Origins of near-infrared-II emission tail and fluorescence enhancement of albumin-chaperoned cyanine dyes from a multiscale computational study

Jiang，Guanyu1; Hu，Zhubin1; Bai，Lang2; Zhong，Cheng3; Lu，Sen4,5; Han，Baoshan4,5; Sun，Zhenrong1; Zhu，Shoujun2; Liang，Yongye6; Sun，Haitao1,7,8

2023

10.1039/d3tc00452j

Journal of Materials Chemistry C   影响因子和分区

2050-7526

2050-7534

Repurposing the commercially available NIR-I cyanine dyes for NIR-II imaging has attracted increasing research interest. The bright tail emission of the present NIR-I dyes can afford high-performance NIR-II imaging with improved quantum yields (QYs) and absorption coefficients, thus accelerating the (pre-) clinical translation of NIR-II imaging. However, the quantum nature of the typically ignored but important NIR-II emission tail of cyanine dyes has never been revealed systematically, and an in-depth understanding of the fluorescence enhancement mechanism for cyanine-protein assemblies remains unclear. In this work, the quantum chemical calculations, molecular dynamics simulations, and fluorescence intensity measurements were used together to study the electronic and optical properties based on two representative cyanine dyes of ICG and IR783 with similar molecular skeletons. Distinct origins of NIR-II tail emission were identified, illustrating their significantly different quantum nature of the excited state: nuclear vibration versus twisted intramolecular charge transfer (TICT). Furthermore, the key roles of bovine serum albumin (BSA) protein through a supramolecular assembly strategy in building high-performance NIR-I cyanine dyes with NIR-II imaging were revealed. A rigid conformation of cyanine with optimal torsion can be maintained in the typically inaccessible hydrophobic domains of the BSA protein to avoid completely falling into the so-called fluorescence quenching trap. Notably, the first water shell plays a dominant role in fluorescence quenching, and the dipole-dipole coupling involved in the energy transfer process between the fluorophore and water is related not only to their distance but also to the relative orientation of each water molecule with respect to the fluorophore. The present study can provide a comprehensive understanding of the nature of NIR-II tail emission for conventional NIR-I dyes and further provide a general rule to explore conventional NIR-I dyes with bright NIR-II tail emission for NIR-II imaging.

SCI ; EI

英语

其他

National Natural Science Foundation of China["12274128","12034008","12250003","12204172"] ; Shanghai Rising Star Program[21QA1402600] ; Program of Introducing Talents of Discipline to Universities 111 Project[B12024] ; ECNU Multifunctional Platform for Innovation[001]

Materials Science ; Physics

Materials Science, Multidisciplinary ; Physics, Applied

WOS:000992727800001

ROYAL SOC CHEMISTRY

20232214173560

Charge transfer ; Energy transfer ; Excited states ; Fluorescence quenching ; Infrared devices ; Mammals ; Molecular dynamics ; Molecules ; Optical properties ; Proteins ; Quantum chemistry ; Quantum theory

Heat Treatment Processes:537.1 ; Light/Optics:741.1 ; Physical Chemistry:801.4 ; Chemical Reactions:802.2 ; Organic Compounds:804.1 ; Atomic and Molecular Physics:931.3 ; Quantum Theory; Quantum Mechanics:931.4

2-s2.0-85160516556

Scopus

1.State Key Laboratory of Precision Spectroscopy,School of Physics and Electronic Science,East China Normal University,Shanghai,200241,China
2.State Key Laboratory of Supramolecular,Structure and Material College of Chemistry,Jilin University,Changchun,130012,China
3.Hubei Key Lab on Organic and Polymeric Optoelectronic Materials,Department of Chemistry,Wuhan University,Wuhan,430072,China
4.Department of General Surgery,Xinhua Hospital,Affiliated with Shanghai Jiao Tong University School of Medicine,Shanghai,200092,China
5.School of Health Science and Engineering,University of Shanghai for Science and Technology,Shanghai,200093,China
6.Department of Materials Science and Engineering,Shenzhen Key Laboratory of Printed Organic Electronics,Southern University of Science and Technology,Shenzhen,518055,China
7.Collaborative Innovation Center of Extreme Optics,Shanxi University,Taiyuan,Shanxi,030006,China
8.NYU-ECNU Center for Computational Chemistry at NYU Shanghai,Shanghai,200062,China

Jiang，Guanyu,Hu，Zhubin,Bai，Lang,et al. Origins of near-infrared-II emission tail and fluorescence enhancement of albumin-chaperoned cyanine dyes from a multiscale computational study[J]. Journal of Materials Chemistry C,2023,11(22):7243-7251.

Jiang，Guanyu.,Hu，Zhubin.,Bai，Lang.,Zhong，Cheng.,Lu，Sen.,...&Sun，Haitao.(2023).Origins of near-infrared-II emission tail and fluorescence enhancement of albumin-chaperoned cyanine dyes from a multiscale computational study.Journal of Materials Chemistry C,11(22),7243-7251.

Jiang，Guanyu,et al."Origins of near-infrared-II emission tail and fluorescence enhancement of albumin-chaperoned cyanine dyes from a multiscale computational study".Journal of Materials Chemistry C 11.22(2023):7243-7251.