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We performed QM/MM simulations to investigate excess-electron attachment to four aqueous DNA nucleotide anions (dRT-). The negative QM/MM vertical electron affinities (-0.86 to -0.59 eV) reveal that aqueous dRT- anions improbably capture the excess electron near 0 eV. Comparing with the calculations in the gas phase and without the background charges, it can be found that first-shell water molecules have a larger contribution to the promotion of the ability of the excess-electron capture and the bulk-water polarization has a small effect on vertical electron affinities. The phosphate group hampers the attachment of the very low-energy excess electron to aqueous dRT-. The large adiabatic electron affinities (1.45-1.96 eV) and vertical detachment energies (1.92-2.44 eV) reveal that stable dRT2- dianions could be formed after dRT- anions catch the higher-energy excess electron (>0.59 eV). We computed the energy changes in the dRT2- structural relaxations. The QM-region conformational changes cause small energy alterations (-0.28 to 0.35 eV). The QM/MM energy decreases are 2.31-2.73 eV which mainly come from QM computations (3.49-4.00 eV) embedded in the background charges. The analysis of excess-electron distributions indicates that the polarization of bulk water and structural relaxations of dianions induce the excess-electron redistributions in the QM region and produce large QM-energy decreases. The MM energy changes are -1.27 to -1.11 eV for four aqueous dianions. The negative values demonstrate that the energy of the MM region would increase in dRT2- structural relaxations. In contrast with the values of the polarized QM computations, about 30% of the energy released by the QM region is transferred to bulk water in the MM region. The large energy dissipation probably suppresses DNA damage by the low-energy electron.
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Nucleotídeos , Água , Água/química , Elétrons , DNA/química , Transferência de EnergiaRESUMO
Self-referencing optical thermometry based on the fluorescence intensity ratio (FIR) have drawn extensive attention as a result of their high sensitivity and non-invasively fast response to temperature. However, it is a great challenge for luminescent materials to achieve simultaneously high absolute and relative temperature sensitivity based on the FIR technique. Herein, we developed a novel optical thermometer by designing hybrid lead-free metal halide (TTPhP)2MnCl4:Sb3+ (TTPhP+ = tetraphenylphosphonium cation) single crystals with multimodal photoluminescence (PL). The large TTPhP+ organic chain resulted in isolated [MnCl4]2- and [SbCl5]2- in the single crystal, which leads to a negligible energy trasfer process within them. Therefore, the two PL bands (band 1 from [MnCl4]2-) with a peak at 518 nm and band 2 (from [SbCl5]2) with a peak at 640 nm exhibit different thermal-quenching effects, which resulted in excellent temperature sensitivity, with the maximum absolute and relative sensitivities reaching 0.236 K-1 and 3.77% K-1 in a temperature range from 300 to 400 K. Both the absolute and relative sensitivities are among the highest values for luminescence thermometry.
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The prominent thermal quenching (TQ) effect of organic-inorganic metal halides limits their applications for lighting and imaging. Herein, we report an organo-metal halide scintillator (TTPhP)2MnCl4 (TTPhP+ = tetraphenylphosphonium cation), which exhibits a weak TQ effect up to 200 °C under ultraviolet-visible light (efficiency loss of 5.5%) and X-ray radiation (efficiency loss of 37%). The light yield of the (TTPhP)2MnCl4 scintillator (37â¯000 photons MeV-1 at 200 °C) under X-ray radiation is >2 times that of the commercial scintillator LuAG:Ce (15â¯000 photons MeV-1 at 200 °C). The microscopic mechanism of the weak TQ effect is demonstrated to be the scintillator having the ability to compensate for the emission losses from trapped charges and the large Mn-Mn distance (10.233 Å) suppressing nonradiative recombination at high temperatures. We further demonstrate the applications of (TTPhP)2MnCl4 as high-power white-light-emitting diodes operated at currents of ≤300 mA and X-ray imaging at 200 °C with a high spatial resolution.
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Crystal facet engineering has been recognized as a powerful strategy to finely modulate the charge separation behavior in semiconductor photocatalysis; however, disclosing the intrinsic roles that the morphologies and crystal facets play on photogenerated charge separation of semiconductor nanocrystals remains elusive. Herein, exemplified on the typical visible-light-responsive photocatalyst bismuth vanadate (BiVO4 ), for the first time, the successful fabrication is reported of well-defined BiVO4 square nanocrystals with precisely controllable (040)/(200) facet proportion, which undergo a dissolution-recrystallization-facet growth process accompanied with tetragonal to monoclinic phase transition. Spatial separation of photogenerated electrons and holes has been evidently demonstrated to take place between (040) and (200) facets of BiVO4 nanocrystals, on which the charge separation efficiency is verified to definitely depend on the facet proportion of (040)/(200). Further theoretical simulation reveals that the matching degree of charge collection length and crystal configuration is considered to be the major factor determining charge separation efficiency of BiVO4 nanocrystals. This study presents a strategy to fabricate morphology-tailored semiconductors, which will be favorable to advance the understanding of spatial charge separation in semiconductor photocatalysis.
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Aggregation-induced enhanced emission (AIEE) molecules have significant applications in optoelectronics, biomedical probes and chemical sensors, and large amounts of AIEE molecules have been reported since the concept of AIEE was proposed. Most aromatic AIEE molecules have complex structures consisting of multiple aromatic rings and/or polycyclic skeletons. In this study, we find that 2-aminophenylboronic acid (2-APBA) with a simple structure is highly emissive in the solid state. Further studies reveal that 2-APBA exists in a dimeric form, and the 2-APBA dimer is a novel AIEE molecule. The underlying AIEE mechanism is that the 2-APBA dimeric units aggregate through intermolecular interactions to produce highly ordered molecular packing without the presence of π-π stacking interactions that would lead to aggregation-caused quenching. Furthermore, the 2-APBA dimer aggregates could reversibly transform into its non-fluorescent monomer form driven by new kinds of dynamic covalent B-N and B-O bonds, illustrating its good potential in molecular recognition, nanogating, chemo/bio-sensing and controlled drug release.
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In the present contribution we carried out a TDDFT and femtosecond transient absorption study of the excited state dynamics of TNT in DMSO solvent. Vertical excitation and excited state relaxation were calculated at the SMD/M06-2X/TZVP level of theory. The electron absorption spectrum for the DMSO solvated TNT was calculated and compared with the experimental results. The results of the electronic excitation energies and the spin-orbital constants imply an intersystem crossing for the S1-T2 transition. The femtosecond time-resolved transient absorption measurements of the TNT in DMSO show the presence of two absorption signals around 650 nm and 540 nm, which are assigned to the population in the lowest singlet and triplet excited states, S1 and T1, respectively. The fast decay of the S1 state population is assigned to an efficient S1-T2 intersystem crossing, which soon internally converts to the T1 state. The slow decay of the T1 population is attributed to the nonradiative transition to the S0 state. The combined theoretical and experimental results present a mechanistic view of the photophysical dynamics of TNT in DMSO solution.
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Lead-free halide perovskites have triggered interest in the field of optoelectronics and photocatalysis because of their low toxicity, and tunable optical and charge-carrier properties. From an application point of view, it is desirable to develop stable multifunctional lead-free halide perovskites. We have developed a series of Cs2 Ptx Sn1-x Cl6 perovskites (0≤x≤1) with high stability, which show switchable photoluminescence and photocatalytic functions by varying the amount of Pt4+ substitution. A Cs2 Ptx Sn1-x Cl6 solid solution with a dominant proportion of Pt4+ shows broadband photoluminescence with a lifetime on the microsecond timescale. A Cs2 Ptx Sn1-x Cl6 solid solution with a small amount of Pt4+ substitution exhibits photocatalytic hydrogen evolution activity. An optical spectroscopy study reveals that the switch between photoluminescence and photocatalysis functions is controlled by sub-band gap states. Our finding provides a new way to develop lead-free multifunctional halide perovskites with high stability.
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All-inorganic zero-dimensional (0D) metal halides have recently received increasing attention due to their excellent photoluminescence (PL) performance and high stability. Herein, we present the successful doping of copper(I) into 0D Cs2 ZnBr4 . The incorporating of Cu+ cations enables the originally weakly luminescent Cs2 ZnBr4 to exhibit an efficient blue emission centered at around 465â nm, with a high photoluminescence quantum yield (PLQY) of 65.3 %. Detailed spectral characterizations, including ultrafast transient absorption (TA) techniques, were carried out to investigate the effect of Cu+ dopants and the origin of blue emission in Cs2 ZnBr4 :Cu. To further study the role of the A-site cation and halogen, A2 ZnCl4 :Cu (A=Cs, Rb) were also synthesized and found to generate intense sky-blue emission (PLQY≈73.1 %). This work represents an effective strategy for the development of environmentally friendly, low-cost and high-efficiency blue-emitting 0D all-inorganic metal halides.
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Lead-free halide double perovskites (DPs) have attracted great attention due to their stability, nontoxicity and good photophysical property. In this work, we report a new, small-bandgap Cs2CuSbCl6 DP nanocrystals (NCs) with a bandgap of 1.66 eV, which is the smallest bandgap in reported lead-free three-dimensional DP NCs. Density functional theory calculations confirm that Cs2CuSbCl6 DP has an indirect bandgap of 1.70 eV, in good agreement with the experimental result. The photophysical property of Cs2CuSbCl6 NCs is studied by the combination of femtosecond transient absorption (TA) and nanosecond TA techniques. In addition, the Cs2CuSbCl6 NCs exhibit good stability exposed in the air. These results show that these NCs will have great potential to be used as a light-absorbing material for photovoltaic applications.
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It is a challenge to rationally design an organic molecule with thermally activated delayed fluorescence (TADF) due to the intrinsically spin-forbidden transition. Meanwhile, those reported TADF organic molecules have difficulty to be directly applied in the field of biological and medical imaging because they usually have no water solubility. Here, a water-soluble TADF organic molecule DCF-BXJ was developed by introducing a flexible propenyl group into the commercial traditional fluorophore DCF (2,7-dichlorofluorescein). The flexible group provides nonradiative rotational motion, which causes an efficient energy level cross between the S1 state and the T2 state of DCF-BXJ. Results of transient absorption spectra and theoretical calculations supported that nonradiative rotational motion of the flexible group can enhance intersystem crossing (ISC) and bring out TADF. This work provides a new mechanism explanation for TADF existing in organic molecules.
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Glutathione S-transferases (GSTs), detoxification enzymes that catalyze the addition of glutathione (GSH) to diverse electrophilic molecules, are often overexpressed in various tumor cells. While fluorescent probes for GSTs have often adopted the 2,4-dinitrobenzenesulfonyl (DNs) group as the receptor unit, they usually suffer from considerable background reaction noise with GSH due to excessive electron deficiency. However, weakening this reactivity is generally accompanied by loss of sensitivity for GSTs, and therefore, finely turning down the reactivity while maintaining certain sensitivity is critical for developing a practical probe. Here, we report a rational semiquantitative strategy for designing such a practical two-photon probe by introducing a parameter adopted from the conceptual density functional theory (CDFT), the local electrophilicity ω k , to characterize this reactivity. As expected, kinetic studies established ω k as efficient to predict the reactivity with GSH, and probe NI3 showing the best performance was successfully applied to detecting GST activities in live cells and tissue sections with high sensitivity and signal-to-noise ratio. Photoinduced electron transfer of naphthalimide-based probes, captured by femtosecond transient absorption for the first time and unraveled by theoretical calculations, also contributes to the negligible background noise.
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Zero-dimensional (0D) lead-free perovskites have unique structures and optoelectronic properties. Undoped and Sb-doped all inorganic, lead-free, 0D perovskite single crystals A2 InCl5 (H2 O) (A=Rb, Cs) are presented that exhibit greatly enhanced yellow emission. To study the effect of coordination H2 O, Sb-doped A3 InCl6 (A=Rb, Cs) are also synthesized and further studied. The photoluminescence (PL) color changes from yellow to green emission. Interestingly, the photoluminescence quantum yield (PLQY) realizes a great boost from <2 % to 85-95 % through doping Sb3+ . We further explore the effect of Sb3+ dopants and the origin of bright emission by ultrafast transient absorption techniques. Furthermore, Sb-doped 0D rubidium indium chloride perovskites show excellent stability. These findings not only provide a way to design a set of new high-performance 0D lead-free perovskites, but also reveal the relationship between structure and PL properties.
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Lead-free halide perovskite nanocrystals (NCs) have recently attracted attention due to their nontoxicity and stability as alternatives to lead-based perovskite NCs. Here, we report undoped and manganese-doped all-inorganic, lead-free double perovskite (DP) NCs: Cs2NaIn x Bi1-x Cl6 (0 < x < 1) and Cs2NaIn x Bi1-x Cl6:Mn (0 ≤ x ≤ 1) NCs. Undoped NCs exhibit blue emission. Through doping Mn2+ ions into Cs2NaIn x Bi1-x Cl6 NCs, we can avoid self-trapped exciton emission and realize bright orange red emission of Mn2+ dopants with the highest photoluminescence quantum efficiency of 44.6%. The photoluminescence (PL) is tunable from yellow emission to orange-red emission corresponding to a red shift from 583 to 614 nm with increasing In content. Interestingly, the PL emission of Mn-doped NCs shows a red shift from the bulk size to the nanoscale. The Mn-doped NCs show good stability in air. In addition, we further prove the process of dark self-trapped state-assisted Mn2+ emission in DP NCs by ultrafast transient absorption techniques.
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The initial yield of a hydrated electron (eaq-) in a solution under laser pulse irradiation was investigated by pump-probe transient absorption spectroscopy. The initial quantum yield of eaq- varies with the concentration of uridine monophosphate (UMP). The variation of the concentration of eaq- is often used to study the prehydrated electron (epre-) and eaq- attachment to UMP. The results of 320 and 260 nm excitations were compared. It was found that with the increase of UMP concentration, the initial yield of eaq- increases at 320 nm excitation, but decreases at 260 nm excitation. The further analysis indicates that some of the epre- attachments to UMP before solvation at 260 nm excitation result in the decrease of the eaq- yield. In addition, the absorption of UMP to 260 nm also causes the decrease of the eaq- yield. After the excitation at 320 nm, the phosphate group of UMP can release electrons more easily than that of water molecules by two-photon absorption, and therefore the eaq- yield increases. With the increase of UMP concentration, the decay rate of eaq- increases because eaq- is captured by UMP. The change of excitation photon does not affect the reaction rate of eaq- attachment to UMP. The longer lifetime of eaq- obtained at 260 nm excitation than 320 nm excitation is induced by the larger eaq- escape probability at 260 nm excitation. Our results show that the femtosecond pulse pump-probe transient absorption spectroscopy method should be cautiously used because of its complexity in studying the epre- attachment to nucleotides in an aqueous solution.
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Elétrons , Uridina Monofosfato , Nucleotídeos , Análise Espectral , ÁguaRESUMO
Carrier multiplication (CM) is an effective mechanism that makes it possible to use hot carriers (HCs) to bypass the Shockley-Queisser limit for solar-cell efficiency. In this paper, we present a detailed study of both CM and HC cooling dynamics in quantum-confined CsPbI3 perovskite nanocrystals (NCs), using femtosecond transient absorption spectroscopy. Our results show that barrierless CM, with an efficiency exceeding 90%, can be achieved in strongly confined NCs on a time scale of âª200 fs. A low CM efficiency (â¼40%), however, is observed in weakly confined NCs. HC cooling dynamics suggests the absence of an intrinsic phonon bottleneck in strongly confined NCs. Furthermore, the biexciton Auger rate increased 4-fold in strongly confined NCs compared to that in weakly confined NCs. These results suggest that the enhanced CM in strongly confined NCs likely originates from enhanced Coulomb coupling and relaxed momentum conservation.
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Intrinsic broadband photoluminescence (PL) of self-trapped excitons (STEs) are systematically studied in lead-free double perovskite nanocrystals (NCs). It is clarified that bandgap (direct/indirect) has important influence on the PL properties of STEs: indirect bandgap NCs exhibit strong exciton-phonon coupling which results in non-radiative STEs, while direct bandgap NCs exhibit moderate exciton-phonon coupling, inducing bright STE PL. Furthermore, by alloying K+ and Li+ ions in Cs2AgInCl6 NCs, the NCs exhibit broadband white-light emission. Charge-carrier dynamics study indicates that the efficient white-light emission originates from the further suppressed non-radiative processes of the STEs in the direct bandgap structure. This work may deepen the understanding of STEs and guide the design of high-performance lead-free perovskites.
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The applications of most fluorescent probes available for Glutathione S-Transferases (GSTs), including NI3 which we developed recently based on 1,8-naphthalimide (NI), are limited by their short emission wavelengths due to insufficient penetration. To realize imaging at a deeper depth, near-infrared (NIR) fluorescent probes are required. Here we report for the first time the designing of NIR fluorescent probes for GSTs by employing the NIR fluorophore HCy which possesses a higher brightness, hydrophilicity and electron-deficiency relative to NI. Intriguingly, with the same receptor unit, the HCy-based probe is always more reactive towards glutathione than the NI-based one, regardless of the specific chemical structure of the receptor unit. This was proved to result from the higher electron-deficiency of HCy instead of its higher hydrophilicity based on a comprehensive analysis. Further, with caging of the autofluorescence being crucial and more difficult to achieve via photoinduced electron transfer (PET) for a NIR probe, the quenching mechanism of HCy-based probes was proved to be PET for the first time with femtosecond transient absorption and theoretical calculations. Thus, HCy2 and HCy9, which employ receptor units less reactive than the one adopted in NI3, turned out to be the most appropriate NIR probes with high-sensitivity and little nonenzymatic background noise. They were then successfully applied to detecting GST in cells, tissues and tumor xenografts in vivo. Additionally, unlike HCy2 with a broad isoenzyme selectivity, HCy9 is specific for GSTA1-1, which is attributed to its lower reactivity and the higher effectiveness of GSTA1-1 in stabilizing the active intermediate via H-bonds based on docking simulations.
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Lead-free halide perovskite nanocrystals (NCs) have drawn wide attention for solving the problem of lead perovskites toxicity and instability. Herein, we synthesize the direct band gap double perovskites undoped and Ag-doped Cs2 NaInCl6 NCs by variable temperature hot injection. The Cs2 NaInCl6 NCs have little photoluminescence because of dark self-trapped excitons (STEs). The dark STEs can be converted into bright STEs by doping with Ag+ to produce a bright yellow emission, with the highest photoluminescence quantum efficiency of 31.1 %. The dark STEs has been directly detected experimentally by ultrafast transient absorption (TA) techniques. The dynamics mechanism is further studied. In addition, the Ag-doped NCs show better stability than the undoped ones. This result provides a new way to enhance the optical properties of lead-free perovskites NCs for high-performance light emitters.
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Low-dimensional metal halides have recently attracted extensive attention owing to their unique structure and photoelectric properties. Herein, we report the colloidal synthesis of all-inorganic low-dimensional cesium copper halide nanocrystals (NCs) by adopting a hot-injection approach. Using the same reactants and ligands, but different reaction temperatures, both 1D CsCu2 I3 nanorods and 0D Cs3 Cu2 I5 NCs can be prepared. Density functional theory indicates that the reduced dimensionality in 1D CsCu2 I3 compared to 0D Cs3 Cu2 I5 makes the excitons more localized, which accounts for the strong emission of 0D Cs3 Cu2 I5 NCs. Subsequent optical characterization reveals that the highly luminescent, strongly Stokes-shifted broadband emission of 0D Cs3 Cu2 I5 NCs arises from the self-trapped excitons. Our findings not only present a method to control the synthesis of low-dimensional cesium copper halide nanocrystals but also highlight the potential of 0D Cs3 Cu2 I5 NCs in optoelectronics.
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An ultraviolet energy dissipation mechanism plays a critical role in the photoprotection effect of sunscreens. In this work, we discovered substitution dependent UV energy dissipation mechanisms of model plant sunscreen methyl sinapate (MS). We found that the initially populated V(ππ*) states of MS and p-OMeMS relax to the ground state nonradiatively along an ultrafast trans-cis photoisomerization in tens of picoseconds. However, for p-HMS, an internal conversion from V(ππ*) to a relative dark V'(ππ*) state occurs in less than 1 ps, leading to a branching of the excited-state relaxations. The V (ππ*) state still relaxes nonradiatively as in the case of MS and p-OMeMS. In contrast, the V'(ππ*) state decays to the ground state mainly by emitting photons, exhibiting a lifetime as long as 5 ns. It is the first time to definitely distinguish the dynamics between V(ππ*) and V'(ππ*) states in the study of sinapates and cinnamates. These results indicate the anticipation of the V'(ππ*) state should be avoided when designing sunscreens.