当前位置：
X-MOL 学术
›
J. Am. Chem. Soc.
›
论文详情
Our official English website, www.x-mol.net, welcomes your
feedback! (Note: you will need to create a separate account there.)
In Search of the Perfect Photocage: Structure–Reactivity Relationships in meso-Methyl BODIPY Photoremovable Protecting Groups
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2017-10-17 , DOI: 10.1021/jacs.7b08532
Tomáš Slanina 1, 2 , Pradeep Shrestha 3 , Eduardo Palao 1 , Dnyaneshwar Kand 4 , Julie A. Peterson 3 , Andrew S. Dutton 3 , Naama Rubinstein 4 , Roy Weinstain 4 , Arthur H. Winter 3 , Petr Klán 1
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2017-10-17 , DOI: 10.1021/jacs.7b08532
Tomáš Slanina 1, 2 , Pradeep Shrestha 3 , Eduardo Palao 1 , Dnyaneshwar Kand 4 , Julie A. Peterson 3 , Andrew S. Dutton 3 , Naama Rubinstein 4 , Roy Weinstain 4 , Arthur H. Winter 3 , Petr Klán 1
Affiliation
|
A detailed investigation of the photophysical parameters and photochemical reactivity of meso-methyl BODIPY photoremovable protecting groups was accomplished through systematic variation of the leaving group (LG) and core substituents as well as substitutions at boron. Efficiencies of the LG release were evaluated using both steady-state and transient absorption spectroscopies as well as computational analyses to identify the optimal structural features. We find that the quantum yields for photorelease with this photocage are highly sensitive to substituent effects. In particular, we find that the quantum yields of photorelease are improved with derivatives with higher intersystem crossing quantum yields, which can be promoted by core heavy atoms. Moreover, release quantum yields are dramatically improved by boron alkylation, whereas alkylation in the meso-methyl position has no effect. Better LGs are released considerably more efficiently than poorer LGs. We find that these substituent effects are additive, for example, a 2,6-diiodo-B-dimethyl BODIPY photocage features quantum yields of 28% for the mediocre LG acetate and a 95% quantum yield of release for chloride. The high chemical and quantum yields combined with the outstanding absorption properties of BODIPY dyes lead to photocages with uncaging cross sections over 10 000 M-1 cm-1, values that surpass cross sections of related photocages absorbing visible light. These new photocages, which absorb strongly near the second harmonic of an Nd:YAG laser (532 nm), hold promise for manipulating and interrogating biological and material systems with the high spatiotemporal control provided by pulsed laser irradiation, while avoiding the phototoxicity problems encountered with many UV-absorbing photocages. More generally, the insights gained from this structure-reactivity relationship may aid in the development of new highly efficient photoreactions.
中文翻译：
寻找完美的光笼：中甲基 BODIPY 光可去除保护基团的结构-反应关系
通过离去基团 (LG) 和核心取代基以及硼取代基的系统变化，完成了对内甲基 BODIPY 光可去除保护基团的光物理参数和光化学反应性的详细研究。使用稳态和瞬态吸收光谱以及计算分析来评估 LG 释放的效率，以确定最佳结构特征。我们发现使用这种光笼进行光释放的量子产率对取代基效应高度敏感。特别是，我们发现具有更高系统间交叉量子产率的衍生物可以提高光释放的量子产率，这可以由核心重原子促进。此外，硼烷基化显着提高了释放量子产率，而在中间甲基位置的烷基化没有影响。较好的 LG 比较差的 LG 更有效地释放。我们发现这些取代基效应是累加的，例如，2,6-二碘-B-二甲基 BODIPY 光笼具有 28% 的普通 LG 醋酸盐量子产率和 95% 的氯化物释放量子产率。高化学和量子产率与 BODIPY 染料出色的吸收特性相结合，导致光笼具有超过 10 000 M-1 cm-1 的非笼化横截面，其值超过了相关光笼吸收可见光的横截面。这些新的光笼在 Nd:YAG 激光（532 nm）的二次谐波附近强烈吸收，有望通过脉冲激光照射提供的高时空控制来操纵和询问生物和材料系统，同时避免了许多吸收紫外线的光笼遇到的光毒性问题。更一般地说，从这种结构-反应性关系中获得的见解可能有助于开发新的高效光反应。
更新日期：2017-10-17
中文翻译：
寻找完美的光笼：中甲基 BODIPY 光可去除保护基团的结构-反应关系
通过离去基团 (LG) 和核心取代基以及硼取代基的系统变化，完成了对内甲基 BODIPY 光可去除保护基团的光物理参数和光化学反应性的详细研究。使用稳态和瞬态吸收光谱以及计算分析来评估 LG 释放的效率，以确定最佳结构特征。我们发现使用这种光笼进行光释放的量子产率对取代基效应高度敏感。特别是，我们发现具有更高系统间交叉量子产率的衍生物可以提高光释放的量子产率，这可以由核心重原子促进。此外，硼烷基化显着提高了释放量子产率，而在中间甲基位置的烷基化没有影响。较好的 LG 比较差的 LG 更有效地释放。我们发现这些取代基效应是累加的，例如，2,6-二碘-B-二甲基 BODIPY 光笼具有 28% 的普通 LG 醋酸盐量子产率和 95% 的氯化物释放量子产率。高化学和量子产率与 BODIPY 染料出色的吸收特性相结合，导致光笼具有超过 10 000 M-1 cm-1 的非笼化横截面，其值超过了相关光笼吸收可见光的横截面。这些新的光笼在 Nd:YAG 激光（532 nm）的二次谐波附近强烈吸收，有望通过脉冲激光照射提供的高时空控制来操纵和询问生物和材料系统，同时避免了许多吸收紫外线的光笼遇到的光毒性问题。更一般地说，从这种结构-反应性关系中获得的见解可能有助于开发新的高效光反应。
京公网安备 11010802027423号