CRY2 interacts with CIS1 to regulate thermosensory flowering via FLM alternative splicing.

Cryptochromes (CRYs) are evolutionarily conserved photolyase-like photoreceptors found in almost all species, including mammals. CRYs regulate transcription by modulating the activity of several transcription factors, but whether and how they affect pre-mRNA processing are unknown. Photoperiod and temperature are closely associated seasonal cues that influence reproductive timing in plants. CRYs mediate photoperiod-responsive floral initiation, but it is largely unknown whether and how they are also involved in thermosensory flowering. We establish here that blue light and CRY2 play critical roles in thermosensory flowering in Arabidopsis thaliana by regulating RNA alternative splicing (AS) to affect protein expression and development. CRY2 INTERACTING SPLICING FACTOR 1 (CIS1) interacts with CRY2 in a blue light-dependent manner and promotes CRY2-mediated thermosensory flowering. Blue light, CRYs, and CISs affect transcriptome-wide AS profiles, including those of FLOWERING LOCUS M (FLM), which is critical for temperature modulation of flowering. Moreover, CIS1 binds to the FLM pre-mRNA to regulate its AS, while CRY2 regulates the RNA-binding activity of CIS1. Thus, blue light regulates thermosensory flowering via a CRY2-CIS1-FLM signaling pathway that links flowering responses to both light and ambient temperature.

Modulating the intersystem crossing mechanism of anthracene carboxyimide-based photosensitizers via structural adjustments and application as a potent photodynamic therapeutic reagent.

Herein, a series of compact anthracene carboxyimide (ACI) based donor-acceptor dyads were prepared by substituting bulky aryl moieties with various electron-donating ability to study the triplet-excited state properties. The ISC mechanism and triplet yield of the dyads were successfully tuned via structural manipulation. Efficient ISC (ΦΔ ≈ 99%) and long-lived triplet state (τT ≈ 122 µs) was observed for the orthogonal anthracene-labeled ACI derivative compared to the Ph-ACI and NP-ACI dyads, which showed fast triplet state decay (τT ≈ 7.7 µs). Femtosecond transient absorption study demonstrated the ultrafast charge separation (CS) and efficient charge recombination (CR) in the orthogonal dyads and ISC occurring via spin-orbit charge transfer (SOCT) mechanism (AN-ACI: τCS = 355 fs, τCR = 2.41 ns; PY-ACI: τCS = 321 fs, τCR = 1.61 ns), while in Ph-ACI and NP-ACI dyads triplet populate following the normal ISC channel (nπ* → ππ* transition), no CS was observed. We found that the attachment of suitable aryl donor moiety (AN- or PY-) to the ACI core can ensure the insertion of the intermediate triplet state, resulting in a small energy gap among charge separated state (CSS) and triplet state, which leads to efficient ISC in these derivatives. The SOCT-ISC-based AN-ACI dyad was confirmed to be a potent photodynamic therapeutic reagent; an ultra-low IC50 value (0.27 nM) that was nearly 214 times lower than that of the commercial Rose Bengal photosensitizer (57.8 nM) was observed.

Charge Separation and Intersystem Crossing in Homo- and Hetero-Compact Naphthalimide Dimers.

Naphthalimide (NI) homo- and hetero-dimers adopting orthogonal geometry were prepared to study photo-induced symmetry-breaking charge transfer (SBCT) and charge recombination (CR)-induced intersystem crossing (ISC). The two moieties in the dimer are connected either at the 3-C or 4-C position of the NI unit. The photophysical properties of the dimers were studied with steady-state and transient absorption spectroscopic methods. Significant CT only occurs for the hetero-dimer, in which one NI unit has a 4-amino substituent and the other NI unit is without it. The CR-induced ISC is most efficient for this dimer (singlet oxygen quantum yield ΦΔ = 50.3%). For the homo-dimer, in which both NI units did not present amino substitution, SBCT was not observed. Based on the electrochemical studies, we propose that the absence of SBCT for the homo-dimer is attributed to its high oxidation potential and low reduction potential. Femtosecond transient absorption (fs TA) spectra show that there is no charge separation (CS) for the homo-dimer. Nanosecond transient absorption spectroscopy indicate the formation of a triplet state with electron delocalization for the homo dimer, with a lifetime of 72.0 µs, while for the hetero dimer a triplet state with an intrinsic lifetime of 206.4 µs is observed. CS (11.6 ps) and slow CR-induced ISC (>1.5 ns) were observed for the hetero-dimer. Time-resolved electron paramagnetic resonance spectra give the zero-field splitting parameters (|D| = 1894 MHz and |E| = 111 MHz) and electron spin polarization patterns (e, e, e, a, a, a) for the triplet state of the hetero-dimer, inferring that the triplet state of the hetero-dimer is confined on the amino-substituted NI moiety.

Revealing the Photophysical and Photochemical Reaction Processes of Carprofen in Different Solutions via Ultrafast Femtosecond to Nanosecond Transient Absorption.

Carprofen (CP), one kind of a nonsteroidal anti-inflammatory drug, exhibits phototoxic side effects in physiology, while its phototoxic mechanism is ambiguous. To uncover CP's photophysical and photochemical reaction processes, femtosecond to nanosecond transient absorption spectroscopies were employed to directly detect excited states and transient intermediates of CP upon UV irradiation in pure acetonitrile (MeCN), MeCN/water 1:1, and acid/alkaline buffer solutions. The transient absorption data together with DFT calculations were integrated to elucidate mechanisms for photochemical reactions of CP in different solutions. The associated photophysical and photochemical reaction pathways are dependent on various solution environments. In a pure MeCN solvent, CP is excited to a singlet state (S1) and rapidly interacts with the solvent to proceed solvent rearrangement (SR). It then undergoes vibrational cooling (VC) and proceeds intersystem crossing (ISC) to produce the lowest triplet state (3CP). 3CP finally decays to the ground state. While in a MeCN/water 1:1 solution, deprotonated S1 of CP experiences SR and VC processes, and then it is promoted to a deprotonated triplet state (3CP-). 3CP- undergoes the parallel reactions: dechlorination to a phenyl radical (2CP-) and decarboxylation to a T1 anion (3CP-(de-CO2)). Finally, both intermediates produce the radical anion species 2CP-(de-CO2). In a pH = 7.4 (MeCN/PBS 1:1) solution, 3CP- can be converted into 2CP-(de-CO2) more quickly. Interestingly, we found that the dechlorination step can be promoted in an alkaline solution. Phenyl and chlorine radicals produced in an aqueous solution may be the root cause of the drug's harmful side effects on the human body. This may be useful to guide the design of related CP drugs with minimal phototoxicity in the pharmaceutical process.

Charge Transfer, Intersystem Crossing, and Electron Spin Dynamics in a Compact Perylenemonoimide-Phenoxazine Electron Donor-Acceptor Dyad.

With phenoxazine (PXZ) as the electron donor and perylene-3,4-dicarboximide (PMI) as the electron acceptor, we prepared a compact, orthogonal electron donor-acceptor dyad (PMI-PXZ) to study the spin-orbit charge transfer-induced intersystem crossing (SOCT-ISC). A weak charge transfer (CT) absorption band, due to S0 → 1CT transition, was observed (ε = 2840 M-1 cm-1 at 554 nm, FWHM: 2850 cm-1), which is different from that of the previously reported analogue dyad with phenothiazine as the electron donor (PMI-PTZ), for which no CT absorption band was observed. A long-lived triplet state was observed (lifetime τT = 182 µs) with nanosecond transient absorption spectroscopy, and the singlet oxygen quantum yield (ΦΔ = 76%) is higher than that of the previously reported analogue dyad PMI-PTZ (ΦΔ = 57%). Ultrafast charge separation (ca. 0.14 ps) and slow charge recombination (1.4 ns) were observed with femtosecond transient absorption spectroscopy. With time-resolved electron paramagnetic resonance spectroscopy (TREPR), we confirmed the SOCT-ISC mechanism, and the electron spin polarization phase pattern of the triplet-state TREPR spectrum is (e, e, a, e, a, a), which is dramatically different from that of PMI-PTZ (a, e, a, e, a, e), indicating that the triplet-state TREPR spectrum of a specific chromophore in the electron donor-acceptor dyads is not only dependent on the geometry of the dyads but also dependent on the structure of the electron donor (or acceptor). Even one-atom variation in the donor structure may cause significant influence on the electron spin selectivity of the ISC of the electron donor-acceptor dyads.

Ultrafast Study of Exciton Transfer in Sb(III)-Doped Two-Dimensional [NH3(CH2)4NH3]CdBr4 Perovskite.

Antimony-based metal halide hybrids have attracted enormous attention due to the stereoactive 5s2 electron pair that drives intense triplet broadband emission. However, energy/charge transfer has been rarely achieved for Sb3+-doped materials. Herein, Sb3+ ions are homogeneously doped into 2D [NH3(CH2)4NH3]CdBr4 perovskite (Cd-PVK) using a wet-chemical method. Compared to the weak singlet exciton emission of Cd-PVK at 380 nm, 0.01% Sb3+-doped Cd-PVK exhibits intense triplet emission located at 640 nm with a near-unity quantum yield. Further increasing the doping concentration of Sb3+ completely quenches singlet exciton emission of Cd-PVK, concurrently with enhanced Sb3+ triplet emission. Delayed luminescence and femtosecond-transient absorption studies suggest that Sb3+ emission originates from exciton transfer (ET) from Cd-PVK host to Sb3+ dopant, while such ET cannot occur with Pb2+-doped Cd-PVK because of the mismatch of energy levels. In addition, density function theory calculations indicate that the introduced Sb3+ likely replace the Cd2+ ions along with the deprotonation of butanediammonium for charge balance, instead of generating Cd2+ vacancies. This work provides a deeper understanding of the ET of Sb3+-doped Cd-PVK and suggests an effective strategy to achieve efficient triplet Sb3+ emission beyond 0D Cl-based hybrids.

Charge separation, charge recombination and intersystem crossing in orthogonal naphthalimide-perylene electron donor/acceptor dyad.

We prepared an orthogonal electron donor/acceptor dyad (NI-Py) with perylene (Py) as electron donor and 4-aminonaphthalimide (NI) as an electron acceptor. The molecule adopts orthogonal geometry due to the steric hindrance exerted by the 4-amino substituents on the NI moiety. The photophysical properties of dyad were studied by steady-state UV-Vis absorption and fluorescence spectroscopies, femtosecond/nanosecond transient absorption spectroscopies and DFT computations. Ground state interaction between the NI and Py units is negligible; however, charge separation occurs upon photoexcitation, indicated by the quenching of the fluorescence of the dyad in polar solvents, i.e. fluorescence quantum yield (ΦF) is 61.9% in toluene and ΦF = 0.2% in methanol. Spin-orbit-coupled charge transfer-induced intersystem crossing (SOCT-ISC) was confirmed by femtosecond transient absorption spectroscopy (charge separation takes 1.7 ps and charge recombination takes 6.9 ns, in CH2Cl2). Nanosecond transient absorption spectra indicated the formation of perylene-localized triplet state, and the triplet state lifetime (175 µs) is much longer than that accessed with the heavy atom effect (3-bromoperylene; 16 µs). The singlet oxygen quantum (ΦΔ) yield of the dyad is 2.2% in hexane and 9.5% in dichloromethane. The low SOCT-ISC efficiency as compared to the previously reported analogue (ΦΔ = 80%) is attributed to the mismatch of the 1CT/Tn state energies, and/or the orientation of the NI and Py units, i.e. orthogonal geometry is not sufficient for achieving efficient SOCT-ISC in compact electron donor/acceptor dyads.

Unprecedentedly Ultrafast Dynamics of Excited States of C═C Photoswitching Molecules in Nanocrystals and Microcrystals.

The C═C photoswitching molecules [1,2-di(4-pyridyl)ethylene (DPE), 4-styrylpyridine (SP), and trans-1,2-stilbene (TS)] show favorable photoisomerization characteristics. Although the solid states of photoswitching molecules are usually used in optical devices, their excited state's evolution has been little explored. Here, the excited state's relaxation of DPE, SP, and TS in nanocrystal/microcrystal suspensions as well as in solution phase was studied to uncover the early events of their excited states. The dynamics of nanocrystal/microcrystal suspensions was tremendously accelerated in comparison to the kinetics obtained in the solution for these molecules under excitation. DPE exhibits the slowest decay rate, while SP shows the fastest decay rate in nanocrystal suspensions or solution, suggesting SP may be the best candidate for the photoswitching device. The intermolecular interactions and space restriction of the crystal lead to the acceleration of the excited state's evolution for DPE, SP, and TS. This provides new insight into the design of optical materials.

The effect of one-atom substitution on the photophysical properties and electron spin polarization: Intersystem crossing of compact orthogonal perylene/phenoxazine electron donor/acceptor dyad.

A perylene (Pery)-phenoxazine (PXZ) compact orthogonal electron donor/acceptor dyad was prepared to study the relationship between the molecular structures and the spin-orbit charge transfer intersystem crossing (SOCT-ISC), as well as the electron spin selectivity of the ISC process. The geometry of Pery-PXZ (80.0°) is different from the previously reported perylene-phenothiazine dyad (Pery-PTZ, 91.5°), although there is only one atom variation for the two dyads. Pery-PXZ shows a high singlet oxygen quantum yield (84%). Femtosecond transient absorption spectra indicate that the charge separation (CS, faster than 120 fs) is faster than the Pery-PTZ analog (CS, 250 fs) and charge recombination (CR, i.e., SOCT-ISC, 5.98 ns) of Pery-PXZ is slower than the Pery-PTZ analog (CR, 0.9 ns). The intrinsic triplet state lifetime of Pery-PXZ is 242 µs vs the lifetime of 181 µs for the Pery-PTZ analog. Moreover, the triplet state lifetime of Pery-PXZ in the solid polymer matrix is extended to 4.45 ms, which indicates that the triplet state of Pery-PXZ in fluid solution is deactivated not only by the triplet-triplet annihilation effect but also by other factors such as vibration coupled relaxation. Interestingly, with pulsed laser excited time-resolved electron paramagnetic resonance spectroscopy, the electron spin polarization (ESP) pattern of the triplet state of the current dyad is opposite to that of Pery-PTZ. These results demonstrated the rich electron spin chemistry of the ISC of compact electron donor/acceptor dyads, e.g., the ESP is dependent on not only the molecular geometry but also the structure of the electron donor (or acceptor).

Defect-Related Broadband Emission in Two-Dimensional Lead Bromide Perovskite Microsheets.

Low-dimensional hybrid lead halide perovskites (LHPs) with broadband emission (BE) have been developed as promising candidates for single-source white-light-emitting diodes. However, the underlying origin of such BE is poorly understood. Herein, dual-emissive [NH3(CH2)8NH3]PbBr4 perovskite microsheets (PMSs) with good dispersibility are successfully prepared. Besides the general narrowband emission (NE) originating from free excitons, BE (∼522 nm) is generated under a Br-poor condition, which is not observed in the single-crystal sample. Unlike self-trapped exciton emission, the BE observed in PMSs is experimentally determined to be related to bromide vacancies (VBr), thereby exhibiting quasisaturation under high excitation intensity. Femtosecond transient absorption spectroscopy first shows that the trapping time of the photogenerated electrons by acceptor-like VBr- is ∼15 ps, slower than that by surface defects (<1 ps). This study provides new insight into the underlying mechanism of BE and an effective approach to manipulating the optical properties of 2D perovskites.

Revealing Ultrafast Energy Dissipation Pathway of Nanocrystalline Sunscreens Oxybenzone and Dioxybenzone.

Two widely used ultraviolet filters, oxybenzone and dioxybenzone, are applied in a variety of areas, particularly in sunscreen cosmetics. Ultrafast femtosecond transient absorption is utilized to trace the excited states and transient states of the nanocrystalline suspension and solution phase of these two molecules. The analysis reveals the intriguing discovery that the transient species of the oxybenzone nanocrystalline suspension have shorter lifetimes than that in solution. The energy dissipation mechanism of these molecules is simulated by density functional theory calculations, and the potential energy surface calculations and the single-crystal structure can well explain the fast decay dynamics of the nanocrystalline transient states of these two molecules.

A bifunctional metal organic framework of type Fe(III)-BTC for cascade (enzymatic and enzyme-mimicking) colorimetric determination of glucose.

A metal organic framework (MOF) of type Fe(III)-BTC (where BTC is 1,3,5-benzenetricarboxylic acid) was utilized to construct an integrated system for cascade colorimetric determination of glucose. The MOF performs a dual function in acting (a) as a peroxidase (POx) mimic, and (b) as a solid support for immobilization of glucose oxidase (GOx). The MOF was prepared by a one-pot method. Glucose is consumed while H2O2 is produced during the enzymatic oxidation by GOx. In the presence of H2O2, the POx mimic catalytically oxidizes 3,3',5,5'-tetramethylbenzidine (TMB) to form a blue-green product. The absorbance of oxidized TMB (measured at 652 nm) increases linearly in the 5.0-100 µM glucose concentration range, and the detection limit is 2.4 µM. The GOx@Fe-BTC MOF was successfully applied to the determination of glucose in serum. Graphical abstract Schematic presentation of a bifunctional metal organic framework of type Fe-BTC for cascade (enzymatic and enzyme-mimicking) colorimetric determination of glucose. The Fe-BTC performs a dual function in acting as both a peroxidase mimic and support for immobilizing glucose oxidase. Using the integrated enzyme, a colorimetric method was successfully applied to one-step detection of glucose in human serum.