New Method for Covalent Fluorescent Biomolecule Labeling with Hemicyanine Dye

Fluorescent chromophore, alkylamino-(tetra-hydronaphthalenylidene)- benzothiazolium derivatives (HBTN dyes), are proposed as covalent labels for proteins via aliphatic amino groups. Spectral-luminescent properties of 3-methyl-2-{(E)-[7-(methylamino)-4,4a,5,6-tetra-hydronaphthalen-2(3H)-ylidene]methyl}-1,3-benzothiazol-3-ium chloride (HBTN, R=Me) and its predecessor, 2-[(E)-(7-methoxy-4,4a,5,6-tetrahydronaphthalen-2(3H)-ylidene)methyl]-3-methyl-1,3-benzothia-zol-3-ium chloride (ABTN), are studied for free dyes and in the presence of DNA and BSA. Considerable spectral-luminescent changes accompany the transformation of ABTN into HBTN that allows monitoring conjugation reaction. In presence of DNA and BSA the HBTN increases its emission in 15 and 4 times respectively and becomes strongly fluorescent. The conditions for labeling are developed and a model conjugate of HBTN dye with BSA is synthesized. It was shown that using of HBTN dye as a fluorescent label allows detection by eye of about 3 μg/band of BSA on polyacrylamide gel upon UV-irradiation.     

New Cross-Linking Quinoline and Quinolone Derivatives for Sensitive Fluorescent Labeling

A variety of contemporary analytical platforms, utilized in technical and biological applications, take advantage of labeling the objects of interest with fluorescent tracers-compounds that can be easily and sensitively detected. Here we describe the synthesis of new fluorescent quinoline and quinolone compounds, whose light emission can be conveniently tuned by simple structural modifications. Some of these compounds can be used as sensitizers for lanthanide emission in design of highly sensitive luminescent probes. In addition, we also describe simple efficient derivatization reactions that allow introduction of amine- or click-reactive cross-linking groups into the fluorophores. The reactivity of synthesized compounds was confirmed in reactions with low molecular weight nucleophiles, or alkynes, as well as with click-reactive DNA-oligonucleotide containing synthetically introduced alkyne groups. These reactive derivatives can be used for covalent attachment of the fluorophores to various biomolecules of interest including nucleic acids, proteins, living cells and small cellular metabolites. Obtained compounds are characterized using NMR, steady-state fluorescence spectroscopy as well as UV absorption spectroscopy.     

New Approach for Fluorescent Peptide Labeling with Pyrylium Cyanine Dyes

New approach for fluorescent peptide labeling with cyanine dyes utilizing the reaction of pyrylium salts with aliphatic aminogroup is proposed. The reaction of two pyrylium cyanines dye acids was investigated. Lysocyme was used as a model peptide for conjugation. The proposed method can be used as a simple and convenient alternative for the known procedures because it does not require preparation of the unstable amino-reactive intermediates from a carboxyl- or sulfo-derivative of cyanine dyes.     

荧光碳点对人血淋巴细胞标记成像

以葡萄糖为碳源,采用溶剂热法合成荧光碳点.用紫外-可见分光光度法和荧光光谱法研究了荧光碳点的发光特性.并将其与鼠抗人CD3抗体、羊抗鼠IgG抗体连接制备两种水溶性复合探针,对人血淋巴细胞进行免疫荧光标记成像.结果表明用该探针对人血淋巴细胞成像清晰,72h后细胞仍然保持明亮的荧光.     

Monitoring the Instant Creation of a New Fluorescent Signal for Evaluation of DNA Conformation Based on Intercalation Complex

Here we report the monitoring the instant creation of a new fluorescent signal (FS) aroused from a positively charged water-soluble fluorogenic probe, ethidium bromide (EtBr) in the presence of a radical initiator, ammonium persulfate (APS) and an accelerator, tetraethylmetilendiamine (TEMED) for evaluation of deoxyribonucleic acid (DNA) conformation. The results revealed that the occurred FS (λ_ex?=?430 nm; λ_max?=?525 nm) is a reduced form of EtBr (λ_ex?=?480 nm; λ_max?=?617 nm) and it is completely distinct from hydroethidine (λ_ex?=?350 nm; λ_max?=?430 nm), which is two-electron reduced form of EtBr. It was noticed that EtBr was reduced to a new FS during the polymerization of N, N dimethyacrylamide (DMAA) too, at 25 °C in the presence of APS and TEMED or at 55 °C with only APS, and the rate of formation of FS was increased upon treatment time. The effect of nanoclays such as Laponite XLG® and Laponite XLS®, which provide a protective environment for DNA in nature, were also investigated through the reduction process of EtBr in the absence and presence of a water soluble monomer DMAA. We demonstrated that DNA conformation might be evaluated by monitoring FS effectuated during the reduction of EtBr in the presence of nanoclays having positively and negatively charged surfaces. Protective property of DNA against the formation of reduced product was elucidated by carrying out the polymerization at 55 °C. The results revealed that the monitoring of formation of FS in the presence of radical initiator could lead to elucidate the conformation of DNA upon formation of intercalator complex.     

Synthesis of BODIPY Derivatives Substituted with Various Bioconjugatable Linker Groups: A Construction Kit for Fluorescent Labeling of Receptor Ligands

The goal of the present study was to design small, functionalized green-emitting BODIPY dyes, which can readily be coupled to target molecules such as receptor ligands, or even be integrated into their pharmacophores. A simple two-step one-pot procedure starting from 2,4-dimethylpyrrole and ω-bromoalkylcarboxylic acid chlorides was used to obtain new ω-bromoalkyl-substituted BODIPY fluorophores (1a–1f) connected via alkyl spacers of different length to the 8-position of the fluorescent dye. The addition of radical inhibitors reduced the amount of side products. The ω-bromoalkyl-substituted BODIPYs were further converted to introduce various functional groups: iodo-substituted dyes were obtained by Finkelstein reaction in excellent yields; microwave-assisted reaction with methanolic ammonia led to fast and clean conversion to the amino-substituted dyes; a hydroxyl-substituted derivative was prepared by reaction with sodium ethylate, and thiol-substituted BODIPYs were obtained by reaction of 1a–1f with potassium thioacetate followed by alkaline cleavage of the thioesters. Water-soluble derivatives were prepared by introducing sulfonate groups into the 2- and 6-position of the BODIPY core. The synthesized BODIPY derivatives showed high fluorescent yields and appeared to be stable under basic, reducing and oxidative conditions. As a proof of concept, 2-thioadenosine was alkylated with bromoethyl-BODIPY 1b. The resulting fluorescent 2-substituted adenosine derivative 15 displayed selectivity for the A₃ adenosine receptor (ARs) over the other AR subtypes, showed agonistic activity, and may thus become a useful tool for studying A₃ARs, or a lead structure for further optimization. The new functionalized dyes may be widely used for fluorescent labeling allowing the investigation of biological targets and processes.     

新型蓝光吡唑啉荧光化合物的合成与红外光谱研究

用已合成的苯并噻唑吡唑啉类化合物作为参考［1,2］,依据Schellhammer经验中化学结构与荧光性关系,在吡唑啉的1-位引入了苯并噻唑基或苯并咪唑基,3-位引入苯基衍生物,使其具有荧光性,5-位引入苯基作为助色团,可使荧光谱红移。考虑3-位苯环上若带有—NH₂的吡唑啉化合物有利荧光性的提高,设计合成了两种目前国内外均未见报道的带有—NH₂的苯并噻唑及苯并咪唑吡唑啉化合物,经荧光检测证明其荧光性能受—NH₂的影响有所增强,荧光发射波长处在蓝绿光的范围内,是两种新型蓝光荧光化合物。经红外光谱分析,确定了带有—NH₂的苯并噻唑基或苯并咪唑基取代的吡唑啉类化合物具有的典型特征吸收峰,确证了化合物的结构。为利用红外光谱分析此类新型化合物的结构提供了便捷的方法。     

Microwave Assisted Synthesis of a New Triplet Iridium(III) Pyrazine Complex

采用微波辅助加热方法,2,3-二苯基吡嗪(DPP)与水合三氯化铱(IrCl₃·3H₂O)反应制备了[Ir(DPP)₃],通过¹H NMR、元素分析和质谱方法对配合物结构进行了表征,并研究了配合物的吸收光谱和光致发光光谱. 结果表明,配合物Ir(DPP)₃在382和504 nm处存在单重态¹MLCT(金属到配体的电荷跃迁)和三重态³MLCT的吸收;在573 nm 处有较强的金属配合物三重态的磷光发射.     

Synthesis of New Quinoline-Conjugated Calixarene as a Fluorescent Sensor for Selective Determination of Cu2+ Ion

Journal of Fluorescence - A novel quinoline-functionalized calix [4] arene derivative (Quin-Calix) has been successfully synthesized at partial cone conformation and duly characterized by using...     

硅包覆上转换纳米晶制备和表征及生物特异性标记研究

以NaYF₄为代表的上转换纳米晶作为细胞及组织标记的研究越来越热。但易团聚,水溶性、生物兼容性差,没有与生物偶联官能团等缺点限制了其应用,因而表面修饰显得尤为重要。作者通过水热和共沉淀相结合方法,制备了NaYF₄∶Yb3+, Er3+上转换纳米晶,并对其包覆二氧化硅壳层。SEM表征硅包覆前后分别为25和250 nm的单分散粒子,说明硅已成功地包覆于纳米晶表面。980 nm激光照射下,样品的PBS胶体溶液呈可视上转换绿光。上转换荧光光谱和寿命均表明二氧化硅壳层对其发光性质影响很小。圆二色谱说明蛋白分子通过戊二醛与纳米晶偶联前后的二级结构基本不变。基于硅片上的抗原抗体荧光免疫识别试验进一步验证了偶联蛋白分子的特异性,表明该上转换纳米晶适合于生物标记。     

金属离子修饰的ZnS/PAMAM纳米复合材料的荧光性能研究

用荧光分光光度法研究了Zn2+,Mn2+,Cd2+,Na+,K+,Ag+,Cu2+和Pb2+等金属离子修饰的ZnS/PAMAM树形分子纳米复合材料的荧光发射性能。结果表明：不同金属离子修饰效果不同。Zn2+,Mn2+和Cd2+修饰后,ZnS/PAMAM树形分子纳米复合材料的荧光发射强度有不同程度提高;Ag+,Cu2+和Pb2+的修饰对荧光有不同程度的猝灭作用;而Na+和K+的修饰对荧光发射无明显影响。与修饰前相比,Cd2+离子修饰的ZnS/PAMAM树形分子纳米复合材料标记的潜指纹发射的蓝色荧光更加明亮,与背景反差更加明显。这对提高潜指纹的显现精度和准确率有很好的借鉴价值。     

Synthesis, Characterization and Reactivity Study of a New Penta-Coordinated Mn(II) Complex

A penta-coordinated Mn(II) compound [dqpMnCl₂] (1) (dqp = 2,6-di-(8-quinoline-yl)-pyridine) has been synthesized and its X-ray crystallographic structure is reported here. Magnetic susceptibility measurements confirmed a high-spin Mn(II) (S = 5/2) center in 1. The X-band EPR spectrum of 1 in dimethylformamide solution exhibits widely distributed transitions in the spectral range from 0 to 700 mT with particularly well-resolved hyperfine lines due to the ⁵⁵Mn (I = 5/2) nucleus. The abundance of highly resolved transition lines in the spectrum facilitated the electron paramagnetic resonance spectral simulation which revealed large zero-field splitting and g-anisotropies. When dissolved, 1 exists in equilibrium with a hexa-coordinated species, the latter probably resulting from disassociation of one chlorido-ligand allowing ligation of two solvent molecules. The redox behavior of 1 was studied and was compared to that of a structural analog for which water oxidation in the presence of a chemical oxidant has been shown. The results from water oxidation trials of 1 are discussed.     

新型镧配合物的合成与荧光性质

在氮气保护下,以无水乙醇为溶剂,制备了硝酸镧与4-氨基-1,2,4-三氮唑缩对二甲氨基苯甲醛(L)配合物,单晶结构分析确定其组成为LaL_3(NO_3)_3·(H_2O)_2·(C_2H_5OH)_2,配合物中La~(3+)分别与3个硝酸根、2个水分子和2个分子乙醇中的氧原子配位,配位数为10,并与4-氨基-1,2,4-三氮唑缩对二甲氨基苯甲醛以氢键形式结合形成立体结构分子.通过元素分析、红外光谱、固体荧光光谱等手段对合成的配体及配合物进行了表征.实验结果表明,4-氨基-1,2,4-三氮唑缩对二甲氨基苯甲醛是一种多晶粉末状的发光材料,固体荧光谱图显示荧光发射峰在451 nm处,为蓝色荧光,色纯度高,荧光量子效率高,而合成的配合物的荧光发射峰则红移至464 nm左右,同时荧光强度显著增强近一倍.     

氮功能化大环化合物及其Ni(Ⅱ)配合物的合成和谱学研究

以丙酮,乙二胺,溴乙酸乙酯为原料合成了三种新的氮功能化四氮杂大环化合物的配合物,用元素分析,电子光谱,红外光谱,氢核磁共振谱和质谱对它们进行了研究。     

含铕配合物荧光纳米纤维的制备及光学性质的研究

通过静电纺丝技术,将发光良好的稀土配合物Eu(DBM)₃·H₂O和Eu(DBM)₄·CPC纳米微粒复合到水溶性的聚乙烯基吡咯烷酮中,制备了具有稀土铕离子红色特性荧光的聚合物纳米纤维。通过对稀土配合物以及聚合物纳米纤维样品扫描电镜和透射电镜的测试,发现当稀土配合物复合到聚合物纳米纤维中后,由于与聚乙烯基吡咯烷酮乙醇溶解性良好,其微观结构发生了变化,得到了50～100 nm左右的比较均匀的线状结构。同时,通过对稀土配合物以及聚合物纳米纤维样品的荧光激发、发射光谱及荧光寿命进行研究,表明稀土配合物在聚合物纳米纤维中比其在粉末状有更高的发光强度及更长的荧光寿命,其原因在于高分子纳米纤维为稀土配合物提供了较稳定的化学环境。     

Synthesis and Characterization of a Fluorescent Water-Borne Polyurethane Based on a Novel Naphthalimide Dye

A waterborne-polyurethane (WPU) dye, based on the fluorescent dye 4-diamino propane-N-allyl-1,8- naphthalimide (WPU-DAN), was synthesized by attaching 4-diamino propane-N-allyl-1,8- naphthalimide (DAN) onto both ends of the polyurethane (PU) chains according to a prepolymer?ionomer process. The synthetic process was confirmed by Fourier transform infrared spectroscopy (FTIR) and UV-visible absorption. The glass transition temperature, molecular weight and average particle sizes were measured. The glass transition temperatures of WPU and WPU-DAN were 46.6 and 49.8°C, respectively. In addition, the particle size distributions of WPU-DAN and WPU were 140 and 134 nm, respectively. The thermal behaviour of WPU-DAN showed improvement compared to WPU. The fluorescence intensity of WPU-DAN was enhanced more than DAN due to the naphthalimide groups attached to the chains, and the fluorescence intensity of WPU-DAN and DAN were increased by increasing temperature. Moreover, the fluorescence intensity of WPU-DAN emulsion was stable during 30 days and no loss of fluorescence intensity occurred for these days.     

New spiro[benzotetraphene-fluorene] Derivatives: Synthesis and Application in Sky-Blue Fluorescent Host Materials

Blue light-emitting spiro[benzotetraphene-fluorene] (SBTF)-based host materials, 3-(1-naphthyl)-10-naphthylspiro[benzo[ij]tetraphene-7,9′-fluorene] (1), 3-(2-naphthyl)-10-naphthylspiro[benzo[ij]tetraphene-7,9′-fluorene] (2), and 3-[2-(6-phenyl)naphthyl]-10-naphthylspiro[benzo[ij]tetraphene-7,9′-fluorene] (3) were designed and prepared via multi-step Suzuki coupling reactions. Introducing various aromatic groups into SBTF core lead to a reduction in band gap and a determination of the color purity and luminescence efficiency. Typical sky-blue fluorescent organic light emitting diodes with the configuration of ITO/N,N′-di(1-naphthyl)-N,N′-bis[(4-diphenylamino)phenyl]-biphenyl-4,4′-diamie (60 nm)/N,N,N′,N′-tetra(1-biphenyl)-biphenyl-4,4′-diamine (30 nm)/host: dopant (30 nm, 5 %)/LG201 (electron transporting layer, 20 nm)/LiF/Al were developed using SBTF derivatives as a host material and p-bis(p-N,N-diphenyl-aminostyryl)benzene (DSA-Ph) as a sky-blue dopant material. A device obtained from three materials doped with DSA-Ph showed color purity of 0.148 and 0.239, a luminance efficiency of 7.91 cd/A, and an external quantum efficiency >4.75 % at 5 V.     

新型吡唑啉类荧光化合物的合成及光谱分析

吡唑啉衍生物作为荧光增白剂具有优良的性质,已被广泛应用于染料工业。根据Schellhammer化学结构与荧光性的经验,在吡唑啉环的1-位引入苯并噻唑基,3-位引入吲哚基,5-位引入苯基衍生物,设计并合成了六种新的吡唑啉衍生物,并且通过红外光谱、1H NMR谱、质谱和元素分析进行了确证。化合物的荧光性能测定结果显示此类化合物具有良好的荧光性,均可吸收353 nm左右紫外光,最大发射波长在430～443 nm之间,是一类很有发展前途的蓝紫色荧光化合物。荧光最大发射波长和荧光强度与取代基有关,在苯并噻唑上引入6-Br基团,化合物的荧光发射波长发生蓝移,且强度增大;而引入CH₃基团,化合物的荧光发射波长发生红移,且强度降低。取代基和溶剂极性对荧光量子产率的影响较小。荧光相对强度与荧光量子产率没有直接关系。     

New emissions in a Nd:YAG small spherical cavity

The strong resonant pumping in a Nd:YAG small sphere modifies the radiative transition possibility distribution between two transition energy levels in the material. Some new emissions which cannot be seen in the bulk material are found for the first time.