摘要
菁染料是一类重要的功能性染料,它们被广泛应用于照相材料光谱增感剂、光盘存储介质、太阳能电池光敏剂、pH探针、非线性光学材料等领域中。特别短波长菁染料具有可穿过细胞膜、无毒、不干扰细胞的正常生理功能、对核酸(DNA／RNA)有较强的亲和性等优点,在生物医学领域的应用得到了广泛的关注,例如应用于凝胶电泳中染色DNA、DNA测序、流式细胞仪、活细胞成像、生物大分子的标记等。目前商品化的膜通透性活细胞荧光探针种类有限,应用范围有限,且价格昂贵,还无法在国内临床分析上普及,极大限制了其在生物医学领域的应用,为了拓宽活细胞荧光探针的种类及应用范围,寻找性能优良的荧光探针,本文以短波长菁染料作为合成目标,将其作为荧光染色剂应用于细胞成像和流式细胞术中,探讨其作为活细胞荧光探针的可能性。本文介绍了菁染料的结构特点、性质特征、应用研究以及近些年来短波长二甲川菁染料、苯乙烯半菁染料及一次甲基份菁染料的合成进展,主要研究内容有以下几个方面：
1.采用微波无溶剂方法合成了七种新型含吲哚核的二甲川菁染料,其中六种未见文献报道,通过元素分析、1HNMR、IR、UV-Vis对产物进行了结构表征。根据微波辐射功率和时间,讨论了杂环季铵盐与吲哚甲醛的反应活性,结果表明：杂环季铵盐的反应活性顺序为：喹啉季铵盐≈2-甲基吡啶季铵盐≈4-甲基吡啶季铵盐>萘噻唑季铵盐≈苯并噻唑季铵盐>苯并吲哚季铵盐>苯并咪唑季铵盐。研究了染料的紫外-可见吸收和荧光光谱性质,结果表明：染料在甲醇中的最大吸收波长位于376.0～484.0nm范围,摩尔消光系数为1.8×104～5.7×104L·mol-1cm-1,其荧光发射波长位于512.6～548.6nm之间,荧光量子产率为0.0018～0.0285,具有53.6～104.6nm的斯托克位移值。染料的吸收波长和杂环碱性具有一定的关系,最大吸收波长随杂环核的碱性减小而增大。研究了染料最大吸收波长和溶剂介电常数的关系,结果表明,随着溶剂介电常数的增大,染料的最大吸收波长蓝移。
2.采用微波无溶剂方法和常规合成方法合成了十三种含喹啉核的二甲川菁染料,均未见文献报道,通过元素分析、1HNMR、IR、UV-Vis对产物进行了结构表征。研究了不同的取代基对季铵盐反应活性的影响,结果发现：取代基的给电子能力的增强,有助于反应进行,并且对于相同的取代基而言,6位取代的染料较7位取代的易合成,且产率也相对较高。利用紫外-可见光谱和荧光光谱技术研究了单纯染料、染料与DNA、BSA在生理条件下的相互作用,探讨其作为DNA、BSA荧光探针的可能性。结果发现：此类染料对DNA具有较好的亲和性,当染料与DNA相互作用后,荧光强度剧增,荧光量子产率最高增大了68.8倍。
3.采用三组份一锅法反应,合成了四种含异噁唑酮核一次甲基份菁染料,其中三种产物未见文献报道,并利用元素分析、1HNMR、R和UV-Vis对其进行了结构表征。此类染料在甲醇中的最大吸收波长位于417.0～429.0nm范围,摩尔消光系数在3.3×104～4.5×104L.mol-1cm-1,其荧光最大发射波长位于476.0～511.6nm之间,具有59.0～82.6nm的斯托克位移值,荧光量子产率值为0.0008～0.0024。利用X射线单晶衍射技术对四种染料分子的晶体结构和空间堆积方式进行了表征和解析。
4.在B3LYP／6-31G*和PBE1PBE／6-31G*水平上分别对七种含吲哚核二甲川菁染料进行了理论研究。采用极化连续模型PCM考虑了溶剂效应对吸收光谱的影响,结果表明：PBE1PBE／6-31G*(PCM)方法更能准确预测染料的吸收光谱性质。通过部分二面角参数和染料的荧光量子产率,说明了染料分子的刚性平面越强,共轭体系越大,则荧光强度就越大。染料的最低能级电子跃迁属于HOMO到LUMO的π→π*跃迁,具有最大的谐振强度,并且从分子轨道图分析得出HOMO→LUMO的电子跃迁源于分子内部的电荷转移。
应用CIS／PCM方法在S1优化构型的基础上,研究了七种含喹啉核二甲川菁染料的荧光发射光谱性质,结果表明：计算所得的λem与实验值的相对偏差为1.7%,此方法可以用来预测染料的最大发射光谱。使用Swizard软件计算出了含喹啉核二甲川菁染料的摩尔消光系数,并且通过计算模拟拟合的吸收光谱图与实验光谱图基本一致。
5.将设计、合成的二十种短波长菁染料作为荧光染色剂应用于H929骨髓瘤细胞和精子细胞的荧光显微成像技术中,结果表明：染料A8、A11、A28和A31在终浓度为1uM～5uM时表现出优良的荧光性能,并且具有膜通透性、无毒、不干扰细胞的正常生理功能、荧光背景干扰小、无光漂白、对核酸(DNA)有较强的亲和性,是一种潜在的活细胞膜通透性荧光探针。将二十种染料应用于细胞存活率的PI复染实验中,与SYBRGreenⅠ比较,染料A8、A28和A31在死细胞中几乎完全被PI替代,没有残留,然而SYBR GreenⅠ残留较多,从而影响细胞存活率的准确性,因此染料A8、A28、A31在PI复染实验中可以作为SYBR GreenⅠ的替代品应用于流式细胞术中。
Cyanine dyes present typical optical properties and act as the most important organic functional dyes in many processes of technological interest like sensitizers in photography, optical recording materials in laser disks, sensitizers in solar cell, pH fluorescence probe, nonlinear optical materials etc. A very attractive additional feature of short-wavelength cyanine dyes is the affinity for biological structures, especially for DNA/RNA. Besides, they are nuclear membrane permeant, tolerated by living cells, photostable, and low cell cytotoxicity. Therefore, they have been utilized in many fields, such as gel staining, DNA sequencing, and flow cytometry, cell imaging, biological macromolecules labeling, etc. However, the types and application areas of the commercial live cell fluorescent dyes are limited, which are expensive and their popularization in clinical analysis are limited. In order to explore the types and application areas of the fluorescent dyes with excellent performance, the short-wavelength cyanine dyes are as the target synthesis compound in the paper. The short-wavelength cyanine dyes are used in live cell imaging and flow cytometry. The possibility of the dyes as the potential fluorescence probe is discussed. The paper presents the structure features, properties and application of cyanine dyes, and the preparation of dimethine cyanine dyes, styryl hemicyanine dyes and monomethine merocyanine dyes in recent years.
The main research included several aspects as the follows:
1. Seven short-wavelength cyanine dyes (six novel compounds) were designed and synthesized by microwave irradiation method. The products were identified by 1H NMR, IR, UV-Vis spectroscopy and elemental analysis. Based on the microwave power and irradiation time, the reaction activity for quaternary salts was discussed. It could be found that the sequence of the reaction acitivity of 1H-indole-3-carbaldehyde and various heterocyclic quaternary salts was:quinoline quaternary≈2-methyl pyridine qunaternary salt≈4-methyl pyridine qunaternary salt> naphthothiazole quaternary salt≈benzothiazole quaternary salt> benzindole quaternary salt> benzimidazole quaternary salt. The dyes absorbed in the region 376.0～484.0 nm and had molar extinction coefficients of 1.8×104～5.7×104 L-mol-1cm-1. Their fluorescence maxima were located at 512.6～548.6 nm, their fluorescence quantum yields were in the range of 0.0018～0.0285 in methanol, and their Stokes shifts were in the range of 53.6～104.6 nm. Theλmax had relationship with the basicity of heterocyclic nucleus, increasingλmax is considered to indicate decreasing basicity of heterocyclic nucleus. Moreover, theλmax was blue-shifted with increasing the solvent dielectric constant.
2. Thirteen novel short-wavelength cyanine dyes were designed and synthesized by microwave irradiation and classical solvent methods. The products were identified by 1H NMR, IR, UV-Vis spectroscopy and elemental analysis. The different substituents on the reactivity of quaternary salts was investigated, the result showed that reaction would took easier with increasing the electron donating ability of the substiuent. For the same substituent, 6-substituted heterocyclic quaternary slats was easier than that of 7-substituted heterocyclic quaternary when reaction with 1H-indole-3-carbaldehyde. The absorption and fluorescence properties of prepared dimethine cyanine dyes in the DNA/BSA presence were investigated, and the dyes had good affinity for DNA. Significant enhancement of the fluorescence intensity was observed for all the dye. The quantum yields of DNA-dyes increased up to 68.8 times compared with quantum yield of free dyes.
3. Four monomethine merocyanine dyes (three novel compounds) were synthesized by one-pot method. The products were identified by1H NMR, IR, UV-Vis spectroscopy and elemental analysis. The dyes absorbed in the region 17.0～429.0 nm and had molar extinction coefficients of 3.3×104～4.5×104 L·mol-1cm-1. Their fluorescence maxima were located at 476.0～511.6 nm, their fluorescence quantum yields were in the range of 0.0008～0.0024 in methanol. and their Stokes shifts were in the range of 59.0-82.6 nm. The crystal structures and packing modes of four monomethine merocyanine dyes were analyzed by X-ray diffraction, which revealed molecular conformation, intra-and intermolecular interactions in solid state of the dyes.
4. B3LYP/6-31G* and PBE1PBE/6-31G* levels were used for investigating the absorption spectra of seven indole dimethine cyanine dyes. The effect of solvent on the absorption and emission spectra of the dyes was taken into account using the polarizable continuum model PCM. The result showed that PBE1PBE/6-31G*(PCM) level gave more reliable description of the absorption characters. Based on the main torsion angles, it could be found that the better planar structural rigidity and the largerπconjugated system of the molecular, the stronger fluorescence it appeared. The lowest energy absorption in dyes was due to the first dipole-allowedπ→π* transition from HOMO to LUMO with largest oscillator strength. From the molecular orbitals, it could be found that the HOMO→LUMO absorption transition involved the intra electron displacement.
CIS/PCM level was used for investigating the emisson spectra of seven quinoline dimethine cyanine dyes on the S1 geometry. The result showed that the average relative deviation is 1.7%, the method could be used for predicting the emission spectra of the dyes. The molar extinction coefficients were calculated by Swizard program, and the shape of simulated absorption spectra are in a principal agreement the experimental spectra.
5. A further objective of this study was to explore the potential applications of the twenty prepared cyanine dyes as fluorescent probes in live cell imaging of H929 myeloma cells and sperms. The result showed that dyes A8、A11、A28 and A31 showed excellent fluorescence in the concentration of 1uM-5uM, and the dyes showed nuclear membrane permeant, low cell cytotoxicity, tolerated by living cells, little background interference, little photobleaching and good affinity for DNA. The dyes represented thus the potential cell-permeant fluorescence probes.
We also investigated effect of the twenty dyes on counterstaining with PI in flow cytometry, the commercial SYBR Green I was taken as the contrastive probe. Another significant advantage of the dyes A8、A28 and A31 was their little remnant and no interference on the accuracy in flow cytometry when counterstaining with PI. However, SYBR Green I and PI existed in the dead cells simultaneously, which affect the accuracy obtained by flow cytometry. The short-wavelength dyes A8、A28 and A31 were able to replace SYBR Green I as fluorescent probes in flow cytometry.
引文
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