Theoretical investigation on the fluorescent sensing mechanism for recognizing formaldehyde: TDDFT calculation and excited-state nonadiabatic dynamics

Inspired by the activity-based sensing method, the hydrazine-modified naphthalene derivative(Naph1) was synthesized and used as a fluorescent probe to detect formaldehyde(FA) in living cells. Through the condensation reaction between the probe Naph1 and analyte FA, researchers observed a ~14 folds enhancement of fluorescent signal around 510 nm in an experiment, realizing the high selectivity and sensitivity detection of FA. However, a theoretical understanding of the sensing mechanism was not provided in the experimental work. Given this, the light-up fluorescent detecting mechanism was in-depth unveiled by performing the time-dependent density functional theory(TDDFT) and the complete active space self-consistent field(CASSCF) theoretical calculations on excited-state intramolecular proton transfer(ESIPT)and non-adiabatic excited-state dynamics simulation. The deactivation channel of S_1/T_2 intersystem crossing(ISC) was turned off to successfully recognize FA. Insight into the ESIPT-based fluorescent detecting mechanism indicated that ESIPT was essential to light-up fluorescent probes. This work would provide a new viewpoint to develop ESIPT-based fluorescent probes for detecting reactive carbon species in vivo or vitio.

Rational molecular engineering towards efficient heterojunction solar cells based on organic molecular acceptors

The selection of photoactive layer materials for organic solar cells(OSCs) is essential for the photoelectric conversion process.It is well known that chlorophyll is an abundant pigment in nature and is extremely valuable for photosynthesis.However,there is little research on how to improve the efficiency of chlorophyll-based OSCs by matching chlorophyll derivatives with excellent non-fullerene acceptors to form heterojunctions.Therefore in this study we utilize a chlorophyll derivative,Ce_(6)Me_(3),as a donor material and investigate the performance of its heterojunction with acceptor materials.Through density functional theory,the photoelectric performances of acceptors,i ncluding the fullerene derivative PC_(71)BM and the terminal halogenated non-fullerene DTBCIC series,are compared in detail.It is found that DTBCIC-C1 has better planarity,light absorption,electron affinity,charge reorganization energy and charge mobility than others.Ce_(6)Me_(3) has good energy level matching and absorption spectral complementarity with the investigated acceptor molecules and also shows good electron donor properties.Furthermore,the designed Ce_(6)Me_(3)/DTBCIC interfaces have improved charge separation and reorganization rates(K_(CS)/K_(CR)) compared with the Ce_(6)Me_(3)/PC_(71)BM interface.This research provides a theoretical basis for the design of photoactive layer materials for chlorophyll-based OSCs.

Remotely excited Raman optical activity using chiral plasmon propagation in Ag nanowires

We experimentally investigated remotely excited Raman optical activity(ROA)using propagating surface plasmons in chiral Ag nanowires.Using chiral fmoc-glycyl-glycine-OH(FGGO)molecules,we first studied the local surface plasmon-enhanced ROA.We found that the Raman intensity can be excited by left-and right-circularly polarized lights and that the circular intensity difference(CID)can be significantly enhanced.Second,by selecting vibrational modes with large Raman and ROA intensities that are not influenced by chemical enhancements,we studied remotely excited ROA imaging and the CID of FGGO molecules by propagating a plasmonic waveguide using Ag chiral nanostructures.When laser light was radiated on one of the Ag terminals,the measured CID of the FGG at the other terminal showed little change compared to the local excited CID.Meanwhile,when the laser light was radiated on the Ag nanowires(not on the terminals)and was coupled to the nearby nanoantenna,the CID of the ROA could be manipulated by altering the coupling angle between the Ag nanowires.To directly demonstrate the propagation of ROA along the nanowire and its remote detection,we also measured the remotely excited ROA spectra.Our experimental method has the potential to remotely determine the chirality of molecular structures and the absolute configuration or conformation of a chiral live cell.