Bioconjugatable, PEGylated Hydroporphyrins for Photochemistry and Photomedicine. Narrow-Band, Near-Infrared-Emitting Bacteriochlorins.
Bioconjugatable, PEGylated Hydroporphyrins for Photochemistry and Photomedicine. Narrow-Band, Near-Infrared-Emitting Bacteriochlorins.
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用于光化学和光医学的生物共轭聚乙二醇化氢卟啉。
DOI：
10.1039/c6nj01155a
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发表时间：
2016
期刊：
影响因子：
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通讯作者：
Lindsey,JonathanS
中科院分区：
文献类型：
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作者：
Zhang,Nuonuo;Jiang,Jianbing;Liu,Mengran;Taniguchi,Masahiko;Mandal,AmitKumar;Evans-Storms,RosemaryB;Pitner,JBruce;Bocian,DavidF;Holten,Dewey;Lindsey,JonathanS
合成细菌叶绿素吸收近红外（NIR）区域，是天然细菌叶绿素的通用类似物。在能源科学和光医学中利用这些生色团需要能够定制它们的物理化学性质，包括掺入单元以赋予水溶性。在此，我们报告的合成，从两个常见的菌绿素积木，五个波长可调，bioconjugatable和水溶性菌绿素沿着与两个nonbioconjugatable基准。每个菌绿素带有短的聚乙二醇（PEG）单元作为水溶性基序。PEG基团位于吡咯β位芳基的3，5位，以抑制水性介质中的聚集。包含单个羧酸的手柄被合并以允许生物缀合。在水中的七种水溶性菌绿素显示出在NIR范围内的Qy吸收（672-819 nm）、尖锐的发射（21-36 nm半峰全宽）和适度的荧光量子产率（0.017-0.13）。每种菌绿素是中性的（非离子），但可溶于有机物（例如，CH 2Cl 2，DMF）和水溶液。使用吸收光谱法，通过改变浓度1000倍（190-690 μM至0.19-0.69 μM），并伴随光程（0.01-10 cm）的倒数变化，评估水溶性。所有的菌绿素在水中表现出优异的溶解度，除了菌绿素-酰亚胺，在较高浓度下产生轻微的聚集。将一种菌绿素与小鼠多克隆IgG抗体缀合，用于流式细胞术，其中补偿珠用于原理证明。B2-NHS的抗体偶联物在紫外激光激发（355 nm）时显示出尖锐信号，NIR发射用730/45 nm带通滤波器测量。总的来说，这项研究提供了一套水溶性菌绿素具有理想的物理性质，用于多个领域。
Synthetic bacteriochlorins absorb in the near-infrared (NIR) region and are versatile analogues of natural bacteriochlorophylls. The utilization of these chromophores in energy sciences and photomedicine requires the ability to tailor their physicochemical properties, including the incorporation of units to impart water solubility. Herein, we report the synthesis, from two common bacteriochlorin building blocks, of five wavelength-tunable, bioconjugatable and water-soluble bacteriochlorins along with two non-bioconjugatable benchmarks. Each bacteriochlorin bears short polyethylene glycol (PEG) units as the water-solubilizing motif. The PEG groups are located at the 3,5-positions of aryl groups at the pyrrolic β-positions to suppress aggregation in aqueous media. A handle containing a single carboxylic acid is incorporated to allow bioconjugation. The seven water-soluble bacteriochlorins in water display Qy absorption into the NIR range (672–819 nm), sharp emission (21–36 nm full-width-at-half-maximum) and modest fluorescence quantum yield (0.017–0.13). Each bacteriochlorin is neutral (non-ionic) yet soluble in organic (e.g., CH2Cl2, DMF) and aqueous solutions. Water solubility was assessed using absorption spectroscopy by changing the concentration ∼1000-fold (190–690 μM to 0.19–0.69 μM) with a reciprocal change in pathlength (0.01–10 cm). All bacteriochlorins showed excellent solubility in water, except for a bacteriochlorin–imide that gave slight aggregation at higher concentrations. One bacteriochlorin was conjugated to a mouse polyclonal IgG antibody for use in flow cytometry with compensation beads for proof-of-principle. The antibody conjugate of B2-NHS displayed a sharp signal upon ultraviolet laser excitation (355 nm) with NIR emission measured with a 730/45 nm bandpass filter. Overall, the study gives access to a set of water-soluble bacteriochlorins with desirable photophysical properties for use in multiple fields.