra rapidly from the echo train data of different SNRs but also is insensitive to the number of the final compressed data points.展开更多
基金the National Natural Science Foundation of China(No.21472153)the National Basic Research Program(973 Program)of China(No.2010CB833200)+1 种基金the SKL of Xiamen University(No.201509)the Program for Changjiang Scholars and Innovative Research Team in University of Ministry of Education,China,for financial support
文摘We describe the design and execution of a novel synthetic route to the tricyclic core of haliclonin A,a tetracyclic marine natural product.The approach features Bachi＇s thiol-medicated free radical cyclization of alkenyl isocyanide to build the bridged ring system,and ring-closing metathesis（RCM） reaction to form the macrocycle.Execution of the synthetic plan ultimately resulted in a diazatricyclic compound.By means of 2D NMR techniques,the structure of this compound was revealed to an unexpected product 8.Analysis of the synthetic pathways allowed concluding that the unexpected product is a result of an ＂unexpected＂ migration of olefinic bond during dioxolanation of the 2-cyclohexenone derivative 7.This investigation also resulted in a concise construction of the functionalized hexahydro-1H-isoindole-1,5（4H）-dione 12 and the macrocyclic tricyclic ring system 8.
基金support from the National Natural Science Foundation of China(42090020,42090025,42272150)the Sinopec Science and Technology Department(No.P20049-1).
文摘The 2D NMR(T_(1)-T_(2))mapping technique,which can be used to separate different proton populations from various sources(hydroxyls,solid organic matter,free water,and free HC)has gained attention in petroleum industry.To separate proton contributions,a fixed straight line is commonly employed to separate different regions representing proton sources on the map.However,some of these regions(Region 1 and 2)might overlap which makes extracting the NMR signal amplitude from these regions inaccurate.In order to solve this issue,in this study,we applied the Gaussian distribution deconvolution method to separate the T_(1)and T_(2)relaxation distributions and then derived the signal amplitude of each region instead of following the common fixed line approach.Next,we employed this method to analyze several shale samples from the literature and compared the results following both methods to verify our methodology.Finally,samples from the Bakken Shale were studied to separate signals from Region 1 and Region 2 and corelated the results with geochemical properties that were obtained from programmed(Rock Eval)pyrolysis.Results demonstrated an improvement in their relation when our approach is employed compared to the fixed line technique to differentiate signal from overlapping regions.This means the Gaussian distribution deconvolution method can be used with confidence to provide us with more accurate petrophysical and geochemical understanding of complex formations.
文摘The Oxytropis, legume genus, is native in the northwest of China, and some of its members have been reported to be toxic to grazing livestock. In the course of studying toxic reason of this legume, a toxic alkaloid was isolated from Oxytropis glabra D C. grown in the Inner Mongolian Autonomous Region. The LD+（50） of （—）-thermopsine（Ⅰ） was shown to be 89.98 mg/kg（in mice）. This paper reports an approach to the structure elucidation of（-）-thermopsine by combining 2D NMR[;H-;H and;H-;C （one-bond and long-range） COSY] and other physicochemical methods. The stereochemistry of compound Ⅰ is also discussed.
基金financially supported by the National Natural Science Foundation of China(grant numbers 22174118,12411530077,and 22374124).
文摘Nuclear magnetic resonance(NMR)spectroscopy is a powerful tool for analyzing molecular structure and composition.However,traditional NMR experiments suffer from long acquisition times,especially in multidimensional NMR spectroscopy.This problem,to some extent,limits broader applications of NMR techniques.Various methods have been proposed to accelerate sampling,including non-uniform sampling(NUS),multi-FID acquisition(MFA),Hadamard encoding,Fourier encoding,spatial encoding Ultrafast 2D NMR(UF2DNMR),and so on.The review focuses on rapid sampling methods developed in contemporary China,introducing their fundamental principles and applications while discussing their respective advantages and disadvantages.
基金supported by the National Key R&D Program of China (2017YFA0207302)the National Natural Science Foundation of China (21332007, 21672176)+1 种基金the Natural Science Foundation of Fujian Province, China (2017J01021)the Program for Changjiang Scholars and Innovative Research Team in University of Ministry of Education, China
文摘Employing triflic anhydride/2-fluoropyridine as an activation system, the coupling reactions of secondary N-aryl amides with terminal alkynes yielded substituted quinolines in moderate to excellent yields. The reaction tolerated both electron-donating and electron-withdrawing groups at the benzamide moiety. Electron-rich aryl acetylenes served as excellent coupling partners, and aliphatic terminal alkynes such as cyclopropyl and conjugate vinyl acetylenes could also be used as reaction partners. By means of 2 D NMR techniques(heteronuclear multiple bond correlation(HMBC), heteronuclear single quantum correlation(HSQC)),nitrilium ions were probed as reactive intermediates which are in contrast with that suggested by Movassaghi on the basis of in situ IR monitoring experiments. On the basis of these results, a plausible mechanism for the formation of quinolines was suggested.
基金supported by the National Natural Science Foundation of China(Nos.21274099,21305098 and 21474067)the Priority Academic Program Development of Jiangsu High Education Institutions
文摘We present here the application of one-dimensional and two-dimensional NMR techniques to characterize the structure of methoxyl end-functionalized polystyrenes （PS）. The peaks in 1H-NMR spectra corresponding to main-chain, side-chain and chain-end groups are assigned by 1H-1H gCOSY, 1H-13C gHSQC and gHMBC spectra. For the first time, the spin-lattice relaxation time （T1） of protons of the chain-ends is revealed to be affected more by polymer molecular weight （MW） than by the protons of the main-chains and the side-chains （almost independent from MW）. As a result, a much higher delay time （dl） for chain-ends （d1〉 20T1） is needed for quantitative NMR measurement when using end-group estimation method to obtain the MW of PS, which is in accordance with the value estimated by GPC. An improved method for the polymer MW determination is established, by combination of different NMR techniques to distinguish the peaks, and a large dl setting to achieve quantitative NMR analysis.
文摘Structural elucidation (automatic determination of the structure of amolecule from its spectra) is frequently hampered by combinatorial explosion when trying to assemblethe identified substructures. We devised a new method which can avoid this pitfall by a systematicexamination of allowed ^(13)C chemical shifts ranges for all substructures chemically possible andcombined with a progressive pruning thanks to neighbouring relationships appearing from 2D NMR. Thismethod is explained by a detailed example.
文摘Bile acids are the main body of enterohepatic circulation in vivo.They have essential functions such as emulsifying fat,bacteriostasis and regulating multiple metabolic pathways as signal molecules.However,the assignments of NMR signals for some lowconcentration bile acids are still needed.This study combined 1D nuclear magnetic resonance(NMR)and 2D NMR techniques including 1He1H correlation spectroscopy(COSY),1He1H total correlation spectroscopy(TOCSY),1H J-resolved spectroscopy(J-Res),1He13C heteronuclear single quantum coherence spectroscopy(HSQC),and 1He13C heteronuclear multiple bond correlation spectroscopy(HMBC)to assign the 1H and 13C signals of six bile acids in aqueous solution at physiological pH(~7.4)and nine bile acids in methanol.These data are of importance to the NMR-based studies on lipid digestion,absorption,and metabolism.
基金funded by National Science and Technology Major Project of the Ministry of Science and Technology of China(2016ZX05033-003-001).
文摘Two-dimensional(2D)nuclear magnetic resonance(NMR)inversion operates with massive echo train data and is an ill-posed problem.It is very important to select a suitable inversion method for the 2D NMR data processing.In this study,we propose a fast,robust,and effective method for 2D NMR inversion that improves the computational efficiency of the inversion process by avoiding estimation of some unneeded regularization parameters.Firstly,a method that combines window averaging(WA)and singular value decomposition(SVD)is used to compress the echo train data and obtain the singular values of the kernel matrix.Subsequently,an optimum regularization parameter in a fast manner using the signal-to-noise ratio(SNR)of the echo train data and the maximum singular value of the kernel matrix are determined.Finally,we use the Butler-Reeds-Dawson(BRD)method and the selected optimum regularization parameter to invert the compressed data to achieve a fast 2D NMR inversion.The numerical simulation results indicate that the proposed method not only achieves satisfactory 2D NMR spectra rapidly from the echo train data of different SNRs but also is insensitive to the number of the final compressed data points.
