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1.
Felix Nußbaumer Raphael Plangger Manuel Roeck Christoph Kreutz 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(39):17210-17217
We present the access to [5-19F, 5-13C]-uridine and -cytidine phosphoramidites for the production of site-specifically modified RNAs up to 65 nucleotides (nts). The amidites were used to introduce [5-19F, 5-13C]-pyrimidine labels into five RNAs—the 30 nt human immunodeficiency virus trans activation response (HIV TAR) 2 RNA, the 61 nt human hepatitis B virus ϵ (hHBV ϵ) RNA, the 49 nt SAM VI riboswitch aptamer domain from B. angulatum, the 29 nt apical stem loop of the pre-microRNA (miRNA) 21 and the 59 nt full length pre-miRNA 21. The main stimulus to introduce the aromatic 19F–13C-spin topology into RNA comes from a work of Boeszoermenyi et al., in which the dipole-dipole interaction and the chemical shift anisotropy relaxation mechanisms cancel each other leading to advantageous TROSY properties shown for aromatic protein sidechains. This aromatic 13C–19F labeling scheme is now transferred to RNA. We provide a protocol for the resonance assignment by solid phase synthesis based on diluted [5-19F, 5-13C]/[5-19F] pyrimidine labeling. For the 61 nt hHBV ϵ we find a beneficial 19F–13C TROSY enhancement, which should be even more pronounced in larger RNAs and will facilitate the NMR studies of larger RNAs. The [19F, 13C]-labeling of the SAM VI aptamer domain and the pre-miRNA 21 further opens the possibility to use the biorthogonal stable isotope reporter nuclei in in vivo NMR to observe ligand binding and microRNA processing in a biological relevant setting. 相似文献
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利用单相机所采集的图像实现了对光滑高反射表面面形的直接检测.首先利用相机获取参考平面在标准平面镜中的镜像,然后通过参考平面上的点与归一化成像平面上图像点之间的密集折返对应关系,求得待测镜面的深度距离,从而实现对高反射表面面形的测量.通过光线追迹将该测量过程转化为求解物空间中关于两对应光线束之间的相交问题.以相位为载体获取面形梯度分布,求得该表面的法向量场,并求解相应的反射光线束.通过光线追迹对该光线束与相应入射光线束求“交点”检测高反射表面.对标准平面镜进行实验检测,测量得到的面形平面度为0.19 mm.采用传统方法与本文所提方法对汽车后视镜进行检测,所得检测结果对应点之间的平均距离为0.15 mm,验证了本文方法检测镜面面形的有效性. 相似文献
4.
Fourier transform infrared (FTIR) smog chamber techniques were used to investigate the atmospheric chemistry of the isotopologues of methane. Relative rate measurements were performed to determine the kinetics of the reaction of the isotopologues of methane with OH radicals in cm3 molecule−1 s−1 units: k(CH3D + OH) = (5.19 ± 0.90) × 10−15, k(CH2D2 + OH) = (4.11 ± 0.74) × 10−15, k(CHD3 + OH) = (2.14 ± 0.43) × 10−15, and k(CD4 + OH) = (1.17 ± 0.19) × 10−15 in 700 Torr of air diluent at 296 ± 2 K. Using the determined OH rate coefficients, the atmospheric lifetimes for CH4–xDx (x = 1–4) were estimated to be 6.1, 7.7, 14.8, and 27.0 years, respectively. The results are discussed in relation to previous measurements of these rate coefficients. 相似文献
5.
A water circulation system with the almost same element composition and socket type was adopted in coral Acropora culture under different seawater pH value conditions and the data of the relationship between boron isotopic compositions of coral and seawater pH value by thermoelectric ionization mass spectrometer were obtained. According to the correlations between αcarb-3 of coral and the pH value of cultured seawater, αcarb-3 was not a constant but related to pH value, indicating that B(OH)3 also incorporated carbonate. Therefore, the theoretical formula could not be used to calculate the seawater pH value from the δ11Bcarb value of the measured marine biological carbonate. The empirical equations obtained experimentally would be an alternative method to calculate the seawater pH value. In addition, the mixed precipitation of CaCO3 and Mg(OH)2 was found in aquaculture tanks with high pH value, and the δ11B of the solid was significantly higher than that of cultured seawater. The result indicated that the presence of Mg(OH)2 had a significant effect on the boron isotope fractionation, which deserved our attention. 相似文献
6.
Chaonan Xie Qin Li Gang Han Huan Liu Jien Yang Jincheng Li 《Biomedical chromatography : BMC》2019,33(5)
Tricaine methanesulfonate is one of most commonly used anesthetics in fish during blood sampling, artificial propagation and long‐distance transportation. In this study, an accurate method for the quantitative determination of tricaine in fish samples by a stable isotope dilution assay coupled with high‐performance liquid chromatography–triple quadrupole mass spectrometry was developed. Tricaine‐D5 was synthesized and used as an isotopically labeled internal standard for the determination of tricaine. The analytical performance of the method was validated for tricaine determination in marine fish and freshwater fish. The determination of tricaine was linear in the range of 2.0–200.0 μg L?1. The limit of detection and limit of quantitation for fish muscle tissues were 1.0 and 4.0 μg kg?1, respectively. Good recoveries were obtained in the range of 92.08–97.50%. The inter‐ and intra‐assay relative standard deviations (RSD values) were investigated, and the values were 0.39–3.01 and 0.85–2.77%, respectively. The values of CCα and CCβ were 10.21–10.43 and 10.42–10.87 μg kg?1, respectively. The clearance of MS‐222 from grass carp was further studied using our method. The results demonstrate that MS‐222 could be well absorbed and rapidly eliminated after bath administration. 相似文献
7.
Emeline Appert Dr. Agnès Martin-Mingot Dr. Omar Karam Dr. Fabien Zunino Dr. Bastien Michelet Dr. Fodil Bouazza Prof. Sébastien Thibaudeau 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(49):e202201583
The field of medicinal chemistry is currently witnessing a deuterium rush owing to the remarkable properties of this element as bioisoster of hydrogen atom. Aromatic hydrogen isotope exchange (HIE) is one of the most studied strategies nowadays as it promises to access deuterium-modified drugs directly from their non-labeled parents. While most of the recent studies focus on metal-catalyzed C−H activation strategy, the use of superacidic conditions has been largely overlooked. This study shows that the use of TfOD as reaction medium allows the late-stage polydeuteration of a broad library of pharmaceuticals bearing a wide array of functional groups, complementing existing procedures. 相似文献
8.
Ronald C. Crouch Jeffrey G. Raab Marius Pelmuş Evgeny Tischenko Michael Frey Alexei V. Buevich Mikhail Reibarkh R. Thomas Williamson Gary E. Martin 《Magnetic resonance in chemistry : MRC》2022,60(2):210-220
Modification of the recently reported 19F-detected 1,1-ADEQUATE experiment that incorporates dual-optimization to selectively invert a wide range of 1JCC correlations in a 1,n-ADEQUATE experiment is reported. Parameters for the dual-optimization segment of the pulse sequence were modified to accommodate the increased size of 1JCC homonuclear coupling constants of poly- and perfluorinated molecules relative to protonated molecules to allow broadband inversion of the 1JCC correlations. The observation and utility of isotope shifts are reported for the first time for 1,1- and 1,n-ADEQUATE correlations. 相似文献
9.
Thomas Özgün Dr. Klaus Bergander Dr. Lei Liu Dr. Constantin G. Daniliuc Prof. Dr. Stefan Grimme Dr. Gerald Kehr Prof. Dr. Gerhard Erker 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(34):11958-11961
The energy profile of a frustrated Lewis pair (FLP) dihydrogen splitting system was determined by a combined experimental kinetic and DFT study. A trimethylene‐bridged phosphane–borane FLP was converted into its endothermic H2‐cleavage product by sequential H+/H? addition. The system could be handled at low temperature, and the kinetics of the H2 elimination were determined to give a rate constant of kHH,exp(299 K)=(2.87±0.1)×10?4 s?1 in solution. The primary kinetic isotope effects were determined; for example, (kHH/kDD)exp=3.19. The system was accurately analyzed by DFT calculations. 相似文献
10.
Multicomponent Molecular Orbital–Climbing Image–Nudged Elastic Band Method to Analyze Chemical Reactions Including Nuclear Quantum Effect 下载免费PDF全文
To analyze the H/D isotope effects on hydrogen transfer reactions in XHCHCHCHY?XCHCHCHYH (X, Y=O, NH, or CH2) including the nuclear quantum effect of proton and deuteron, we propose a multicomponent molecular orbital‐climbing image‐nudged elastic band (MC_MO–CI–NEB) method. We obtain not only transition state structures but also minimum‐energy paths (MEPs) on the MC_MO effective potential energy surface by using MC_MO–CI–NEB method. We find that nuclear quantum effect affects not only stationary‐point geometries but also MEPs and electronic structures in the reactions. We clearly demonstrate the importance of including nuclear quantum effects for H/D isotope effect on rate constants (kH/kD). 相似文献