Origin of the low-energy tail in the photoluminescence spectrum of CsPbBr3 nanoplatelets: a femtosecond transient absorption spectroscopic study.

CsPbBr3 nanoplatelets (NPLs), as some of the two-dimensional lead halide perovskites, have been intensively investigated due to their outstanding photophysical and photoelectric properties. However, there remain unclear fundamental issues on their carrier kinetics and the low-energy tail in their photoluminescence (PL) spectrum. In this paper, we synthesized CsPbBr3 NPLs with five [PbBr6]4- monolayers and performed comprehensive studies by using steady-state absorption, PL, and femtosecond transient absorption (fs-TA) spectroscopic measurements. We determined both the biexciton Auger recombination time (7 ± 2 ps) and trapped exciton lifetime (110 ± 15 ps) of the five monolayer CsPbBr3 NPLs. We also investigated the origin of the low-energy tail emission in their PL spectrum. More importantly, we found that a negative ΔA feature in the energy range of 2.45-2.55 eV appears in their fs-TA spectrum at 2, 4 and 10 ps delay times, which could help them act as a laser gain medium. The low-energy tail emission in their PL spectrum overlaps well with the negative ΔA feature in the energy range of 2.45-2.55 eV in their fs-TA spectrum at 2, 4 and 10 ps delay times.

Unravelling the doping effect of potassium ions on structural modulation and photocatalytic activity of graphitic carbon nitride.

Graphitic carbon nitride (GCN), as a promising photocatalyst, has been intensely investigated in the photocatalytic fields, but its performance is still unsatisfactory. To date, metal ion doping has been proven to be an effective modification method to improve the photocatalytic activity of GCN. More importantly, comprehensive understanding of the doping mechanism will be of benefit to synthesize efficient GCN based photocatalysts. In this work, K+-doped GCN samples were prepared via heating the mixture of the preheated melamine and a certain amount of KCl at different synthetic temperatures. XRD and Raman characterization studies indicated that the introduction of K+ could improve its crystallinity at higher temperature but reduce its crystallinity at lower temperature. Moreover, FTIR and SEM-EDS measurements implied that K+ are found dominantly in the surface of the ion-doped sample prepared at lower temperature, while they are found both in the surface and bulk of the ion-doped sample prepared at higher temperature. These observations revealed that K+ distributed in the surface of the ion-doped GCN could inhibit its crystal growth, while K+ distributed inside of the ion-doped GCN could promote its crystallinity. Owing to the greater inducing effect of the bulk K+ than the disturbing effect of the surface K+, the improvement of the crystallinity for K+-doped GCN was achieved. As a result, the K+-doped GCN with higher crystallinity yielded an obviously higher H2 evolution rate than that with lower crystallinity under visible light irradiation (>420 nm). Besides, it was observed that the K+-doped GCN prepared at higher temperature exhibits significantly greater adsorption capacity for methylene blue than the K+-doped GCN prepared at lower temperature. This work would provide an insight into optimizing metal ion doped GCN with high photocatalytic activity.

Electrostatic interaction mechanism of visible light absorption broadening in ion-doped graphitic carbon nitride.

Broadening the light response of graphitic carbon nitride (CN) is helpful to improve its solar energy utilization efficiency in photocatalytic reaction. In this work, a facile synthesis method was developed via the treatment of potassium-doped CN (CN-K) with H2O2 in isopropanol solvent. Various characterizations indicate the basic structure of CN-K treated with H2O2 (CN-K-OOH) resembles that of CN-K, while it presents light absorption up to 650 nm. A series of control experiments and TGA-MS measurements suggest the weak electrostatic attraction between potassium ions and hydroperoxyl groups inside CN-K-OOH is responsible for its enhanced visible light absorption. As a consequence, compared to pristine CN, the photodegradation organic pollutant ability of CN-K-OOH is obviously improved under visible light irradiation (>470 nm). The current synthesis strategy might be universal and it could be applied to other cations.

A comparison study of sodium ion- and potassium ion-modified graphitic carbon nitride for photocatalytic hydrogen evolution.

It is well known that modifying graphitic carbon nitride (GCN) is an imperative strategy to improve its photocatalytic activity. In this study, Na-doped and K-doped graphitic carbon nitride (GCN-Na and GCN-K) were prepared via the simple thermal polymerization of a mixture of melamine and NaCl or KCl, respectively. The structure characterization showed that both Na+ and K+ intercalation could reduce the interlayer distance of GCN and introduce cyano defects in GCN, while K+ apparently had a stronger influence on the structure variation of GCN. The chemical composition data showed that both Na+ and K+ could easily interact with GCN, while K-doping caused a greater change in the C/N ratio than Na-doping. Moreover, compared to GCN-Na-5 (5 represents weight ratio of alkali halide to melamine), the conduction and valence bands of GCN-K-5 both shifted upward based on the electronic and optical measurements. Consequently, GCN-K-5 yielded an H2 evolution rate around 4 times higher than that of GCN-Na-5 under visible light irradiation (>420 nm). The cation size effect on GCN was proposed to be mainly responsible for the variation in the structure, optical and electronic properties of ion-doped GCNs, and hence the enhanced photocatalytic H2 evolution. The current work can provide new insight into optimizing photocatalysts for enhanced photocatalytic performances.

Photon induced quantum yield regeneration of cap-exchanged CdSe/CdS quantum rods for ratiometric biosensing and cellular imaging.

Full water-dispersion of commercial hydrophobic CdSe/CdS core/shell quantum rods (QRs) was achieved by cap-exchange using a dihydrolipoic acid zwitterion ligand at a low ligand:QR molar ratio (LQMR) of 1000. However, this process almost completely quenched the QR fluorescence, greatly limiting its potential in downstream fluorescence based applications. Fortunately, we found that the QR fluorescence could be recovered by exposure to near ultra-violet to blue light radiation (e.g. 300-450 nm). These "reborn" QRs were found to be compact, bright, and stable, and were resistant to non-specific adsorption, which make them powerful fluorescent probes in broad biomedical applications. We demonstrated their potential in two model applications: first, the QRs were conjugated with His8-tagged small antibody mimetic proteins (also known as Affimers) for the sensitive detection of target proteins via a Förster resonance energy transfer (FRET) readout strategy and second, the QR surface was functionalized with biotins for targeted imaging of cancer cells.

Direct Observation of Surface Polarons in Capped CuInS2 Quantum Dots by Ultrafast Pump-Probe Spectroscopies.

Semiconductor nanocrystals are mostly prepared by colloid chemistry with organic surfactant molecules, and their surface polarization effect on the carrier relaxations are critical to their optoelectronic applications. Until now, the surface polarization effect and detailed photophysical processes of these capped quantum dots (QDs) are still unclear. Here, we studied the dynamics of the photoinduced carriers and capping molecule  vibrations of capped CuInS2 quantum dots by using the femtosecond pump-probe system in both visible and IR zones. It is identified that the capping  molecular vibrations exhibit significant Fermion bleaching nature, whose relaxation profile is in good agreement with the radiative recombination dynamics of QDs in the visible region. These results demonstrate that the extrinsic surface polarons form by the coupling of photoinduced carriers and surface ligand vibrations, and take part in the photophysical processes of these QDs. This finding is helpful for the QD design and applications in photoelectronic devices.

Ultrafast Excited-State Intermolecular Proton Transfer in Indigo Oligomer.

It has been a long-lasting debate whether indigo undergoes excited-state proton transfer and how this contributes to its photostability. A prevailing point of view is that a sub-picosecond excited-state intramolecular single proton transfer occurs; however, it has been studied mostly under dilute solution conditions. In this work, excited-state structural dynamics of indigo oligomers formed at millimolar concentration in dimethyl sulfoxide is investigated using femtosecond visible pump spectroscopy, infrared and visible probe spectroscopies, and steady-state infrared and fluorescence spectroscopies. Experimental evidence indicates the presence of transient intermolecular electronic excited-state proton transfer, which is supported by quantum-chemistry computations. The formed enol species disappears with a time constant of 200-300 fs, followed by a relatively slow nonradiative relaxation to the electronic ground state. Our results reveal new photochemistry of indigo particularly in its oligomeric state.

Photophysics and Photocatalysis of Melem: A Spectroscopic Reinvestigation.

Graphitic carbon nitride (g-CN) is one potential metal-free photocatalyst. The photocatalytic mechanism of g-CN is related to the heptazine ring building unit. Melem is the simplest heptazine-based compound and g-CN is its polymeric product. Thus, studies on the photophysical properties of melem will help to understand the photocatalytic mechanism of heptazine-based materials. Herein, the spectroscopic features of melem were systematically explored through measuring its absorption spectrum, fluorescence spectrum, and fluorescence decay. Both fluorescence spectroscopy and fluorescence decay measurements show that the condensation of melamine to melem causes stronger photoluminescence, whereas the condensation of melem to g-CN causes weaker photoluminescence. In addition, all observations reveal that a mixture of monomer melem and its higher condensates is more easily obtained during the preparation of melem, and that the higher condensates of melem affect the photophysical properties of melem dominantly. The photocatalytic hydrogen evolution of melem has also been measured and the monomer melem has negligible photoinduced water-splitting activity.

Dissecting Multivalent Lectin-Carbohydrate Recognition Using Polyvalent Multifunctional Glycan-Quantum Dots.

Multivalent protein-carbohydrate interactions initiate the first contacts between virus/bacteria and target cells, which ultimately lead to infection. Understanding the structures and binding modes involved is vital to the design of specific, potent multivalent inhibitors. However, the lack of structural information on such flexible, complex, and multimeric cell surface membrane proteins has often hampered such endeavors. Herein, we report that quantum dots (QDs) displayed with a dense array of mono-/disaccharides are powerful probes for multivalent protein-glycan interactions. Using a pair of closely related tetrameric lectins, DC-SIGN and DC-SIGNR, which bind to the HIV and Ebola virus glycoproteins (EBOV-GP) to augment viral entry and infect target cells, we show that such QDs efficiently dissect the different DC-SIGN/R-glycan binding modes (tetra-/di-/monovalent) through a combination of multimodal readouts: Förster resonance energy transfer (FRET), hydrodynamic size measurement, and transmission electron microscopy imaging. We also report a new QD-FRET method for quantifying QD-DC-SIGN/R binding affinity, revealing that DC-SIGN binds to the QD >100-fold tighter than does DC-SIGNR. This result is consistent with DC-SIGN's higher trans-infection efficiency of some HIV strains over DC-SIGNR. Finally, we show that the QDs potently inhibit DC-SIGN-mediated enhancement of EBOV-GP-driven transduction of target cells with IC50 values down to 0.7 nM, matching well to their DC-SIGN binding constant (apparent Kd = 0.6 nM) measured by FRET. These results suggest that the glycan-QDs are powerful multifunctional probes for dissecting multivalent protein-ligand recognition and predicting glyconanoparticle inhibition of virus infection at the cellular level.

Interaction between triethanolamine and singlet or triplet excited state of xanthene dyes in aqueous solution.

Triethanolamine (TEOA) has been often used as a hole-scavenger in dye-sensitized semiconductor photocatalytic systems. However, the femtosecond time-resolved kinetics of the interaction between a sensitized dye and TEOA has not been reported in literatures. Herein, we selected four commonly used xanthene dyes, such as fluorescein, dibromofluorescein, eosin Y, and erythrosine B, and studied their ultrafast fluorescence quenching dynamics in the presence of TEOA in aqueous solution, respectively, by using both femtosecond transient absorption and time-resolved fluorescence measurements. We obtained the electron transfer rate from TEOA to each photoexcited xanthene dye in 2.0 M TEOA solution. We also obtained the intersystem crossing rate of each xanthene dye in aqueous solution with fluorescence quantum yield and lifetime measurements. Finally we found that TEOA mainly interacts with the singlet excited-state of fluorescein, dibromofluorescein, and eosin Y, and that TEOA can interact with both the singlet and triplet excited-states of erythrosine B in high concentration of TEOA aqueous solution.

Charge carrier kinetics of carbon nitride colloid: a femtosecond transient absorption spectroscopy study.

Carbon nitrides (CN) have been widely used in photocatalytic applications. However, the charge carrier kinetics of CN after light excitation remains unclear. Herein, we prepared a stable and transparent CN colloid in an aqueous tetraethylammonium hydroxide solution and investigated its carrier kinetics using both femtosecond transient absorption and picosecond time-resolved fluorescence spectroscopy. We found that a new and positive absorption band appears in the femtosecond transient absorption spectrum of the CN colloid, which could be attributed to the absorption of the photogenerated electron/hole pairs (or the electronic excited state) of the CN colloid after light excitation. Moreover, we found that the charge carrier kinetics obtained from the femtosecond transient absorption measurements is dramatically different from that obtained from the picosecond time-resolved fluorescence measurements, indicating that the photophysical process of the CN colloid after light excitation is complicated. With the results obtained from both the femtosecond transient absorption and picosecond time-resolved fluorescence measurements, we proposed a schematic to understand the photophysics and charge carrier kinetics of the CN colloid. We believe that the current study is also significant for researchers to understand the photophysics and charge carrier kinetics of bulk CN.

Fluorescence quenching of coumarin 153 by hydroxyl-functionalized room temperature ionic liquids.

Steady-state absorption and fluorescence as well as time-resolved fluorescence of coumarin 151 (C151) and coumarin 153 (C153) were measured in hydroxyl-functionalized ionic liquids ([HOEmim][BF4] and [HOEmim][N(CN)2]) and in nonhydroxyl-functionalized ionic liquids ([Emim][BF4] and [Emim][N(CN)2]). Both the steady-state fluorescence and time-resolved fluorescence observations reveal that hydroxyl-functionalized ionic liquid quenches the fluorescence of C153 while the nonhydroxyl-functionalized ionic liquid does not. We also measured the time-resolved fluorescence anisotropy of C151 and C153 in both [HOEmim][BF4] and [Emim][BF4]. It is found that the ratio of the rotational relaxation lifetime of C153 in [HOEmim][BF4] with respect to that in [Emim][BF4] is about 15% larger than that of C151 in [HOEmim][BF4] with respect to that in [Emim][BF4], indicating extra interaction between C153 and [HOEmim][BF4] exists except the effect of the viscosity of ionic liquid.

Time-Resolved Study on Xanthene Dye-Sensitized Carbon Nitride Photocatalytic Systems.

Dye sensitization is a promising strategy to extend the visible light absorption of carbon nitride (C3N4) and increase the photocatalytic hydrogen evolution efficiency of C3N4 under visible light irradiation. However, the interaction dynamics between C3N4 and a sensitized dye has not been reported in the literature. Herein, we selected four commonly used xanthene dyes such as fluorescein, dibromofluorescein, eosin Y, and erythrosine B and prepared their corresponding dye-sensitized-C3N4 composites. For the first time, we derived the electron transfer rate from the LUMO of each photoexcited xanthene dye to the conduction band of C3N4 using picoesecond time-resolved fluorescence measurements. We also obtained the reduction potentials of all selected xanthene dyes and C3N4 with cyclic voltammetry measurements. The cyclic voltammetry measurements gave a consistent result with the picosecond time-resolved fluorescence measurements. Besides, the possibility of the selected xanthene dye as an acceptor for the hole of the photoexcited C3N4 was also discussed. We believe this study is significant for the researcher to understanding the fundamental aspects in the xanthene dye-sensitized-C3N4 photocatalytic systems.

A sensitive fluorescence anisotropy method for detection of lead (II) ion by a G-quadruplex-inducible DNA aptamer.

Sensitive and selective detection of Pb(2+) is of great importance to both human health and environmental protection. Here we propose a novel fluorescence anisotropy (FA) approach for sensing Pb(2+) in homogeneous solution by a G-rich thrombin binding aptamer (TBA). The TBA labeled with 6-carboxytetramethylrhodamine (TMR) at the seventh thymine nucleotide was used as a fluorescent probe for signaling Pb(2+). It was found that the aptamer probe had a high FA in the absence of Pb(2+). This is because the rotation of TMR is restricted by intramolecular interaction with the adjacent guanine bases, which results in photoinduced electron transfer (PET). When the aptamer probe binds to Pb(2+) to form G-quadruplex, the intramolecular interaction should be eliminated, resulting in faster rotation of the fluorophore TMR in solution. Therefore, FA of aptamer probe is expected to decrease significantly upon binding to Pb(2+). Indeed, we observed a decrease in FA of aptamer probe upon Pb(2+) binding. Circular dichroism, fluorescence spectra, and fluorescence lifetime measurement were used to verify the reliability and reasonability of the sensing mechanism. By monitoring the FA change of the aptamer probe, we were able to real-time detect binding between the TBA probe and Pb(2+). Moreover, the aptamer probe was exploited as a recognition element for quantification of Pb(2+) in homogeneous solution. The change in FA showed a linear response to Pb(2+) from 10 nM to 2.0 µM, with 1.0 nM limit of detection. In addition, this sensing system exhibited good selectivity for Pb(2+) over other metal ions. The method is simple, quick and inherits the advantages of aptamer and FA.

Ultrafast fluorescence quenching dynamics of Atto655 in the presence of N-acetyltyrosine and N-acetyltryptophan in aqueous solution: proton-coupled electron transfer versus electron transfer.

We studied the ultrafast fluorescence quenching dynamics of Atto655 in the presence of N-acetyltyrosine (AcTyr) and N-acetyltryptophan (AcTrp) in aqueous solution with femtosecond transient absorption spectroscopy. We found that the charge-transfer rate between Atto655 and AcTyr is about 240 times smaller than that between Atto655 and AcTrp. The pH value and D2O dependences of the excited-state decay kinetics of Atto655 in the presence of AcTyr and AcTrp reveal that the quenching of Atto655 fluorescence by AcTyr in aqueous solution is via a proton-coupled electron-transfer (PCET) process and that the quenching of Atto655 fluorescence by AcTrp in aqueous solution is via an electron-transfer process. With the version of the semiclassical Marcus ET theory, we derived that the electronic coupling constant for the PCET reaction between Atto655 and AcTyr in aqueous solution is 8.3 cm(-1), indicating that the PCET reaction between Atto655 and AcTyr in aqueous solution is nonadiabatic.

Specific and sensitive fluorescence anisotropy sensing of guanine-quadruplex structures via a photoinduced electron transfer mechanism.

Fluorescence anisotropy (FA) is a homogeneous, ratiometric, and real-time analytical technology. By selective labeling of a guanine (G)-quadruplex motif with tetramethylrhodamine (TMR), here, it is established that a large reduction in FA response can be specifically associated with the unfolding → folding transition of G-quadruplex structures. On the basis of fluorescence intensity, polarization and lifetime analysis, and molecular docking simulation, the mechanism was found to be that the labeled fluorophore (TMR) can intramolecularly interact with adjacent G bases in an unfolded G-quadruplex motif, which allows for the photoinduced electron transfer (PET) occurring between the fluorophore and G bases, leading to a short fluorescence lifetime. Upon the folding of the motif to form a stable G-quadruplex structure, the intramolecular interactions and the concomitant PET could be eliminated with an increased fluorescence lifetime, leading to a large reduction in the FA response. On the basis of this mechanism, a novel, specific, and sensitive FA approach was developed for the detection of biologically and functionally important G-quadruplex structures. The approach is examined and validated using one normal G-quadruplex motif, five mutants, and six small cations and is potentially applicable to the study of G-quadruplexes at single molecule level, ligand screening, profiling of highly ordered DNA nanostructures, and biosensing.

Structural heterogeneity in the collision complex between organic dyes and tryptophan in aqueous solution.

The heterogeneity on photoinduced electron transfer (PET) kinetics between a labeled fluorophore and an amino acid residue has been extensively studied in biopolymers. However in aqueous solutions, the heterogeneity on PET kinetics between a fluorophore and a quencher has rarely been reported. Herein, we selected four commonly used fluorophores, such as tetramethylrhodamine (TMR), Rhodamine B (RhB), Alexa fluor 546 (Alexa546), and Atto655, and studied their respective PET kinetics in 50 mM tryptophan solutions with femtosecond transient absorption spectroscopy to explore the structural heterogeneity in their corresponding collision complexes. We measured the decay of the first excited electronic state of respective fluorophore with and without 50 mM tryptophan in aqueous solutions, and derived the charge separation rate in their corresponding collision complexes. We found that the PET process of all selected fluorophores in 50 mM tryptophan solutions has two charge separation rates, which indicates that the relevant states in the collision complex between respective fluorophore and tryptophan have strong structural heterogeneity. These femtosecond PET measurements are in agreement with Vaiana's molecular dynamics simulation (J. Am. Chem. Soc.2003, 125, 14564). In addition, with the obtained PET kinetic parameters, we derived the relative brightness of the collision complex between respective fluorophore and tryptophan, which are important parameters for the PET based fluorescence correlation spectroscopy study involving these fluorophores in biopolymers.

Photophysics and locations of IR125 and C152 in AOT reverse micelles.

Many fluorescent chromophores have been employed to investigate the nature and dynamics of the water confined in reverse micelles (RMs). However, some questions remain as to the location of a probe in a RM and the diameter of the RM at which the physical characteristic of the water inside RMs becomes similar to that of bulk water. In this work, we systematically studied the photophysics of IR125 and C152 in AOT RMs at different w(0) by means of static absorption and fluorescence spectroscopy as well as time-resolved fluorescence spectroscopy. We obtained the absorption maxima, fluorescence emission maxima, fluorescence lifetime, and reorientation time of IR125 and C152 in AOT RMs at corresponding w(0). We found that all obtained photophysical parameters of IR125 and C152 in AOT RMs as a function of w(0) have a distinct changeover point around w(0) = 8, indicating that there is a dramatic change in the nature of the water confined in AOT RMs around w(0) = 8. The observed changeover point around w(0) = 8 is well in agreement with the Satpati's report (ChemPhysChem, 2009, 10, 2966). In addition, we observed that the measured reorientation time of IR125 in AOT RMs increases with the increase of w(0), which is opposite to the trend of change in the measured reorientation time of C152 in AOT RMs with the increase of w(0). We found that IR125 prefers to reside in the water pool of AOT RMs and that C152 prefers to reside in the outer side of the interfacial region or the nonpolar n-heptane phase of AOT RMs. Furthermore, we found that the time-resolved fluorescence anisotropy of IR125 in smaller w(0) AOT RMs primarily measures the reorientation of RMs and the time-resolved fluorescence anisotropy of IR125 in larger w(0) AOT RMs measures the reorientation of IR125 in the water pool confined in RMs. This work demonstrated that IR125 is an excellent probe to study the nature and dynamics of the water confined in AOT RMs.

Photophysical properties of Atto655 dye in the presence of guanosine and tryptophan in aqueous solution.

Atto655 has been widely used as an excellent probing dye through photoinduced electron transfer (PET) for biochemical processes in oligonucleotides or polypeptides. However, its photophysical properties in the presence of the quenchers guanosine and tryptophan have not been carefully studied. In this work, we investigated the dynamics of PET between Atto655 and the two quenchers in aqueous solution with femtosecond transient absorption experiments. We derived that the charge separation rate is 8.1 × 10(9) s(-1) and the charge recombination rate is 7.7 × 10(10) s(-1) for the collision complex between Atto655 and guanosine and that the corresponding values for the collision complex between Atto655 and tryptophan are 4.0 × 10(11) and 5.0 × 10(12) s(-1), respectively. These experimental results are quite consistent with the prediction of Marcus-type theory for electron transfer. The implications of this work for the data analysis of PET-based fluorescence correlation spectroscopy are discussed.

Ultrafast photoinduced electron transfer between tetramethylrhodamine and guanosine in aqueous solution.

Photoinduced electron transfer based fluorescence correlation spectroscopy (PET-FCS) is a powerful tool to study biomolecular processes. However, some questions remain as to how to correctly interpret the PET-FCS data. In this work, we studied the PET process between tetramethylrhodamine and guanosine by means of femtosecond transient absorption spectroscopy. We derived that the charge separation rate is 4.1 × 10(9) s(-1) and the charge recombination rate is 5.2 × 10(10) s(-1) for the current system, supporting the three-state model and the interpretation on PET-FCS experiments given by Qu et al. (J. Phys Chem. B, 2010, 114, 8235). At the limit that both the charge separation and recombination rates are much faster than the process that PET-FCS reveals, the three-state model can be simplified to an equivalent two-state model with a dark state whose brightness is nonzero. We propose ways to obtain the brightness of the dark state with additional experiments, which is necessary for a PET-FCS study.