Progress on Si-Rhodamine Fluorescent Probes
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摘要: 近年来，罗丹明染料因其良好的荧光性能，在化学和生物化学领域倍受关注。但罗丹明染料的荧光波长通常都小于600 nm，具有较强的生物背景荧光的干扰，很大程度上限制了其在生物成像等领域的实际应用。将罗丹明母核的氧原子替换为硅原子，所发展的硅罗丹明不仅具备传统罗丹明荧光染料的优点，还可将荧光波长红移至近红外波段，很好地解决了罗丹明荧光波长较短的问题。本文主要综述了硅罗丹明荧光探针的研究进展，重点聚焦该荧光团波长红移原理、荧光波长和荧光量子产率的调控，以及硅罗丹明探针的设计机理与应用。Abstract: Rhodamine dyes are widely used as fluorescent probes owing to their high absorption coefficient, broad fluorescence in the visible region of electromagnetic spectrum, high fluorescence quantum yield and photostability. A great interest in the development of new synthetic procedures for preparation of rhodamine derivatives has arisen in recent years because the probe must be covalently linked to another (bio)molecule or surface for most applications. To date, the emission wavelength of rhodamine dyes is always less than 600 nm, which restricts the practical application of rhodamines in living systems due to the serious background fluorescence interference. In this critical review the strategies for modification of rhodamine dyes and a discussion on the variety of applications of these new derivatives as fluorescent probes are given. Upon replacing the oxygen bridge atom by silicon, the resulting Si-rhodamines have been developed as novel near-infrared (NIR) fluorescent cores with remaining the key advantages of conventional rhodamine chromophore, and also generating the bathochromic shift in their emission wavelengths to NIR region. Based on the essential properties of Si-rhodamine, this paper mainly focuses on the principle of the red shift in the emission wavelength, the regulation of fluorescence wavelength and fluorescence quantum yield, and the design mechanism and application of Si-rhodamine fluorescent probes.
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Key words:
- Si-rhodamine /
- fluorescence /
- probe /
- NIR region
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图 1 常见的荧光探针母体分子结构（按照结构和波长分类）
Figure 1. Common chromophores as fluorescent probes for chemoselective bioimaging (sorted by structure and emission color)
图 2 罗丹明染料荧光性质的内在和外在影响因素
Figure 2. Intrinsic and extrinsic influence factors on rhodamine fluorescent properties
图 7 硅罗丹明荧光探针螺环机理
Figure 7. SiR-based fluorescent probes with the spirocyclization mechanism
表 1 Pyronine Y和TMDHS光物理性质和能级的相关数据
Table 1. Relative data about photophysical properties and orbital energy of pyronine Y and TMDHS
Materials λabs/nm λem/nm EHOMO/eV ELUMO/eV Pyronine Y 522 569 −5.64 −3.74 TMDHS 641 659 −5.50 −3.92 abs—Absorption; em—Emission 
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表 2 硅罗丹明光物理性质相关数据
Table 2. Relative data about photophysical properties of SiR-NIRs
SiR-NIRs λabs/nm λem/nm φf1/eV SiR600 593 613 0.38 SiR650 646 660 0.31 SiR680 674 689 0.35 SiR700 691 712 0.12 SiR720 721 740 0.05 SiR664 646 664 0.54 φfl—Fluorescence quantum efficiency
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[1] ZHENG H, ZHAN X Q, BIAN Q N, et al. Advances in modifying fluorescein and rhodamine fluorophores as fluorescent chemosensors[J]. Chemical Communications, 2013, 49(5): 429-447. doi: 10.1039/C2CC35997A [2] ZHOU L, ZHANG X, WANG Q, et al. Molecular engineering of a TBET-based two-photon fluorescent probe for ratiometric imaging of living cells and tissues[J]. Journal of the American Chemical Society, 2014, 136(28): 9838-9841. doi: 10.1021/ja504015t [3] CHEN X, PRADHAN T, WANG F, et al. Fluorescent chemosensors based on spiroring-opening of xanthenes and related derivatives[J]. Chemical Reviews, 2011, 112(3): 1910-1956. [4] GUPTA V K, MERGU N, KUMAWAT L K. A new multifunctional rhodamine-derived probe for colorimetric sensing of Cu(II) and Al(III) and fluorometric sensing of Fe(III) in aqueous media[J]. Sensors and Actuators: B. Chemical, 2016, 223: 101-113. doi: 10.1016/j.snb.2015.09.060 [5] MAHATO P, SAHA S, SURESH E, et al. Ratiometric detection of Cr3+ and Hg2+ by a naphthalimide-rhodamine based fluorescent probe[J]. Inorganic Chemistry, 2012, 51(3): 1769-1777. doi: 10.1021/ic202073q [6] SUN Y Q, LIU J, LV X, et al. Rhodamine-inspired far-red to near-infrared dyes and their application as fluorescence probes[J]. Angewandte Chemie: Internation Edition, 2012, 51(31): 7634-7636. doi: 10.1002/anie.201202264 [7] IKENO T, NAGANO T, HANAOKA K. Silicon-substituted xanthene dyes and their unique photophysical properties for fluorescent probes[J]. Chemistry: An Asian Journal, 2017, 12(13): 1435-1446. doi: 10.1002/asia.v12.13 [8] KOIDE Y, KAWAGUCHI M, URANO Y, et al. A reversible near-infrared fluorescence probe for reactive oxygen species based on Te-rhodamine[J]. Chemical Communications, 2012, 48(25): 3091-3093. doi: 10.1039/c2cc18011a [9] KOIDE Y, URANO Y, HANAOKA K, et al. Evolution of group 14 rhodamines as platforms for near-infrared fluorescence probes utilizing photoinduced electron transfer[J]. ACS Chemical Biology, 2011, 6(6): 600-608. doi: 10.1021/cb1002416 [10] 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]. Journal of the American Chemical Society, 2011, 133(15): 5680-5682. doi: 10.1021/ja111470n [11] KUSHIDA Y, NAGANO T, HANAOKA K. Silicon-substituted xanthene dyes and their applications in bioimaging[J]. Analyst, 2015, 140(3): 685-695. doi: 10.1039/C4AN01172D [12] LIU J, SUN YQ, ZHANG H, et al. Sulfone-Rhodamines: A new class of near-infrared fluorescent dyes for bioimaging[J]. ACS Applied Materials and Interfaces, 2016, 8(35): 22953-22962. doi: 10.1021/acsami.6b08338 [13] BEST Q A, SATTENAPALLY N, DYER D J, et al. pH-dependent Si-fluorescein hypochlorous acid fluorescent probe: Spirocycle ring-opening and excess hypochlorous acid-induced chlorination[J]. Journal of the American Chemical Society, 2013, 135(36): 13365-13370. doi: 10.1021/ja401426s [14] EGAWA T, HANAOKA K, KOIDE Y, et al. Development of a far-red to near-infrared fluorescence probe for calcium ion and its application to multicolor neuronal imaging[J]. Journal of the American Chemical Society, 2011, 133(36): 14157-14159. doi: 10.1021/ja205809h [15] KOIDE Y, URANO Y, HANAOKA K, et al. Development of NIR fluorescent dyes based on Si-rhodamine for in vivo imaging[J]. Journal of the American Chemical Society, 2012, 134(11): 5029-5031. doi: 10.1021/ja210375e [16] WANG T, ZHAO Q J, HU H G, et al. Spirolactonized Si-rhodamine: A novel NIR fluorophore utilized as a platform to construct Si-rhodamine-based probes[J]. Chemical Communications, 2012, 48(70): 8781-8783. doi: 10.1039/c2cc34159j [17] KUSHIDA Y, HANAOKA K, KOMATSU T, et al. Red fluorescent scaffold for highly sensitive protease activity probes[J]. Bioorganic and Medicinal Chemistry Letters, 2012, 22(12): 3908-3911. doi: 10.1016/j.bmcl.2012.04.114 [18] LUKINAVICIUS G, REYMOND L, UMEZAWA K, et al. Fluorogenic probes for multicolor imaging in living cells[J]. Journal of the American Chemical Society, 2016, 138(30): 9365-9368. doi: 10.1021/jacs.6b04782 [19] GRIMM J B, ENGLISH B P, CHEN J, et al. A general method to improve fluorophores for live-cell and single-molecule microscopy[J]. Nature Methods, 2015, 12(3): 244-250. doi: 10.1038/nmeth.3256 [20] GRIMM J B, MUTHUSAMY A K, LIANG Y, et al. A general method to fine-tune fluorophores for live-cell and in vivo imaging[J]. Nature Methods, 2017, 14(10): 987-994. doi: 10.1038/nmeth.4403 [21] GRIMM J B, BROWN T A, TKACHUK A N, et al. General synthetic method for Si-fluoresceins and Si-rhodamines[J]. ACS Central Science, 2017, 3(9): 975-985. doi: 10.1021/acscentsci.7b00247 [22] SHEN S, YU J, LU Y, et al. Near-infrared probes based on fluorinated Si-rhodamine for live cell imaging[J]. RSC Advances, 2017, 7(18): 10922-10927. doi: 10.1039/C6RA28455H [23] LEMMETYINEN H, NIKOLAI V T, ALEXANDER E, et al. Photoinduced intra- and intermolecular electron transfer in solutions and in solid organized molecular assemblies[J]. Physical Chemistry Chemical Physics, 2011, 13(2): 397-412. [24] TANG J, GUO Z, ZHANG Y, et al. Rational design of a fast and selective near-infrared fluorescent probe for targeted monitoring of endogenous nitric oxide[J]. Chemical Communications, 2017, 53(76): 10520-10523. doi: 10.1039/C7CC05971J [25] 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. doi: 10.1016/j.biomaterials.2017.04.023 [26] ZHU W, CHAI X, WANG B, et al. Spiroboronate Si-rhodamine as a near-infrared probe for imaging lysosomes based on the reversible ring-opening process[J]. Chemical Communications, 2015, 51(47): 9608-9611. doi: 10.1039/C5CC02496J [27] BREWER T F, CHANG C J. An aza-cope reactivity-based fluorescent probe for imaging formaldehyde in living cells[J]. Journal of the American Chemical Society, 2015, 137(34): 10886-10889. doi: 10.1021/jacs.5b05340 [28] WANG B, CUI X, ZHANG Z, et al. A six-membered-ring incorporated Si-rhodamine for imaging of copper (II) in lysosomes[J]. Organic and Biomolecular Chemistry, 2016, 14(28): 6720-6728. doi: 10.1039/C6OB00894A [29] DING Z, TAN J, FENG G, et al. Nanoscale metal-organic frameworks coated with poly (vinyl alcohol) for ratiometric peroxynitrite sensing through FRET[J]. Chemical Science, 2017, 8(7): 5101-5106. doi: 10.1039/C7SC01077J [30] MYOCHIN T, HANAOKA K, IWAKI S, et al. Development of a series of near-infrared dark quenchers based on Si-rhodamines and their application to fluorescent probes[J]. Journal of the American Chemical Society, 2015, 137(14): 4759-4765. doi: 10.1021/jacs.5b00246 [31] UMEZAWA K, YOSHIDA M, KAMIYA M, et al. Rational design of reversible fluorescent probes for live-cell imaging and quantification of fast glutathione dynamics[J]. Nature Chemistry, 2017, 9(3): 279-286. doi: 10.1038/nchem.2648 -
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