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Reactivation of Ni-TiO2 catalysts in hydrogen flow and in supercritical 2-propanol—Comparative study by electron spin resonance in situ Ni-TiO2催化剂在氢流和超临界2-丙醇中的反应——电子自旋共振原位比较研究
IF 2 3区 化学 Q3 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2023-09-08 DOI: 10.1002/mrc.5385
Irina Kandarakova, Stanislav Yakushkin, Nikolay Nesterov, Alexey Philippov, Oleg Martyanov

Highly dispersed Ni-TiO2 catalyst has been studied in the process of preparation and under catalytic transfer hydrogenation reaction conditions in supercritical 2-propanol (250°C, 70 bar) using electron spin resonance in situ. Electron spin resonance in situ has been used to study the process of the catalyst passivation and subsequent reduction of the oxide layer in the gas flow. Reduction of the NiO layer on the surface of passivated Ni nanoparticles has been detected in supercritical 2-propanol, which is in agreement with kinetic modeling data. It has been found that the reduction of the nickel oxide layer in supercritical 2-propanol occurs at a lower temperature compared with the reduction in hydrogen flow, according to in situ electron spin resonance study.

在超临界2-丙醇(250°C,70 bar)的电子自旋共振。原位电子自旋共振已被用于研究气流中催化剂钝化和随后氧化层还原的过程。在超临界2-丙醇中检测到钝化Ni纳米颗粒表面NiO层的还原,这与动力学建模数据一致。根据原位电子自旋共振研究,已经发现,与氢流中的还原相比,在超临界2-丙醇中氧化镍层的还原发生在更低的温度下。
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引用次数: 0
Mapping of 1H NMR chemical shifts relationship with chemical similarities for the acceleration of metabolic profiling: Application on blood products 加速代谢谱的1h NMR化学位移关系与化学相似性的映射:在血液制品上的应用。
IF 2 3区 化学 Q3 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2023-09-04 DOI: 10.1002/mrc.5392
Panteleimon G. Takis, Varvara A. Aggelidou, Caroline J. Sands, Alexandra Louka

One-dimensional (1D) proton-nuclear magnetic resonance (1H-NMR) spectroscopy is an established technique for the deconvolution of complex biological sample types via the identification/quantification of small molecules. It is highly reproducible and could be easily automated for small to large-scale bioanalytical, epidemiological, and in general metabolomics studies. However, chemical shift variability is a serious issue that must still be solved in order to fully automate metabolite identification. Herein, we demonstrate a strategy to increase the confidence in assignments and effectively predict the chemical shifts of various NMR signals based upon the simplest form of statistical models (i.e., linear regression). To build these models, we were guided by chemical homology in serum/plasma metabolites classes (i.e., amino acids and carboxylic acids) and similarity between chemical groups such as methyl protons. Our models, built on 940 serum samples and validated in an independent cohort of 1,052 plasma-EDTA spectra, were able to successfully predict the 1H NMR chemical shifts of 15 metabolites within ~1.5 linewidths (Δv1/2) error range on average. This pilot study demonstrates the potential of developing an algorithm for the accurate assignment of 1H NMR chemical shifts based solely on chemically defined constraints.

一维质子核磁共振(1h - nmr)波谱是一种成熟的技术,通过小分子的鉴定/定量来反褶积复杂的生物样品类型。它具有很高的可重复性,可以很容易地自动化用于小型到大规模的生物分析,流行病学和一般代谢组学研究。然而,为了使代谢物鉴定完全自动化,化学位移可变性仍然是一个必须解决的严重问题。在此,我们展示了一种策略,以增加分配的置信度,并基于最简单的统计模型(即线性回归)有效地预测各种核磁共振信号的化学位移。为了建立这些模型,我们以血清/血浆代谢物类别(即氨基酸和羧酸)的化学同源性和化学基团(如甲基质子)之间的相似性为指导。我们的模型建立在940份血清样本上,并在1052份血浆edta光谱的独立队列中进行了验证,能够成功预测15种代谢物的1 H NMR化学位移,平均误差范围为1.5线宽(Δv1/2)。这项初步研究表明,开发一种仅基于化学定义约束的1 H NMR化学位移精确分配算法的潜力。
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引用次数: 0
Differentiation of patients with and without prostate cancer using urine 1H NMR metabolomics 尿1h NMR代谢组学鉴别前列腺癌患者与非前列腺癌患者。
IF 2 3区 化学 Q3 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2023-09-01 DOI: 10.1002/mrc.5391
Anna-Laura Hasubek, Xiaoyu Wang, Ella Zhang, Marta Kobus, Jiashang Chen, Lindsey A. Vandergrift, Annika Kurreck, Felix Ehret, Sarah Dinges, Annika Hohm, Marlon Tilgner, Alexander Buko, Piet Habbel, Johannes Nowak, Nathaniel D. Mercaldo, Andrew Gusev, Adam S. Feldman, Leo L. Cheng

Prostate cancer (PCa) is one of the most prevalent cancers in men worldwide. For its detection, serum prostate-specific antigen (PSA) screening is commonly used, despite its lack of specificity, high false positive rate, and inability to discriminate indolent from aggressive PCa. Following increases in serum PSA levels, clinicians often conduct prostate biopsies with or without advanced imaging. Nuclear magnetic resonance (NMR)-based metabolomics has proven to be promising for advancing early-detection and elucidation of disease progression, through the discovery and characterization of novel biomarkers. This retrospective study of urine-NMR samples, from prostate biopsy patients with and without PCa, identified several metabolites involved in energy metabolism, amino acid metabolism, and the hippuric acid pathway. Of note, lactate and hippurate—key metabolites involved in cellular proliferation and microbiome effects, respectively—were significantly altered, unveiling widespread metabolomic modifications associated with PCa development. These findings support urine metabolomics profiling as a promising strategy to identify new clinical biomarkers for PCa detection and diagnosis.

前列腺癌(PCa)是世界范围内最常见的男性癌症之一。血清前列腺特异性抗原(PSA)筛查是常用的检测方法,但它缺乏特异性,假阳性率高,无法区分惰性和侵袭性前列腺癌。随着血清PSA水平的升高,临床医生通常在有或没有先进成像的情况下进行前列腺活检。基于核磁共振(NMR)的代谢组学已被证明有希望通过发现和表征新的生物标志物来推进疾病进展的早期检测和阐明。这项回顾性研究对有和没有前列腺癌的前列腺活检患者的尿液核磁共振样本进行了研究,发现了一些参与能量代谢、氨基酸代谢和马尿酸途径的代谢物。值得注意的是,乳酸和马粪酸——分别参与细胞增殖和微生物组效应的关键代谢物——被显著改变,揭示了与PCa发展相关的广泛代谢组学修饰。这些发现支持尿液代谢组学分析作为鉴别前列腺癌检测和诊断的新临床生物标志物的一种有前景的策略。
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引用次数: 0
Corrected solid-state 13C nuclear magnetic resonance peak assignment and side-group quantification of hydroxypropyl methylcellulose acetyl succinate pharmaceutical excipients 羟丙基甲基纤维素乙酰琥珀酸酯药用辅料的校正固态13C核磁共振峰分配和侧基定量
IF 2 3区 化学 Q3 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2023-08-30 DOI: 10.1002/mrc.5390
Zhaoxi Zheng, Yongchao Su, Klaus Schmidt-Rohr

Hydroxypropyl methylcellulose acetyl succinate (HPMCAS) is widely used as a pharmaceutical excipient, making a detailed understanding of its tunable structure important for formulation design. Several recently reported peak assignments in the solid-state 13C NMR spectrum of HPMCAS have been corrected here using peak integrals in quantitative spectra, spectral editing, empirical chemical-shift predictions based on solution NMR, and full spectrum simulation analogous to deconvolution. Unlike in cellulose, the strong peak at 84 ppm must be assigned to C2 and C3 methyl ethers, instead of regular C4 of cellulose. The proposed assignment of signals at <65 ppm to OCH sites, including C5 of cellulose, could not be confirmed. CH2 spectral editing showed two resolved OCH2 bands, a more intense one from O-CH2 ethers of C6 at >69 ppm and a smaller one from its esters and possibly residual CH2-OH groups, near 63 ppm. The strong intensities of resolved signals of acetyl, succinoyl, and oxypropyl substituents indicated the substitution of >85% of the OH groups in HPMCAS. The side-group concentrations in three different grades of HPMCAS were quantified.

羟丙基甲基纤维素乙酰琥珀酸酯(HPMCAS)是一种广泛应用的药用辅料,详细了解其可调结构对制剂设计具有重要意义。最近报道的HPMCAS固态13C NMR光谱中的几个峰分配已经在这里使用定量光谱中的峰积分、光谱编辑、基于溶液NMR的经验化学位移预测以及类似于去卷积的全谱模拟进行了校正。与纤维素不同,84处的强峰值 ppm必须分配给C2和C3甲基醚而不是纤维素的常规C4。在<;65 ppm到OCH位点,包括纤维素的C5,不能得到证实。CH2光谱编辑显示两个解析的OCH2带,一个来自C6的O-CH2醚的更强的带,在>;69 ppm和一个较小的来自其酯和可能残留的CH2-OH基团,接近63 ppm。乙酰基、琥珀酰基和氧丙基取代基的解析信号的强强度表明>;HPMCAS中85%的OH基团。对三种不同级别HPMCAS的副组浓度进行了定量。
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引用次数: 0
Solution and solid-state 33S NMR studies of 33S-labeled taurine 33S标记牛磺酸的溶液和固态33S NMR研究
IF 2 3区 化学 Q3 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2023-08-23 DOI: 10.1002/mrc.5387
Yuichi Masuda, Shinobu Ohki, Yuuki Mogami, Kenzo Deguchi, Kenjiro Hashi, Atsushi Goto, Tadashi Shimizu, Kazuhiko Yamada

Sulfur-33(33S) stable-isotope labeled taurine, 2-aminoethanesulfonic acid, has been synthesized, and a series of solution and solid-state 33S nuclear magnetic resonance (NMR) experiments at 14.1 and 18.8 T, respectively, have been carried out at room temperature. The single peak of a solution 33S NMR spectrum in 0.1-mM [33S]-taurine in D2O can be observed with the signal-to-noise (S/N) ratio of 9 in 40,000 scans, which paves the way toward in vivo analysis of pharmacokinetics and metabolism of 33S-labeled taurine. Undistorted magic-angle-spinning (MAS) and static 33S NMR spectra of polycrystalline [33S]-taurine are observed with sufficient S/N ratios for analysis, and the magnitudes of 33S EFG and CS tensors can be obtained.

合成了硫33(33S)稳定同位素标记的牛磺酸2-氨基乙磺酸,并在室温下分别在14.1和18.8T下进行了一系列溶液和固体33S核磁共振(NMR)实验。D2O中0.1-mM[33S]-牛磺酸溶液的33S NMR谱的单峰可以在40000次扫描中观察到,信噪比(S/N)为9,这为体内分析33S标记的牛磺酸的药代动力学和代谢铺平了道路。观察了多晶[33S]-牛磺酸的无畸变魔角自旋(MAS)和静态33S NMR谱,具有足够的S/N比进行分析,可以获得33S EFG和CS张量的大小。
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引用次数: 0
Penindolacid A, a new indole alkaloid from the marine-derived fungus Penicillium sp. Penindolacid A是一种新的吲哚类生物碱,产自海洋真菌青霉菌。
IF 2 3区 化学 Q3 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2023-08-23 DOI: 10.1002/mrc.5389
Jin-Xin Zhang, Bao-Dan Zhang, Ying Shi, Ya-Nan Zhai, Jin-Wei Ren, Lei Cai, Li-Yan Sun, Ling Liu

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引用次数: 0
Use of carbon-13 NMR to identify known natural products by querying a nuclear magnetic resonance database—An assessment 使用碳13核磁共振通过查询核磁共振数据库来鉴定已知的天然产物评估。
IF 2 3区 化学 Q3 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2023-08-15 DOI: 10.1002/mrc.5386
Jean-Marc Nuzillard

The quick identification of known organic low molecular weight compounds, also known as structural dereplication, is a highly important task in the chemical profiling of natural resource extracts. To that end, a method that relies on carbon-13 nuclear magnetic resonance (NMR) spectroscopy, elaborated in earlier works of the author's research group, requires the availability of a dedicated database that establishes relationships between chemical structures, biological and chemical taxonomy, and spectroscopy. The construction of such a database, called acd_lotus, was reported earlier, and its usefulness was illustrated by only three examples. This article presents the results of structure searches carried out starting from 58 carbon-13 NMR data sets recorded on compounds selected in the metabolomics section of the biological magnetic resonance bank (BMRB). Two compound retrieval methods were employed. The first one involves searching in the acd_lotus database using commercial software. The second one operates through the freely accessible web interface of the nmrshiftdb2 database, which includes the compounds present in acd_lotus and many others. The two structural dereplication methods have proved to be efficient and can be used together in a complementary way.

快速鉴定已知的有机低分子量化合物,也称为结构去复制,是天然资源提取物化学分析中的一项非常重要的任务。为此,作者研究小组的早期工作中阐述了一种依赖于碳-13核磁共振(NMR)光谱的方法,该方法需要一个专门的数据库来建立化学结构、生物和化学分类学以及光谱之间的关系。这样一个名为acd_lotus的数据库的构建在前面已经报道过了,它的有用性只通过三个例子来说明。本文介绍了从生物磁共振库(BMRB)代谢组学部分中选择的化合物上记录的58个碳-13 NMR数据集开始进行的结构搜索的结果。采用了两种复合检索方法。第一个是使用商业软件在acd_lotus数据库中进行搜索。第二个是通过nmrshiftdb2数据库的可自由访问的web界面进行操作,该数据库包括acd_lotus和许多其他数据库中的化合物。这两种结构去复制方法已被证明是有效的,并且可以以互补的方式一起使用。
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引用次数: 1
Removing acoustic ringing baseline curvature in 13C NMR spectra for quantitative analyses 用于定量分析的13C NMR谱中消除声学振铃基线曲率
IF 2 3区 化学 Q3 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2023-08-07 DOI: 10.1002/mrc.5384
Joseph K. Vasquez, Zhe Zhou, Brian Clark, Ad J. Kimenai, Benjamin R. Reiner, Nathan J. Rau, Dan Baugh III, Donald V. Eldred, Manjiri Paradkar, Chen Zheng, Jim DeFelippis, Janece M. Potter, Xiao Hua Qiu, Xiaohong Zong, Wenshiue Owen Young, Thomas Fitzgibbons, Aitor Moreno, Christoph Freudenberger, Maksim Mayzel

13C nuclear magnetic resonance (NMR) is traditionally considered an insensitive technique, requiring long acquisition times to measure dilute functionalities on large polymers. With the introduction of cryoprobes and better electronics, sensitivity has improved in a way that allows measurements to take less than 1/20th the time that they previously did. Unfortunately, a high Q-factor with cryoprobes creates baseline curvature related to acoustic ringing that affects quantitative NMR analyses. Manual baseline correction is commonly used to compensate for the baseline roll, but it is a time-intensive process. The outcome of manual baseline correction can vary depending on processing parameters, especially for complicated spectra. Additionally, it can be challenging to distinguish between broad peaks and baseline rolls. A new anti-ring pulse sequence (zgig_pisp) was previously reported to improve on the incumbent single pulse experiment (zgig). The original report presented limited comparison data with 13C NMR, but a thorough validation is needed before broader implementation can be considered. In this work, we report the round-robin testing and comparison of zgig_pisp and zgig pulse sequences. During the testing phase, we found that zgig_pisp is practically equivalent to zgig to ±2% for the majority of integrals examined. Additionally, a short broadband inversion pulse (BIP) was demonstrated as an alternative to the originally reported adiabatic CHIRP shaped pulse. The zgig_pisp pulse sequence code for Bruker spectrometers is also simplified.

13C核磁共振(NMR)传统上被认为是一种不灵敏的技术,需要很长的采集时间来测量大聚合物上的稀释官能团。随着冷冻探针和更好的电子设备的引入,灵敏度得到了提高,使测量所需的时间比以前减少了1/20。不幸的是,冷冻探针的高Q因子会产生与声学振铃相关的基线曲率,从而影响定量NMR分析。手动基线校正通常用于补偿基线滚动,但这是一个耗时的过程。手动基线校正的结果可能因处理参数而异,尤其是对于复杂的光谱。此外,区分宽峰值和基线滚动可能具有挑战性。先前报道了一种新的反环脉冲序列(zgig_isp),以改进现有的单脉冲实验(zgig)。最初的报告提供了有限的与13C NMR的比较数据,但在考虑更广泛的实施之前,需要进行彻底的验证。在这项工作中,我们报告了zgig_isp和zgig脉冲序列的循环测试和比较。在测试阶段,我们发现对于所检查的大多数积分,zgig_disp实际上相当于zgig到±2%。此外,短宽带反转脉冲(BIP)被证明是最初报道的绝热CHIRP形状脉冲的替代方案。对Bruker光谱仪的zgig_ isp脉冲序列编码也进行了简化。
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引用次数: 0
Anisotropic NMR data acquisition with a prototype 400 MHz cryogen-free NMR spectrometer 各向异性核磁共振数据采集与原型400兆赫无低温核磁共振光谱仪
IF 2 3区 化学 Q3 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2023-08-02 DOI: 10.1002/mrc.5380
Maria Victoria Silva Elipe, Ikenna Edward Ndukwe, Armando Navarro-Vázquez

High-temperature superconducting (HTS) materials have recently been incorporated into the construction of HTS cryogen-free magnets for nuclear magnetic resonance (NMR) spectroscopy. These HTS NMR spectrometers do not require liquid cryogens, thereby providing significant cost savings and facilitating easy integration into chemistry laboratories. However, the optimal performance of these HTS magnets against standard cryogen NMR magnets must be evaluated, especially with demanding modern NMR applications such as NMR in anisotropic media. The stability of the HTS magnets over time and their performance with complex pulse sequence experiments are the main unknown factors of this new technology. In this study, we evaluate the utility of our prototype 400 MHz cryogen-free power-driven HTS NMR spectrometer, installed in the fumehood of a chemistry laboratory, for stereochemical analysis of three commercial natural products (artemisinin, artemether, and dihydroartemisinin) via measurement of anisotropic NMR data, in particular, residual dipolar couplings. The accuracy of measurement of the anisotropic NMR data with the HTS magnet spectrometer is evaluated through the CASE-3D fitting protocol, as implemented in the Mestrenova-StereoFitter software program.

高温超导(HTS)材料最近被纳入到核磁共振(NMR)光谱的高温超导无低温磁体的构建中。这些HTS核磁共振光谱仪不需要液态冷冻,从而提供了显著的成本节约,并易于集成到化学实验室。然而,必须评估这些高温超导磁体对标准低温核磁共振磁体的最佳性能,特别是在要求苛刻的现代核磁共振应用中,如各向异性介质中的核磁共振。高温超导磁体随时间的稳定性及其在复杂脉冲序列实验中的性能是这项新技术的主要未知因素。在这项研究中,我们评估了我们的原型400 MHz无低温功率驱动的HTS核磁共振光谱仪的实用性,该光谱仪安装在化学实验室的油气室中,通过测量三种商业天然产物(青蒿素、蒿甲醚和双氢青蒿素)的各向异性核磁共振数据,特别是残余的偶极耦合,来进行立体化学分析。在Mestrenova-StereoFitter软件程序中,通过CASE-3D拟合方案对HTS磁谱仪测量各向异性核磁共振数据的精度进行了评估。
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引用次数: 0
Automated nuclear magnetic resonance fingerprinting of mixtures 混合物的自动核磁共振指纹识别
IF 2 3区 化学 Q3 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2023-07-29 DOI: 10.1002/mrc.5381
Thomas Specht, Justus Arweiler, Johannes Stüber, Kerstin Münnemann, Hans Hasse, Fabian Jirasek

Nuclear magnetic resonance (NMR) spectroscopy is a powerful tool for qualitative and quantitative analysis. However, for complex mixtures, determining the speciation from NMR spectra can be tedious and sometimes even unfeasible. On the other hand, identifying and quantifying structural groups in a mixture from NMR spectra is much easier than doing the same for components. We call this group-based approach “NMR fingerprinting.” In this work, we show that NMR fingerprinting can even be performed in an automated way, without expert knowledge, based only on standard NMR spectra, namely, 13C, 1H, and 13C DEPT NMR spectra. Our approach is based on the machine-learning method of support vector classification (SVC), which was trained here on thousands of labeled pure-component NMR spectra from open-source data banks. We demonstrate the applicability of the automated NMR fingerprinting using test mixtures, of which spectra were taken using a simple benchtop NMR spectrometer. The results from the NMR fingerprinting agree remarkably well with the ground truth, which was known from the gravimetric preparation of the samples. To facilitate the application of the method, we provide an interactive website (https://nmr-fingerprinting.de), where spectral information can be uploaded and which returns the NMR fingerprint. The NMR fingerprinting can be used in many ways, for example, for process monitoring or thermodynamic modeling using group-contribution methods—or simply as a first step in species analysis.

核磁共振(NMR)光谱是一种强大的定性和定量分析工具。然而,对于复杂的混合物来说,从核磁共振光谱中确定物种可能会很繁琐,有时甚至是不可行的。另一方面,从核磁共振光谱中识别和量化混合物中的结构基团要比对成分进行同样的分析容易得多。我们将这种基于基团的方法称为 "核磁共振指纹识别"。在这项工作中,我们展示了 NMR 指纹识别甚至可以自动执行,无需专业知识,只需基于标准 NMR 图谱,即 13C、1H 和 13C DEPT NMR 图谱。我们的方法基于支持向量分类 (SVC) 的机器学习方法,该方法是在数以千计来自开源数据库的标记纯成分 NMR 图谱上训练出来的。我们使用测试混合物演示了自动 NMR 指纹识别的适用性,这些混合物的光谱是使用简单的台式 NMR 光谱仪采集的。核磁共振指纹识别的结果与基本真实值非常吻合,而基本真实值是通过样品的重量制备得知的。为方便该方法的应用,我们提供了一个互动网站(https://nmr-fingerprinting.de),可在该网站上传光谱信息并返回 NMR 指纹。核磁共振指纹图谱可用于多种用途,例如,使用基团贡献法进行过程监控或热力学建模,或仅仅作为物种分析的第一步。
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引用次数: 0
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Magnetic Resonance in Chemistry
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