一种用于光诱导反应体系的原位NMR装置的设计与应用

doi:10.11938/cjmr20243120

摘要/Abstract

摘要：

利用原位核磁共振（NMR）技术结合新设计的光反应装置对光激发的氟超敏化现象进行了系统性研究, 证实了光反应装置的有效性. 该反应装置由光源、光路、同轴准直连接器和溶液混匀系统四部分组成，通过标准信噪比值（S/N）计算公式对9种含氟芳香化合物与6种光敏剂的组合进行了检测. 此外，还通过对光促开环反应的连续监测进一步验证了装置的适配性. 综合结果分析，该光反应装置可以很好地与市售液体NMR谱仪适配以应用于光化学反应的检测和研究.

关键词: 原位核磁共振（NMR）, 氟超敏化, 光化学反应, 原位反应监测

Abstract:

In the present study, a systematic investigation of photoexcited fluorine supersensitization is carried out using in situ nuclear magnetic resonance (NMR) technique in combination with a newly designed photoresponsive device, and the validity of the photoresponsive device is confirmed. The reaction device consists of a light source, a light path, a coaxial collimating connector, and a solution mixing system, and the combination of nine fluorinated aromatic compounds with six photosensitizers is tested by the standard signal-to-noise (S/N) formula. In addition, the device's suitability is further verified by continuously monitoring the photopromoted open-loop reaction. The results show that the photoreactor can be well adapted to the commercially available NMR spectrometer for photochemical reaction detection and research.

Key words: in situ nuclear magnetic resonance (NMR), fluorine supersensitization, photochemical reactions, in situ reaction monitoring

中图分类号:

O482.53

沈志强, 邓亚博, 杨培菊, 胡霄雪, 黄晓卷, 许传芝, 宋焕玲. 一种用于光诱导反应体系的原位NMR装置的设计与应用[J]. 波谱学杂志, 2025, 42(1): 22-33.

SHEN Zhiqiang, DENG Yabo, YANG Peiju, HU Xiaoxue, HUANG Xiaojuan, XU Chuanzhi, SONG Huanling. Design and Application of an in situ NMR Device for Light-Induced Reaction Systems[J]. Chinese Journal of Magnetic Resonance, 2025, 42(1): 22-33.

图/表 14

图1

图2

图3

图4

图5

图6

图7

图8

表1

图9

表2

图10

表3

图11

参考文献 21

[1]	MANOILOV K Y, VERKHUSHA V V, SHCHERBAKOVA M D. A guide to the optogenetic regulation of endogenous molecules[J]. Nat Methods 2021, 18(9): 1027-1037. doi: 10.1038/s41592-021-01240-1 pmid: 34446923
[2]	BRECHUN K E, ARNDT K M. WOOLLEY G A. Strategies for the photo-control of endogenous protein activity[J]. Curr Opin Struct Biol, 2017, 45: 53-58.
[3]	ZHANG F, WANG X, LIU H, et al. Recent advances and applications of semiconductor photocatalytic technology[J]. Appl Sci, 2019, 9(12): 2489.
[4]	XIONG S, YIN X, WANG Q, et al. Photoacoustic spectroscopy gas detection technology research progress[J]. Appl Spectrosc, 2023, 78(2): 135-158.
[5]	NOLTE D D. Coherent light scattering from cellular dynamics in living tissues[J]. Rep Prog Phys, 2024, 87(3): 036601.
[6]	RAPP T L, DEFOREST C A. Targeting drug delivery with light: A highly focused approach[J]. Adv Drug Deliv Rev, 2021, 171: 94-107.
[7]	SUN C L, WANG C, BOULATOV R. Applications of photoswitches in the storage of solar energy[J]. Chem Photo Chem, 2019, 3(6): 268-283.
[8]	MILLS A, ROURKE O. In situ, simultaneous irradiation and monitoring of a photocatalyzed organic oxidation reaction in a TiO₂-coated NMR tube[J]. J Org Chem, 2015, 80 (20): 10342-10345. doi: 10.1021/acs.joc.5b01001 pmid: 26414339
[9]	LIAO Y X, GENG F S, SHEN M, et al. Solid-state NMR study on sodium intercalation at low voltage window for Na₃V₂(PO₄)₃ as an anode[J]. Magn Reson Lett, 2024, 4(2): 100093.
[10]	WANG H, TAO Z Q, JIANG G S, et al. In situ investigation of HdeA in bacterial outer membrane vesicles using NMR spectroscopy[J]. Chinese J Magn Reson, 2024, 41(1): 1-8.
	王欢, 陶志清, 姜国胜, 等. HdeA在细菌外膜囊泡环境下的原位NMR研究[J]. 波谱学杂志, 2024, 41(1): 1-8. doi: 10.11938/cjmr20233069
[11]	JIANG Y, ZHAO M, PENG Z Q, et al. Progress in in-situ electrochemical nuclear magnetic resonance for battery research[J]. Magn Reson Lett, 2024, 4(2): 200099.
[12]	BRAMHAM J E, GOLOVANOV A P. Sample illumination device facilitates in situ lightcoupled NMR spectroscopy without fibre optics[J]. Commun Chem, 2022, 5(1): 90.
[13]	PAULULAT T, RABE M, BERDNIKOVA D, et al. Modification of an NMR probe for monitoring of photoreactions[J]. J Magn Reson, 2021, 327: 106990
[14]	LIU W Q, SONG Y H, WANG X L, et al. In operando nuclear magnetic resonance spectroscopy study on photocatalytic methanol reforming[J]. Chinese J Magn Reson, 2019 36(3): 298-308.
	刘文卿, 宋艳红, 王雪璐, 等. 光催化甲醇重整机理的原位核磁共振研究[J]. 波谱学杂志, 2019 36(3): 298-308. doi: 10.11938/cjmr20182680
[15]	WANG R D, XU B B, SONG Y H, et al. Methanol-water interaction in photocatalytic methanol reforming-An operando NMR study[J]. Chinese J Magn Reson, 2021, 38(1): 43-57.
	王睿迪, 徐贝贝, 宋艳红, 等. 原位核磁共振技术研究光催化甲醇重整过程中甲醇与水的相互作用[J]. 波谱学杂志, 2021, 38(1): 43-57. doi: 10.11938/cjmr20202818
[16]	YE M, YANG Y N, ZHANG R, et al. Effects of co-catalysts and wavelength of light on the products of photocatalytic methanol reforming: an operando NMR study[J]. Chinese J Magn Reson, 2019, 36(4): 490-501.
	叶曼, 杨以宁, 张燃, 等. 原位核磁共振技术研究共催化剂类型以及光照波长对甲醇光催化重整产物的影响[J]. 波谱学杂志, 2019, 36(4): 490-501. doi: 10.11938/cjmr20192727
[17]	NIU X X, BAI Z J, YANG Y, et al. A quantitative study of photocatalytic reduction of Cr(VI) by Operando low-field NMR relaxometry[J]. Chinese J Magn Reson, 2021, 38(3): 403-413.
	牛星星, 白志杰, 杨翼, 等. 原位低场核磁共振弛豫法定量监测光催化Cr (VI) 还原反应[J]. 波谱学杂志, 2021, 38(3): 403-413. doi: 10.11938/cjmr20202815
[18]	XU B B, ZHOU M, MAN Y, et al. Cooperative motion in water-methanol clusters controls the reaction rates of heterogeneous photocatalytic reactions[J]. J Am Chem Soc, 2021, 143: 10940-10947
[19]	XU B B, ZHOU M, RAN Z, et al. Solvent water controls photocatalytic methanol reforming[J]. J Phys Chem Lett, 2020, 11: 3738-3744.
[20]	WANG X L, LIU W Q, YanYan Y, et al. Operando NMR spectroscopic analysis of proton transfer in heterogeneous photocatalytic reactions[J]. Nat Commun, 2016, 7: 11918. doi: 10.1038/ncomms11918 pmid: 27311326
[21]	OTOKIKO T, SHUJI K, SHIGEORI T. Cycloaddition of pyridinium methylides with electron-deficient olefins and silica-gel mediated elimination of pyridines from the cycloadducts: A new method of alkylation or hydroalkylidenation of olefins[J]. B Chem Soc Jpn, 1987, 60(4): 1489-1495.

编号	色素浓度/（mg/mL）	S/N（黑暗）	S/N（光照）
1	0.00015	5.17±2.0304	14.68±5.1055
2	0.00060	4.42±3.0952	39.40±3.5547
3	0.00117	3.90±3.1919	54.47±4.6659
4	0.00170	3.46±2.0815	77.08±2.7838
5	0.00268	3.62±4.1743	81.00±3.1994

编号	色素浓度/（mg/mL）	S/N（黑暗）	S/N（光照）
1	0.00015	5.51±3.1228	7.16±3.3184
2	0.00060	5.13±2.0593	10.31±3.5414
3	0.00117	4.54±2.5472	18.59±2.6619
4	0.00170	5.26±2.2379	21.19±2.4043
5	0.00268	4.45±2.2104	24.17±1.5945

	增敏倍率	S/N值（黑暗）	S/N值（光照）		增敏倍率	S/N值（黑暗）	S/N值（光照）
透明	3.65	5.26	19.18	透明	3.65	5.26	19.18
漆L	2.24	4.82	10.79	喷砂L	2.34	4.78	11.18
漆M	1.99	5.36	10.66	喷砂M	2.08	4.50	9.36
漆H	2.26	4.57	10.31	喷砂H	1.88	4.09	7.67