线粒体靶向的近红外HClO/ClO－荧光探针的研究进展

doi:10.19894/j.issn.1000-0518.210583

摘要/Abstract

摘要：

HClO/ClO^-作为细胞质中一种重要的活性氧（ROS），源自线粒体，参与各种生理和病理过程，因此快速有效检测HClO/ClO^-具有重要的生物学及生理学意义。荧光分析法因其灵敏度高、响应时间快、选择性高、成本低和操作简便等优点而备受关注。更重要的是，使用荧光探针可以在体外和体内可视化检测。近年来，为了研究HClO/ClO^-在细胞中的作用，已发展了一些靶向线粒体的荧光HClO/ClO^-探针。其中，发射波长位于短波区域的探针存在背景荧光强、组织穿透性差等不足，因此，开发具有远红外至近红外发射的HClO/ClO^-探针具有重要意义。本文围绕用于检测HClO/ClO^-的线粒体靶向近红外荧光探针的最新动态展开讨论，将探针检测HClO/ClO^-的反应类型分为不饱和双键的氧化、硫醚的氧化、氨基或酰肼的氧化和多位点的氧化等几个类别进行了归纳总结，希望为新一代高效灵敏、生物兼容性好的靶向性HClO/ClO^-荧光探针的发展提供一定的帮助。

关键词: 线粒体, 荧光探针, 近红外, 次氯酸

Abstract:

As an important reactive oxygen species （ROS）， HClO/ClO^- can retrospect to mitochondria and participates in various physiological and pathological processes. Therefore， it is particularly important to develop an effective method to detect HClO/ClO^- in the biology and physiology. Fluorescence analysis has attracted much attention because of its high sensitivity， fast response time， low cost， and easy operation. More importantly， the use of fluorescent probes can visualize the detection process in vitro and in vivo. In recent years， to study the role of hypochlorous acid in cells， many mitochondria-targeted fluorescent HClO/ClO^- probes have been designed and synthesized. Among them， some probes in the short-wavelength region suffer from some shortages， such as high autofluorescence and poor tissue penetration. Therefore， it is of great significance to develop HClO/ClO^- probes with far-infrared to near-infrared emission. This article focuses on the latest developments of mitochondrial-targeted near-infrared fluorescent probes used to detect HClO/ClO^- and summarizes their possible reaction mechanisms which are mainly divided into the oxidation of unsaturated double bonds， the oxidation of thioethers， the oxidation of amino groups or hydrazides and oxidation multi-sites. It is expected to be beneficial to develop the novel specific fluorescent probes in the monitoring of physiological and pathological HClO/ClO^-.

Key words: Mitochondria, Fluorescent probe, Near infrared, Hypochlorous acid

中图分类号:

O652.1

黄蕊, 叶长青, 李亚军, 邱盟峯, 李达谅, 鲍红丽. 线粒体靶向的近红外HClO/ClO^－荧光探针的研究进展[J]. 应用化学, 2022, 39(3): 407-424.

Rui HUANG, Chang-Qing YE, Ya-Jun LI, Mong-Feng CHIOU, Da-Liang LI, Hong-Li BAO. Progress of Mitochondria⁃Targeted Near⁃Infrared HClO/ClO^- Fluorescent Probes[J]. Chinese Journal of Applied Chemistry, 2022, 39(3): 407-424.

图/表 19

图1 探针CMBI的合成路线和与ClO-的反应机制［51］

Fig.1 The synthetic route of probe CMBI and the reaction mechanism with ClO-［51］

图2 探针羟基取代的香豆素-半菁和与ClO-的反应机制［54］

Fig.2 The reaction mechanism of probe OH-substituted coumarin-hemicyanine dye with ClO-［54］

图3 探针NSSN的合成路径［59］

Fig.3 Synthesis path of probe NSSN［59］

图4 HClO存在下探针NSSN的反应机制［59］

Fig.4 The reaction mechanism of probe NSSN in the presence of HClO［59］

图5 探针C3H对HClO的响应机制［64］

Fig.5 The response mechanism of probe C3H to HClO［64］

图6 Mito?NCHO和Mito?NClO的合成路径［65］

Fig.6 Synthesis path of Mito?NCHO and Mito?NClO［65］

图7 探针Mito?NClO对ClO-的反应机制［65］

Fig.7 The reaction mechanism of Mito?NClO probe to ClO-［65］

图8 探针Cy7?NphS对HClO和MPO的响应机制［69］

Fig.8 The response mechanism of Cy7?NphS probe to HClO and MPO［69］

图9 探针L对HClO的响应机制［70］

Fig.9 The response mechanism of probe L to HClO［70］

图10 探针MXS对HClO的响应机制［71］

Fig.10 The response mechanism of probe MXS to HClO［71］

图11 探针CVS对HClO的响应机制［76］

Fig.11 The response mechanism of probe CVS to HClO［76］

图12 探针NB?OCl对ClO-的响应机制［80］

Fig.12 The response mechanism of probe NB?OCl to ClO-［80］

图13 探针NCS?BOD?OCH3 对ClO-的反应机制［81］

Fig.13 The reaction mechanism of probe NCS?BOD?OCH3 to ClO-［81］

图14 探针Mito?TP?ClO对ClO-的响应机制［84］

Fig.14 The response mechanism of Mito?TP?ClO probe to ClO-［84］

图15 荧光探针Cy7?Nil对不同浓度HClO/ClO-的荧光响应过程［86］

Fig.15 Fluorescence response process of Cy7?Nil fluorescent probe to different concentrations of HClO/ClO-［86］

图16 探针P?HClO?SO2 的合成方法［48］

Fig.16 Synthesis method of probe P?HClO?SO2［48］

图17 探针P?HClO?SO2 在线粒体中对HClO-SO2循环的检测［96］

Fig.17 The detection of the HClO-SO2 cycle in the mitochondria by the probe P?HClO?SO2［96］

图18 探针D6的反应机理［62］

Fig.18 Reaction mechanism of probe D6［62］

表1 探针的性能

Table 1 Probe performance

序号

No.

化合物名称

Compound's name

化合物结构

Compound's structure

荧光量子产率

Quantum yield（Φ）

皮尔森或重叠系数

Pearson's/overlap coefficient

检测限

Detection limit

响应时间

Response time

参考文献 110

1	LIN M T， BEAL M F. Mitochondrial dysfunction and oxidative stress in neurodegenerative diseases［J］. Nature，2006， 443（7113）： 787-795.
2	ADEGOKE O， FORBES P B C. Challenges and advances in quantum dot fluorescent probes to detect reactive oxygen and nitrogen species： a review［J］. Anal Chim Acta，2015， 862： 1-13.
3	HARRISON J E， SCHULTZ J. Studies on the chlorinating activity of myeloperoxidase［J］. J Biol Chem，1976， 251（5）： 1371-1374.
4	YAP Y W， WHITEMAN M， BAY B H， et al. Hypochlorous acid induces apoptosis of cultured cortical neurons through activation of calpains and rupture of lysosomes［J］. J Neurochem，2006， 98（5）： 1597-1609.
5	CHENG G， FAN J， SUN W， et al. A highly specific BODIPY-based probe localized in mitochondria for HClO imaging［J］. Analyst，2013， 138（20）： 6091-6096.
6	HOU J T， WU M Y， LI K， et al. Mitochondria-targeted colorimetric and fluorescent probes for hypochlorite and their applications for in vivo imaging［J］. Chem Commun，2014， 50（63）： 8640-8643.
7	ZHANG L J， ZHAO X， YANG D， et al. A new water-soluble and mitochondria-targeted fluorescence probe for ratiometric detection of hypochlorous acid in living cells［J］. Sens Actuators B： Chem， 2018， 276： 8-12.
8	WANG W， NING J Y， LIU J T， et al. A mitochondria-targeted ratiometric fluorescence sensor for the detection of hypochlorite in living cells［J］. Dyes Pigm，2019， 171： 107708.
9	WANG T R， ZHANG X F， HUANG X Q， et al. Rapid and selective visualization of mitochondrial hypochlorite by a red region water-soluble fluorescence probe［J］. Spectrochim Acta A： Mol Biomol Spectrosc，2021， 247： 119115.
10	MOBERG L， KARLBERG B. An improved N，N′-diethyl-p-phenylenediamine （DPD） method for the determination of free chlorine based on multiple wavelength detection［J］. Anal Chim Acta，2000， 407（1/2）： 127-133.
11	ZHANG L J， WANG Z Y， CAO X J， et al. An effective ICT-based and ratiometric fluorescent probe for sensing sulfite［J］. Sens Actuators B，2016， 236： 741-748.
12	YUAN L， LIN W， ZHAO S， et al. A unique approach to development of near-infrared fluorescent sensors for in vivo imaging［J］. J Am Chem Soc，2012， 134（32）： 13510-13523.
13	JUNG H S， HAN J H， KIM Z H， et al. Coumarin-Cu（II） ensemble-based cyanide sensing chemodosimeter［J］. Org Lett，2011， 13（19）： 5056-5059.
14	GAO M， YU F， CHEN H， et al. Near-infrared fluorescent probe for imaging mitochondrial hydrogen polysulfides in living cells and in vivo［J］. Anal Chem，2015， 87（7）： 3631-3638.
15	GUO Z， PARK S， YOON J， et al. Recent progress in the development of near-infrared fluorescent probes for bioimaging applications［J］. Chem Soc Rev，2014， 43（1）： 16-29.
16	YUAN L， LIN W， ZHENG K， et al. Far-red to near infrared analyte-responsive fluorescent probes based on organic fluorophore platforms for fluorescence imaging［J］. Chem Soc Rev，2013， 42（2）： 622-661.
17	KOIDE Y， URANO Y， HANAOKA K， et al. Development of an Si-rhodamine-based far-red to near-infrared fluorescence probe selective for hypochlorous acid and its applications for biological imaging［J］. J Am Chem Soc，2011， 133（15）： 5680-5682.
18	SUN M， YU H， ZHU H， et al. Oxidative cleavage-based near-infrared fluorescent probe for hypochlorous acid detection and myeloperoxidase activity evaluation［J］. Anal Chem，2013， 86（1）： 671-677.
19	LI H， GUAN L， ZHANG X， et al. A cyanine-based near-infrared fluorescent probe for highly sensitive and selective detection of hypochlorous acid and bioimaging［J］. Talanta， 2016， 161： 592-598.
20	LIN Q S， HUANG Y L， FAN X X， et al. A ratiometric fluorescent probe for hypochlorous acid determination： excitation and the dual-emission wavelengths at NIR region［J］. Talanta，2017， 170： 496-501.
21	WU L， WU I C， DUFORT C C， et al. Photostable ratiometric Pdot probe for in vitro and in vivo imaging of hypochlorous acid［J］. J Am Chem Soc，2017， 139（20）： 6911-6918.
22	WANG X， MIN J， WANG W， et al. A novel porphyrin-based near-infrared fluorescent probe for hypochlorite detection and its application in vitro and in vivo［J］. Analyst，2018， 143（11）： 2641-2647.
23	XI L L， GUO X F， WANG C L， et al. A near-infrared ratiometric fluorescent probe for rapid and selective detection of hypochlorous acid in aqueous solution and living cells［J］. Sens Actuators B： Chem，2018， 255： 666-671.
24	HUANG Y， HE N， WANG Y， et al. Detection of hypochlorous acid fluctuation via a selective near-infrared fluorescent probe in living cells and in vivo under hypoxic stress［J］. J Mater Chem B，2019， 7（15）： 2557-2564.
25	GAO G， ZHAO P， ZHOU J， et al. A commercially available NIR fluorescence probe for the detection of hypochlorite and its application in cell imaging［J］. Microchem J，2020， 159： 105311.
26	LIN X， CHEN Y， BAO L， et al. A two-photon near-infrared fluorescent probe for imaging endogenous hypochlorite in cells， tissue and living mouse［J］. Dyes Pigm，2020， 174： 108113.
27	LIU L， WEI P， YUAN W， et al. Detecting basal myeloperoxidase activity in living systems with a near-infrared emissive “turn-on” probe［J］. Anal Chem，2020， 92（16）： 10971-10978.
28	NIE J， SUN H， MIAO B， et al. A novel coumarin-based ratiometric near-infrared fluorescence probe for hypochlorous acid in living cells［J］. Dyes Pigm，2020， 181： 108590.
29	XU L， WU M， ZHAO L， et al. A novel highly sensitive and near-infrared fluorescent probe for detecting hypochlorite and its application in actual water sample and bioimaging［J］. Talanta，2020， 215： 120892.
30	YANG J， ZHENG W， SHEN Y， et al. A novel near-infrared fluorescent probe based on phenoxazine for the specific detection of HOCl［J］. J Lumin，2020， 226： 117460.
31	ZHANG M， ZUO M， WANG C， et al. Monitoring neuroinflammation with an HOCl-activatable and blood-brain barrier permeable upconversion nanoprobe［J］. Anal Chem，2020， 92（7）： 5569-5576.
32	ZHENG W， YANG J， SHEN Y， et al. The near-infrared fluorescent probes based on phenoxazine for the rapid detection of hypochlorous acid［J］. Dyes Pigm，2020， 179： 108404.
33	FAN G， WANG N， ZHANG J， et al. BODIPY-based near-infrared fluorescent probe for diagnosis drug-induced liver injury via imaging of HClO in cells and in vivo［J］. Dyes Pigm，2021： 110073.
34	JIA X， WEI C， LI Z， et al. Selective imaging of HClO in the liver tissue in vivo using a near-infrared hepatocyte-specific fluorescent probe［J］. Chem Asian J，2021， 16（14）： 1967-1972.
35	KAFUTI Y S， ZENG S， QIAN M， et al. A novel NIR fluorescent probe with fast response and large stokes shift for the detection and imaging of hypochlorous acid in living cells［J］. Dyes Pigm，2021： 110067.
36	ZHANG H， LIU J， LIU C， et al. Imaging lysosomal highly reactive oxygen species and lighting up cancer cells and tumors enabled by a Si-rhodamine-based near-infrared fluorescent probe［J］. Biomaterials，2017， 133： 60-69.
37	WANG J， CHENG D， ZHU L， et al. Engineering dithiobenzoic acid lactone-decorated Si-rhodamine as a highly selective near-infrared HOCl fluorescent probe for imaging drug-induced acute nephrotoxicity［J］. Chem Commun， 2019， 55（73）： 10916-10919.
38	WU W L， MA H L， XI L L， et al. A novel lipid droplets-targeting ratiometric fluorescence probe for hypochlorous acid in living cells［J］. Talanta，2019， 194： 308-313.
39	CAO C， ZHOU X， XUE M， et al. Dual near-infrared-emissive luminescent nanoprobes for ratiometric luminescent monitoring of ClO^– in living organisms［J］. ACS Appl Mater Interfaces，2019， 11（17）： 15298-15305.
40	WANG S， LIU L， FAN Y， et al. In vivo high-resolution ratiometric fluorescence imaging of inflammation using NIR-II nanoprobes with 1550 nm emission［J］. Nano Lett，2019， 19（4）： 2418-2427.
41	GE X， LOU Y， SU L， et al. Single wavelength laser excitation ratiometric NIR-II fluorescent probe for molecule imaging in vivo［J］. Anal Chem，2020， 92（8）： 6111-6120.
42	WU P， ZHU Y， CHEN L， et al. A fast-responsive off⁃on near-infrared-II fluorescent probe for in vivo detection of hypochlorous acid in rheumatoid arthritis［J］. Anal Chem，2021， 93（38）： 13014-13021.
43	ZHANG M， WANG Z， WANG C， et al. Visualizing oxidative stress level for timely assessment of ischemic stroke via a ratiometric near-infrared-II luminescent nanoprobe［J］. ACS Nano，2021， 15（7）： 11940-11952.
44	WANG L， LIU J， ZHANG H， et al. Discrimination between cancerous and normal cells/tissues enabled by a near-infrared fluorescent HClO probe［J］. Sens Actuators B： Chem，2021， 334： 129602.
45	ZHANG Y Y， CHEN X Z， LIU X Y， et al. A highly selective and ultrafast near-infrared fluorescent turn-on and colorimetric probe for hypochlorite in living cells［J］. Anal Chim Acta，2019， 1078： 135-141.
46	DENG Y， FENG S， XIA Q， et al. A novel reaction-based fluorescence probe for rapid imaging of HClO in live cells， animals， and injured liver tissues［J］. Talanta，2020， 215： 120901.
47	HE M， YE M， WANG Z， et al. A ratiometric near-infrared fluorescent probe with a large emission peak shift for sensing and imaging hypochlorous acid［J］. Sens Actuators B： Chem，2021， 343： 130063.
48	ZHANG H， YIN X， HONG J， et al. A NIR fluorescence probe having significant fluorescence turn-on signal at 700 nm and large Stokes shift for rapid detection of HOCl in vivo［J］. Talanta，2021， 223： 121768.
49	TONG H， ZHANG Y， MA S， et al. A pinacol boronate caged NIAD-4 derivative as a near-infrared fluorescent probe for fast and selective detection of hypochlorous acid［J］. CHIN Chem Lett，2018， 29（1）： 139-142.
50	ZHOU Z， YUAN X， LONG D， et al. A pyridine-Si-rhodamine-based near-infrared fluorescent probe for visualizing reactive oxygen species in living cells［J］. Spectrochim Acta A： Mol Biomol Spectrosc，2021， 246： 118927.
51	XU J， YUAN H， QIN C， et al. A mitochondria-targeted near-infrared probe for colorimetric and ratiometric fluorescence detection of hypochlorite in living cells［J］. RSC Adv，2016， 6（109）： 107525-107532.
52	XU J， PAN J， JIANG X， et al. A mitochondria-targeted ratiometric fluorescent probe for rapid， sensitive and specific detection of biological SO₂ derivatives in living cells［J］. Biosens Bioelectron，2016， 77： 725-732.
53	LIU Y， LI K， XIE K X， et al. A water-soluble and fast-response mitochondria-targeted fluorescent probe for colorimetric and ratiometric sensing of endogenously generated SO₂ derivatives in living cells［J］. Chem Commun， 2016， 52（16）： 3430-3433.
54	LAN J S， LIU L， ZENG R F， et al. Rational modulation of coumarin-hemicyanine platform based on OH substitution for higher selective detection of hypochlorite［J］. Chem Comm，2020， 56（8）： 1219-1222.
55	LIU J， SUN Y Q， ZHANG H， et al. A carboxylic acid-functionalized coumarin-hemicyanine fluorescent dye and its application to construct a fluorescent probe for selective detection of cysteine over homocysteine and glutathione［J］. RSC Adv，2014， 4（110）： 64542-64550.
56	ZHANG L J， WANG Z Y， LIU J T， et al. A rational design of ratiometric fluorescent probes based on new ICT/FRET platform and imaging of endogenous sulfite in living cells［J］. Sens Actuators B： Chem，2017， 253： 19-26.
57	HUANG Y， ZHANG Y， HUO F， et al. A near-infrared ratiometric fluorescent probe with large stokes based on isophorone for rapid detection of ClO^- and its bioimaging in cell and mice［J］. Sens Actuators B： Chem，2019， 287： 453-458.
58	XIONG K， HUO F， ZHANG Y， et al. A NIR ratiometric fluorescent probe for the ‘naked-eye’ detection of endogenous hypochlorous acid in practical samples［J］. Anal Methods，2019， 11（13）： 1751-1756.
59	HUANG Y， ZHANG Y， HUO F， et al. Mitochondrial-targeted near-infrared “dual mode” fluorescent dyes with large Stokes shift for detection of hypochlorous acid and its bioimaging in cell and mice［J］. Dyes Pigm，2020， 179： 108387.
60	REN H， HUO F，YIN C. An ESIPT-based colorimetric and fluorescent probe with large Stokes shift for the sensitive detection of hypochlorous acid and its bioimaging in cells［J］. New J Chem，2021， 45（10）： 4724-4728.
61	PANG Q， LI T， YIN C， et al. Comparing the abundance of HClO in cancer/normal cells and visualizing in vivo using a mitochondria-targeted ultra-fast fluorescent probe［J］. Analyst，2021， 146（10）： 3361-3367.
62	OUSHIKI D， KOJIMA H， TERAI T， et al. Development and application of a near-infrared fluorescence probe for oxidative stress based on differential reactivity of linked cyanine dyes［J］. J Am Chem Soc，2010， 132（8）： 2795-2801.
63	CHENG G， FAN J， SUN W， et al. A near-infrared fluorescent probe for selective detection of HClO based on Se-sensitized aggregation of heptamethine cyanine dye［J］. Chem Commun，2014， 50（8）： 1018-1020.
64	JIANG C， LI Y， YAN L， et al. A ratiometric fluorescence mitochondrial-targeted probe for imaging HOCl in vitro and in vivo［J］. Dyes Pigm，2022， 198： 109975.
65	ZHAO X J， JIANG Y R， CHEN Y X， et al. A new “off-on” NIR fluorescence probe for determination and bio-imaging of mitochondrial hypochlorite in living cells and zebrafish［J］. Spectrochim Acta A： Mol Biomol Spectrosc，2019， 219： 509-516.
66	YUAN L， LIN W，CHEN H. Analogs of Changsha near-infrared dyes with large Stokes shifts for bioimaging［J］. Biomaterials，2013， 34（37）： 9566-9571.
67	CHENG X， JIA H， LONG T， et al. A “turn-on” fluorescent probe for hypochlorous acid： convenient synthesis， good sensing performance， and a new design strategy by the removal of C N isomerization［J］. Chem Comm，2011， 47（43）： 11978.
68	WANG Y， XIA J， HAN J， et al. A fast-responsive fluorescent probe based on BODIPY dye for sensitive detection of hypochlorite and its application in real water samples［J］. Talanta，2016， 161： 847-853.
69	TIAN F， JIA Y， ZHANG Y， et al. A HClO-specific near-infrared fluorescent probe for determination of Myeloperoxidase activity and imaging mitochondrial HClO in living cells［J］. Biosens Bioelectron，2016， 86： 68-74.
70	JIAO X， HUANG K， HE S， et al. A mitochondria-targeted near-infrared fluorescent probe with a large Stokes shift for real-time detection of hypochlorous acid［J］. Org Biomol Chem，2019， 17（1）： 108-114.
71	GONG J， LIU C， CAI S， et al. Novel near-infrared fluorescent probe with a large Stokes shift for sensing hypochlorous acid in mitochondria［J］. Org Biomol Chem，2020， 18（38）： 7656-7662.
72	CARTER K P， YOUNG A M， PALMER A E. Fluorescent sensors for measuring metal ions in living systems［J］. Chem Rev，2014， 114（8）： 4564-4601.
73	YANG Y， ZHAO Q， FENG W， et al. Luminescent chemodosimeters for bioimaging［J］. Chem Rev，2012， 113（1）： 192-270.
74	BEIJA M， AFONSO C A M， MARTINHO J M G. Synthesis and applications of Rhodamine derivatives as fluorescent probes［J］. Chem Soc Rev，2009， 38（8）： 2410.
75	QUANG D T， KIM J S. Fluoro- and chromogenic chemodosimeters for heavy metal ion detection in solution and biospecimens［J］. Chem Rev，2010， 110（10）： 6280-6301.
76	ZHENG A， LIU H， PENG C， et al. A mitochondria-targeting near-infrared fluorescent probe for imaging hypochlorous acid in cells［J］. Talanta，2021， 226： 122152.
77	MA H， ZHANG J， ZHANG Z， et al. A fast response and red emission probe for mammalian thioredoxin reductase［J］. Chem Commun，2016， 52（81）： 12060-12063.
78	GUO T， CUI L， SHEN J， et al. A highly sensitive long-wavelength fluorescence probe for nitroreductase and hypoxia： selective detection and quantification［J］. Chem Comm，2013， 49（92）： 10820.
79	HO N H， WEISSLEDER R， TUNG C H. A self-immolative reporter for β-galactosidase sensing［J］. ChemBioChem，2007， 8（5）： 560-566.
80	ZHU B， WU L， ZHANG M， et al. A highly specific and ultrasensitive near-infrared fluorescent probe for imaging basal hypochlorite in the mitochondria of living cells［J］. Biosens Bioelectron，2018， 107： 218-223.
81	SHEN B X， QIAN Y， QI Z Q， et al. Near-infrared BODIPY-based two-photon ClO^- probe based on thiosemicarbazide desulfurization reaction： naked-eye detection and mitochondrial imaging［J］. J Mater Chem B，2017， 5（29）： 5854-5861.
82	SHEN B X， QIAN Y. A novel triphenylamine-BODIPY dendron： click synthesis， near-infrared emission and a multi-channel chemodosimeter for Hg²⁺and Fe³⁺［J］. J Mater Chem B，2016， 4（47）： 7549-7559.
83	SHEN B X， QIAN Y. Click synthesis， Hg²⁺ sensor and intramolecular fluorescence resonance energy transfer in novel BODIPY dendrons［J］. Sens Actuators B： Chem，2017， 239： 226-234.
84	MAO G J， GAO G Q， LIANG Z Z， et al. A mitochondria-targetable two-photon fluorescent probe with a far-red to near-infrared emission for sensing hypochlorite in biosystems［J］. Anal Chim Acta，2019， 1081： 184-192.
85	MAO G J， WANG Y Y， DONG W P， et al. A lysosome-targetable two-photon excited near-infrared fluorescent probe for visualizing hypochlorous acid-involved arthritis and its treatment［J］. Spectrochim Acta A，2021， 249： 119326.
86	LIN X， QIN W， CHEN Y， et al. Construction of a multi-signal near-infrared fluorescent probe for sensing of hypochlorite concentration fluctuation in living animals［J］. Sens Actuators B： Chem，2020， 324： 128732.
87	MAO Z， FENG W， LI Z， et al. NIR in， far-red out： developing a two-photon fluorescent probe for tracking nitric oxide in deep tissue［J］. Chem Sci，2016， 7（8）： 5230-5235.
88	REN H Y， LIU B F， KONG F， et al. Improved Nile red staining of Scenedesmus sp. by combining ultrasonic treatment and three-dimensional excitation emission matrix fluorescence spectroscopy［J］. Algal Res，2015， 7： 11-15.
89	KREDER R， PYRSHEV K A， DARWICH Z， et al. Solvatochromic Nile red probes with FRET quencher reveal lipid order heterogeneity in living and apoptotic cells［J］. ACS Chem Biol，2015， 10（6）： 1435-1442.
90	HAN J， JOSE J， MEI E， et al. Chemiluminescent energy-transfer cassettes based on fluorescein and Nile red［J］. Angew Chem Int Ed，2007， 46（10）： 1684-1687.
91	NJIOJOB C N， OWENS E A， NARAYANA L， et al. Tailored near-infrared contrast agents for image guided surgery［J］. J Med Chem，2015， 58（6）： 2845-2854.
92	WANG X， LV J， YAO X， et al. Screening and investigation of a cyanine fluorescent probe for simultaneous sensing of glutathione and cysteine under single excitation［J］. Chem Commun，2014， 50（97）： 15439-15442.
93	CHEN G， SONG F， WANG J， et al. FRET spectral unmixing： a ratiometric fluorescent nanoprobe for hypochlorite［J］. Chem Commun，2012， 48（24）： 2949.
94	KIYOSE K， AIZAWA S， SASAKI E， et al. Molecular design strategies for near-infrared ratiometric fluorescent probes based on the unique spectral properties of aminocyanines［J］. Chem Eur J，2009， 15（36）： 9191-9200.
95	LIU L， JIANG L， YUAN W， et al. Dual-modality detection of early-stage drug-induced acute kidney injury by an activatable probe［J］. ACS Sens， 2020， 5（8）： 2457-2466.
96	ZUO Y， WANG X， GOU Z， et al. Reversible polysiloxane-based near-infrared fluorescent probe for monitoring the redox cycles between HClO/SO₂ in mitochondria and in vivo［J］. Sens Actuators B： Chem，2021， 344： 130217.
97	AN Z， SHAN T， HE H， et al. Contradiction or unity？ thermally stable fluorescent probe for in situ fast identification of self-sort or co-assembly of multicomponent gelators with sensitive properties［J］. ACS Appl Mater Interfaces，2021， 13（7）： 8774-8781.
98	LI Y， ZHANG L， LI C. Highly transparent and scratch resistant polysiloxane coatings containing silica nanoparticles［J］. J Colloid Interface Sci，2020， 559： 273-281.
99	BAHRAMI Z， AKBARI A， EFTEKHARI-SIS B. Double network hydrogel of sodium alginate/polyacrylamide cross-linked with POSS： swelling， dye removal and mechanical properties［J］. Int J Biol Macromol，2019， 129： 187-197.
100	YU J， LIU Y. Cyclic polysiloxanes with linked cyclotetrasiloxane subunits［J］. Angew Chem Int Ed，2017， 56（30）： 8706-8710.
101	REN Z， YAN S. Polysiloxanes for optoelectronic applications［J］. Prog Mater Sci，2016， 83： 383-416.
102	YE Y， ZHANG D， LIU T， et al. Improvement of anticorrosion ability of epoxy matrix in simulate marine environment by filled with superhydrophobic POSS-GO nanosheets［J］. J Hazard Mater，2019， 364： 244-255.
103	WANG S， GU K， YAN C， et al. POSS： a morphology-tuning strategy to improve the sensitivity and responsiveness of dissolved oxygen sensor［J］. Ind Eng Chem Res，2019， 58（19）： 7761-7768.
104	KAVUNCUOGLU H， YALCIN H， DOGAN M. Production of polyhedral oligomeric silsesquioxane（POSS） containing low density polyethylene （LDPE） based nanocomposite films for minced beef packaging for extension of shelf life［J］. Lwt，2019， 108： 385-391.
105	LIU J， YU H， LIANG Q， et al. Preparation of polyhedral oligomeric silsesquioxane based cross-linked inorganic-organic nanohybrid as adsorbent for selective removal of acidic dyes from aqueous solution［J］. J Colloid Interface Sci，2017， 497： 402-412.
106	KAKUTA T， NARIKIYO H， JEON J H， et al. Development of highly-sensitive detection system in ¹⁹F NMR for bioactive compounds based on the assembly of paramagnetic complexes with fluorinated cubic silsesquioxanes［J］. Bioorg Med Chem，2017， 25（4）： 1389-1393.
107	ZHOU Z， HAN Z， LU Z R. A targeted nanoglobular contrast agent from host-guest self-assembly for MR cancer molecular imaging［J］. Biomaterials，2016， 85： 168-179.
108	ZHANG Y， SHEN H Y， HAI X， et al. Polyhedral oligomeric silsesquioxane polymer-caged silver nanoparticle as a smart colorimetric probe for the detection of hydrogen sulfide［J］. Anal Chem，2016， 89（2）： 1346-1352.
109	QIAN M， MURRAY V J， WEI W， et al. Resistance of POSS polyimide blends to hyperthermal atomic oxygen attack［J］. ACS Appl Mater Interfaces，2016， 8（49）： 33982-33992.
110	DING G， ZUO Y， GAI F， et al. A POSS-assisted fluorescent probe for the rapid detection of HClO in mitochondria with a large emission wavelength in dual channels［J］. J Mater Chem B，2021， 9（34）： 6836-6843.

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