光谱学与光谱分析
光譜學與光譜分析
광보학여광보분석
SPECTROSCOPY AND SPECTRAL ANALYSIS
2014年
11期
3034-3039
,共6页
查佳玉%林英慧%徐俊超%张有来%曾林涛
查佳玉%林英慧%徐俊超%張有來%曾林濤
사가옥%림영혜%서준초%장유래%증림도
BODIPY%光谱性质%近红外%细胞成像%Stokes位移
BODIPY%光譜性質%近紅外%細胞成像%Stokes位移
BODIPY%광보성질%근홍외%세포성상%Stokes위이
BODIPY%Spectroscopic properties%Near-infrared region%Cell imaging%Stokes shift
传统的BODIPY荧光染料具有荧光量子效率高、摩尔消光系数大、紫外吸收和荧光发射峰窄等优点，然而这类荧光染料普遍存在荧光发射波长短和Stokes位移小的缺点，因而限制了它们在体内生物传感及成像方面的广泛应用。为了得到荧光发射波长较长和Stokes位移大的BODIPY荧光染料，以BODIPY母核为基本结构，通过在它的8位连接吸电子性质的酯基来增加分子内电荷转移程度，同时在其3，5位引入供电子的芳香取代基增加分子的π共轭结构，合成得到了一类8位酯基取代的新型BODIPY荧光染料。所得到的新型BODIPY荧光染料的化学结构经过1 H NMR ，13C NMR和 HR-MS得以确认。光谱测试结果表明，这类染料的紫外吸收光谱（λabs＝536 nm ）和荧光发射光谱（λem ＝592 nm ）与普通的BODIPY相比都发生显著红移（80 nm），并且保持了较高的荧光量子效率（Ф＝0.43）。此外，这类BODIPY荧光染料的紫外可见吸收光谱和荧光发射光谱几乎完全分开，S to kes位移长达60 nm ，可以有效地避免自吸收和生物样品的背景干扰。密度泛函理论计算结果表明，这种相对较大的Stokes位移主要是由于染料分子在基态和激发态下不同的几何构型所造成的。该类化合物的光物理性能受溶剂的影响小，是一类性能优良的新型荧光染料。细胞成像结果表明，染料1具有良好的细胞渗透性和光稳定性，可以实现对细胞的荧光成像。
傳統的BODIPY熒光染料具有熒光量子效率高、摩爾消光繫數大、紫外吸收和熒光髮射峰窄等優點，然而這類熒光染料普遍存在熒光髮射波長短和Stokes位移小的缺點，因而限製瞭它們在體內生物傳感及成像方麵的廣汎應用。為瞭得到熒光髮射波長較長和Stokes位移大的BODIPY熒光染料，以BODIPY母覈為基本結構，通過在它的8位連接吸電子性質的酯基來增加分子內電荷轉移程度，同時在其3，5位引入供電子的芳香取代基增加分子的π共軛結構，閤成得到瞭一類8位酯基取代的新型BODIPY熒光染料。所得到的新型BODIPY熒光染料的化學結構經過1 H NMR ，13C NMR和 HR-MS得以確認。光譜測試結果錶明，這類染料的紫外吸收光譜（λabs＝536 nm ）和熒光髮射光譜（λem ＝592 nm ）與普通的BODIPY相比都髮生顯著紅移（80 nm），併且保持瞭較高的熒光量子效率（Ф＝0.43）。此外，這類BODIPY熒光染料的紫外可見吸收光譜和熒光髮射光譜幾乎完全分開，S to kes位移長達60 nm ，可以有效地避免自吸收和生物樣品的揹景榦擾。密度汎函理論計算結果錶明，這種相對較大的Stokes位移主要是由于染料分子在基態和激髮態下不同的幾何構型所造成的。該類化閤物的光物理性能受溶劑的影響小，是一類性能優良的新型熒光染料。細胞成像結果錶明，染料1具有良好的細胞滲透性和光穩定性，可以實現對細胞的熒光成像。
전통적BODIPY형광염료구유형광양자효솔고、마이소광계수대、자외흡수화형광발사봉착등우점，연이저류형광염료보편존재형광발사파장단화Stokes위이소적결점，인이한제료타문재체내생물전감급성상방면적엄범응용。위료득도형광발사파장교장화Stokes위이대적BODIPY형광염료，이BODIPY모핵위기본결구，통과재타적8위련접흡전자성질적지기래증가분자내전하전이정도，동시재기3，5위인입공전자적방향취대기증가분자적π공액결구，합성득도료일류8위지기취대적신형BODIPY형광염료。소득도적신형BODIPY형광염료적화학결구경과1 H NMR ，13C NMR화 HR-MS득이학인。광보측시결과표명，저류염료적자외흡수광보（λabs＝536 nm ）화형광발사광보（λem ＝592 nm ）여보통적BODIPY상비도발생현저홍이（80 nm），병차보지료교고적형광양자효솔（Ф＝0.43）。차외，저류BODIPY형광염료적자외가견흡수광보화형광발사광보궤호완전분개，S to kes위이장체60 nm ，가이유효지피면자흡수화생물양품적배경간우。밀도범함이론계산결과표명，저충상대교대적Stokes위이주요시유우염료분자재기태화격발태하불동적궤하구형소조성적。해류화합물적광물이성능수용제적영향소，시일류성능우량적신형형광염료。세포성상결과표명，염료1구유량호적세포삼투성화광은정성，가이실현대세포적형광성상。
BODIPY dyes have some unique properties including high fluorescence quantum yield ,large extinc-tion coefficiency ,narrow absorption and emission band .However ,most of BODIPY dyes display short emis-sion wavelength and small Stokes shift ,which limits their applications in biosensing and bioimaging in vivo . For bioimaging application ,a fluorescent dye with long emission wavelength and large Stokes shift is highly desired .To push the absorption and emission spectrum of BODIPY to red and even far-red region ,a COOEt group was introduced to the meso position ,and some aromatic group was attached to the 3 ,5 position of BODIPY core .The structure of resulting compounds were comfirmed by 1 H NMR ,13 C NMR and HR-MS . Dye-1 displays a strong UV-Vis absorption band centered at 536 nm and a sharp emission band is located at 592 nm ,which is significantly red-shifted (80 nm) compared to ordinary BODIPY analogs .In addition ,the meso-COOEt substituted BODIPYs exhibit high quantum yield and red to far-red emission .Notably surprisingly , the meso-COOEt substituted BODIPYs display almost separated UV-Vis absorption and emission spectra with a large Stokes shift (~60 nm) .Time-dependent density functional theory calculations were conducted to un-derstand the structure-optical properties relationship ,and it was revealed that the large Stokes shift was resul-ted from the geometric change from the ground state to the first excited singlet state .The spectroscopic prop-erties of these BODIPY dyes display very subtle solvent-dependence effect .Furthermore ,BODIPY was tested for its ability of imaging in living cells .The results indicate that Dye-1 is a water-soluble and membrane-per-meable probe .Therefore ,these BODIPYs are a new family dyes with excellent spectroscopic properties and can be good candidates for bioimaging in living cells .
