Time-resolved Fluorescence Spectra Research Articles

Bisphenol a modification and how its structure influences human serum albumin binding force

Bisphenol A (BPA) is an environmental hormone with substantial physiological toxicity to the human body. Three electron-withdrawing derivatives of BPA are synthesized in this study to reduce its toxicity. The interaction mechanism between BPA and its three derivatives with human serum albumin (HSA) is investigated using molecular docking, electrochemistry, circular dichroism spectrum analysis, and fluorescence spectroscopy. Temperature-dependent tests and time-resolved fluorescence spectra reveal that all four compounds dynamically quench the internal fluorescence of HSA. Based on molecular docking and site competition outcomes, four compounds are primarily bound to site I's active pocket. Thermodynamic parameters indicate that the compounds’ interaction with HSA is spontaneous, and introducing weak electron-withdrawing groups changes the action force. Circular dichroism and synchronous fluorescence measurements suggest four compounds impact HSA's structure. The substituents' electron attraction capacity determines their impact. Electrochemical studies examine the effect of electron-absorbing groups on the BPA and HSA binding capacity. Pharmacokinetics showed that nitro-substituted BPA may be a potential superior substitute for BPA. These results indicate crucial practical value, providing theoretical support for future research.

On-the-fly simulation of time-resolved fluorescence spectra and anisotropy.

We combine on-the-fly trajectory surface hopping simulations and the doorway-window representation of nonlinear optical response functions to create an efficient protocol for the evaluation of time- and frequency-resolved fluorescence (TFRF) spectra and anisotropies of the realistic polyatomic systems. This approach gives the effective description of the proper (e.g., experimental) pulse envelopes, laser field polarizations, and the proper orientational averaging of TFRF signals directly from the well-established on-the-fly nonadiabatic dynamic simulations without extra computational cost. To discuss the implementation details of the developed protocol, we chose cis-azobenzene as a prototype to simulate the time evolution of the TFRF spectra governed by its nonadiabatic dynamics. The results show that the TFRF is determined by the interplay of several key factors, i.e., decays of excited-state populations, evolution of the transition dipole moments along with the dynamic propagation, and scaling factor of the TFRF signals associated with the cube of emission frequency. This work not only provides an efficient and effective approach to simulate the TFRF and anisotropies of realistic polyatomic systems but also discusses the important relationship between the TFRF signals and the underlining nonadiabatic dynamics.

Impact of Mo doping on photo-sensing properties of ZnO thin films for advanced photodetection applications

This work explored the impact of Mo-doping on the structural, optical, photophysical, and electrical characteristics of ZnO thin films and their potential application to the UV light detection properties was investigated. The hexagonal structure of the films without any impurities or extra phases was confirmed by X-ray diffraction and FT-Raman spectroscopy. The crystallite size reduced from 36 nm to 25 nm with the addition of 3 wt% of Mo in ZnO. The EDX/SEM e-mapping verified the elemental composition and uniform Mo doping throughout the films. The FESEM images revealed spherical nanoparticles with smaller grains size for higher Mo-doping levels. The absorption spectra were recorded from UV to NIR range, and the bandgap was observed to increase from 3.25 eV for pure ZnO to 3.42 for 3% Mo-doped ZnO sample. The Mo-doped ZnO film showed PL quenching, which indicates charge transfer and suppression of defect sates in the ZnO films via Mo-doping. The time-resolved fluorescence spectra (TRFS) of these films revealed that the carrier lifetime increased from 80 ps for pure ZnO to 144 ps for 3% Mo-doped ZnO thin film. The electrical parameters including resistivity, carrier mobility, concentrations, and sheet resistance of fabricated films were evaluated by Hall-effect measurement. The resistivity and mobility were observed to decrease from 9.33×104 Ω.cm, 55.1 cm2/V.s to 2.03×103 Ω.cm 15.4 cm2/V.s for 3% Mo-doped ZnO thin film, while carrier density increased. The photodetection study demonstrated that the responsivity, detectivity, external quantum efficiency and response time of devices were significantly enhanced with Mo idoping.

Truxene-to-Fluorenone Energy Transfer in a Robust Mesoporous Zn-MOF.

A new metal-organic framework (MOF; [Zn4O(hett)4/3(fluo)1/2(bdc)1/2]n; TFT-MOF) constructed on chromophoric ligands 5,5',10,10',15,15'-hexaethyltruxene-2,7,12-triacetate (hett), 9-fluorenone-2,7-dicarboxylate (fluo), terephthalate (bdc), and the Zn4O node has been prepared and identified by powder X-ray diffraction. This luminescent MOF exhibits large mesoporous pores of 2.7 nm based on computer modeling using density functional theory (DFT) calculations. The steady-state and time-resolved fluorescence spectra and photophysical parameters of TFT-MOF have been investigated and compared with those of the free ligands and their basic chromophores. All in all, TFT-MOF exhibits particularly efficient singlet-singlet energy-transfer processes described as 1(hett)* → (fluo) and 1(bdc)* → (fluo), leading to fluorescence arising for the fluo lumophore operating only through Förster resonance energy transfer (FRET) with an efficiency of transfer of up to >95%. This experimental conclusion was corroborated by DFT and time-dependent DFT (TDDFT). For the 1(hett)* → (fluo) process, the approximated overall rate constant of energy transfer was evaluated to be at most 2.04 × 1010 s-1 (using a Stern-Volmer approach of solution data and the relationship between distance and concentration). This process was analyzed using the Förster theory, where two intrapore energy transfer paths of center-to-center distances of 13 and 25 Å have been identified. TFT-MOF photosensitizes the formation of singlet oxygen (1O2 (1Σg)) as detected by its phosphorescence signal at 1275 nm.

Classification of Dairy Products by Time-Correlated Single Photon Counting Fluorescence and Principal Component Analysis (PCA)

A transient fluorescence spectroscopy system based on time-correlated single photon counting (TCSPC) technology was constructed. Time-resolved fluorescence spectra of pure, modified and fresh milk were obtained using this system. A method for differentiating these dairy products was established by principal component analysis (PCA). The measured time-resolved fluorescence spectra of the dairy products were directly substituted into the principal component analysis model without fitting. The results showed that the two largest principal components, PC1 and PC2, had variance contribution values of 48.18% and 32.1%, respectively. The results were plotted as a two-dimensional graph of PC1 × PC2. The results showed that the coordinates of the dairy products were clearly distinguished in the two-dimensional plot, with pure milk in the fourth quadrant, modified milk in the second and third quadrants, and fresh milk in the first quadrant. It is inferred that the time-resolved fluorescence spectra were changed due to the different heat treatment of the dairy products. Compared with fluorescence spectroscopy, time-resolved fluorescence spectroscopy is less susceptible to instrumental variation. Data from different instruments can be compared. The developed method does not require any processing and fitting of fluorescence lifetimes to milk, which has the advantages of easy identification, simple operation, and short identification time.

Independent and simultaneous photocatalytic decontamination and disinfection of water over In2O3/TiO2 heterojunctions

We have explored the application of In2O3/TiO2 heterojunctions to the photocatalytic removal of a substance classified as a pollutant of emerging concern, such as the anti-inflammatory drug sodium diclofenac (DCF), from aqueous solutions. In addition, the study of water disinfection by means of photocatalysis, simultaneously with the elimination of DCF, has been carried out with the same catalysts, by using bacterial populations of the genus Enterococcus faecalis. The In2O3/TiO2 catalysts with different indium amounts consist of bi-phasic samples with anatase TiO2 and In2O3 phases, without evidence in In doping into the titania structure, and show, according to UV–vis and time-resolved fluorescence spectra, light absorption into the visible range and interfacial charge transfer from the conduction band of In2O3 to that of TiO2. Complete photocatalytic removal of DCF was achieved by using all catalysts after 120 min of irradiation, being the most active the catalyst with 5% of In2O3, in agreement with its highest efficiency of interfacial charge transfer revealed by fluorescence lifetime. In contrast, in terms of DCF mineralization, the 5In2O3/TiO2 catalyst did not outperform the pristine TiO2, the higher mineralization percentage being achieved with 1% In. Simultaneous decontamination and disinfection experiments show that the 5% In2O3/TiO2 heterojunction outperforms the activity of titania for DFC removal in the presence of Enterococcus faecalis, but not for the inactivation of bacteria.

Spectroscopic studies on the supramolecular interactions of methyl benzoate derivatives with p-sulfocalix[6]arene macrocycles

This paper is a continuation of our previous research and aims to further investigate and elucidate the nature and mechanisms of noncovalent supramolecular interactions between four methyl benzoate derivatives (I-IV), which are capable of exhibiting Twisted Intramolecular Charge Transfer (TICT) and/or Excited State Intramolecular Proton Transfer (ESIPT)‐type behavior, and chemical and biological nanocavities. Photophysical and photochemical properties of molecules I-IV in aqueous solution in the presence of well-recognized macrocyclic host p-sulfocalix[6]arenes (SCA[6]) have been studied using steady-state, time-resolved and 1H NMR spectroscopic techniques. The changes in the ground- and excited-state spectroscopic characteristics (absorption and fluorescence spectra, time-resolved fluorescence spectra, fluorescence decay times and 1H NMR spectra) undergo significant modifications upon encapsulation of the investigated methyl benzoate derivative in the macromolecular cavity. For the two compounds (I and II), the interactions with the macrocycles with a hydrophobic SCA[6] cavity lead to the formation of stable inclusion complexes with 1:1 stoichiometry, both in the ground and excited state, while the stoichiometry of the III-SCA[6] and IV-SCA[6] complexes in the ground and excited states is 1:2. The values of the equilibrium constants have been determined from the spectroscopic data using Benesi-Hildebrand and nonlinear regression procedures. The location of the organic molecule inside the SCA[6] has been investigated by 1H NMR experiments. The changes in macrocyclic compound-induced NMR chemical shifts clearly indicate that the chemical structure of inclusion complexes is very different for methyl benzoate derivative-SCA[6] and methyl benzoate derivative-CB[7] systems. Finally, we have shown, using time-dependent fluorescence Stokes shift, that very fast solvation dynamics of pure water is markedly different from that of the confined water molecule in SCA[6] system.

O-phenylenediamine Derived Fluorescent Carbon Quantum dots for Detection of Hg(II) in Environmental Water.

With the expansion of human activities, the consequent influx of mercury (Hg) into the food chain and the environment is seriously threatening human life. Herein, nitrogen and sulfur co-doped fluorescent carbon quantum dots (yCQDs) were prepared via a hydrothermal method using o-phenylenediamine (OPD) and taurine as precursors. The morphological characteristics as well as spectral features of yCQDs indicated that the photoluminescence mechanism should be the molecular state fluorophores of 2, 3-diaminophenothiazine (oxOPD), which is the oxide of OPD. The as-synthesized yCQDs exhibited sensitive recognition of Hg2+. According to the investigation in combination of UV-Vis absorption spectra, time-resolved fluorescence spectra and quantum chemical calculations, the abundant functional groups on the surface of yCQDs allowed Hg2+ to bind with yCQDs through various interactions, and the formed complexes significantly inhibited the absorption of excitation light, resulting in the static fluorescence quenching of yCQDs. The proposed yCQDs was utilized for Hg2+ sensing with the limit of detection calculated to be 4.50 × 10- 8M. Furthermore, the recognition ability of yCQDs for Hg2+ was estimated in tap water, lake water and bottled water, and the results indicated that yCQDs have potential applications in monitoring Hg2+.

Kernelizing: A way to increase accuracy in trilinear decomposition analysis of multiexponential signals

The unmixing of multiexponential decay signals into monoexponential components using soft modelling approaches is a challenging task due to the strong correlation and complete window overlap of the profiles. To solve this problem, slicing methodologies, such as PowerSlicing, tensorize the original data matrix into a three-way data array that can be decomposed based on trilinear models providing unique solutions. Satisfactory results have been reported for different types of data, e.g., nuclear magnetic resonance or time-resolved fluorescence spectra. However, when decay signals are described by only a few sampling (time) points, a significant degradation of the results can be observed in terms of accuracy and precision of the recovered profiles.In this work, we propose a methodology called Kernelizing that provides a more efficient way to tensorize data matrices of multiexponential decays. Kernelizing relies on the invariance of exponential decays, i.e., when convolving a monoexponential decaying function with any positive function of finite width (hereafter called “kernel”), the shape of the decay (determined by the characteristic decay constant) remains unchanged and only the preexponential factor varies. The way preexponential factors are affected across the sample and time modes is linear, and it only depends on the kernel used. Thus, using kernels of different shapes, a set of convolved curves can be obtained for every sample, and a three-way data array generated, for which the modes are sample, time and kernelizing effect. This three-way array can be afterwards analyzed by a trilinear decomposition method, such as PARAFAC-ALS, to resolve the underlying monoexponential profiles. To validate this new approach and assess its performance, we applied Kernelizing to simulated datasets, real time-resolved fluorescence spectra collected on mixtures of fluorophores and fluorescence-lifetime imaging microscopy data. When the measured multiexponential decays feature few sampling points (down to fifteen), more accurate trilinear model estimates are obtained than when using slicing methodologies.

Improved photocatalytic H2O2 production of boron doped g-C3N4 by controllably co-modifying nanosized PDI and Ag

Herein, boron-doped g-C3N4 (BCN) is first modified with perylene diimide (PDI) nanosheets driven by the π−π interactions, and subsequently decorated with nanosized Ag through the photodeposition method. The optimal PDI/BCN-Ag photocatalyst achieves a H2O2 production rate of 143 μmol g−1 h−1 without any sacrificial agents under visible light irradiation, which is about13-fold improvement compared with pristine g-C3N4. The boosted photoactivity is mainly ascribe to the enhanced charge separation due to the cascade S-scheme charge transfer between the coupled PDI and BCN, and the promoted oxygen activation from the introduced nanosized Ag by means of the time-resolved surface photovoltage responses and fluorescence spectra, kelvin probe measurement analyses, O2 temperature-programmed desorption and electron paramagnetic resonance spectroscopy. Notably, there is a dual channel for H2O2 production on PDI/BCN-Ag. The two-electron oxygen reduction dominated by the produced •O2− radicals occurs on the Ag nanoparticles, whereas the two-electron water oxidation occurs on the PDI.

Photoexcimerisation of pure acriflavine dye in water and alcohol

The light emission properties of acriflavine have been extensively utilised in its applications as dye laser active media, as photosensitizer, as fluorescent and FRET (Fluorescence Resonance Energy Transfer) agent for sensing mechanism etc. However, studies on the photochemical and photophysical properties of acriflavine and its aggregates are very limited and little is known about its emission characteristics in different media. The present study was undertaken to acquire a comprehensive understanding of the aggregation process and emission characteristics of the solution of pure acriflavine dye in water and alcohol, namely the propanol, methanol, ethanol and butanol. This study includes confirming the photoexcimerisation of acriflavine by concentration dependent UV–Visible spectroscopy, steady state fluorescence spectroscopy and time resolved fluorescence spectroscopy at room temperature. The present study shows the monomer and excimer fluorescence emission of acriflavine in the range 495–528 nm and 549–587 nm respectively (monomer and excimer emission peak wavelength varies for different solvents). The nature of the excimer emission band of acriflavine around 575 nm for all the solvents has been tested through temperature dependent steady state fluorescence spectroscopy and also from time resolved fluorescence spectra it has been found that the excimer band does not originate from any triplet excited state. The pH dependent emission spectra for fixed concentration of acriflavine in the solvents reveals red shifts in the monomer and the excimer fluorescence maxima. The excimerisation of acriflavine in water, propanol and methanol is found as static process from excited dimers, whereas in ethanol and butanol it is the result of dynamic diffusion process between a photoexcited and a ground state monomer. The excimerisation process of the acriflavine has been quantified by evaluating the monomer-excimer equilibrium concentration i.e., the critical concentration in the cited solvents. At the critical concentration the monomer and the excimer are found to be fluoresced with equal intensity. The acriflavine solutions specifically at the critical concentration in the cited solvents will enhance its photophysical and photochemical applications by extending them up to the new range of excimer emission radiation at the wavelength in-between 549 nm and 587 nm. Hence, this report shows that, by using acriflavine solutions of certain concentrations in any one of the cited solvents as an active medium of a dye laser and thereby obtaining both the monomer and excimer emission band, the wavelength of the laser can be tuned from 495 nm to 587 nm.

A Novel Type of Tetradentate Dipyridyl-Derived Bis(pyrazole) Ligands for Highly Efficient and Selective Extraction of Am3+ Over Eu3+ From HNO3 Solution

ABSTRACT The extraction of Am3+ and Eu3+ with 6,6’-bis(5-alkyl-1H-pyrazol-3-yl)-2,2’-bipyridine (BPzBPy, alkyl = i-Bu, n-Bu, n-Oct) from HNO3 medium and the complexation of BPzBPy with Eu3+ were investigated. By using meta-nitrobenzotrifluoride (F-3) as a diluent, iBu-BPzBPy ligand in combination with 2-bromohexanoic acid was able to extract Am3+ over Eu3+ with the nature of significantly high efficiency, relatively fast extraction kinetics, and easy stripping. Slope analysis showed the formation of a 1:2 metal/ligand extraction species. The analyses of electrospray ionization mass spectrometry (ESI-MS), Fourier transform infrared (FT-IR) and time-resolved laser fluorescence spectrum (TRLFS) revealed that the composition of the extracted complex was [Eu(H2O)L2]A3 (L = ligand; HA = 2-bromohexanoic acid). The complexation of iBu-BPzBPy ligand with Eu3+ was an enthalpy-driven spontaneous, exothermic, and entropy-decreasing process. Besides, the complex stability constants were also obtained via UV–vis spectrophotometric titration. Combining the results of solvent extraction and complexation studies, a cation exchange extraction model was also proposed.

Biochemical and spectroscopic characterization of PSI-LHCI from the red alga Cyanidium caldarium.

Light-harvesting complexes (LHCs) have been diversified in oxygenic photosynthetic organisms, and play an essential role in capturing light energy which is transferred to two types of photosystem cores to promote charge-separation reactions. Red algae are one of the groups of photosynthetic eukaryotes, and their chlorophyll(Chl) a-binding LHCs are specifically associated with photosystem I (PSI). In this study, we purified three types of preparations, PSI-LHCI supercomplexes, PSI cores, and isolated LHCIs, from the red alga Cyanidium caldarium, and examined their properties. The polypeptide bands of PSI-LHCI showed characteristic PSI and LHCI components without contamination by other proteins. The carotenoid composition of LHCI displayed zeaxanthins, β-cryptoxanthins, and β-carotenes. Among the carotenoids, zeaxanthins were enriched in LHCI. On the contrary, both zeaxanthins and β-cryptoxanthins couldnot be detected from PSI, suggesting that zeaxanthins and β-cryptoxanthins are bound to LHCI but not PSI. A Qy peak of Chl a in the absorption spectrum of LHCI was shifted to a shorter wavelength than those in PSI and PSI-LHCI. This tendency is in line with the result of fluorescence-emission spectra, in which the emission maxima of PSI-LHCI, PSI, and LHCI appeared at 727, 719, and 677nm, respectively. Time-resolved fluorescence spectra of LHCI represented no 719 and 727-nm fluorescence bands from picoseconds to nanoseconds. These results indicate that energy levels of Chls around/within LHCIs and within PSI are changed by binding LHCIs to PSI. Based on these findings, we discuss the expression, function, and structure of red algal PSI-LHCI supercomplexes.

Unambiguous spectral characterization on triplet energy transfer from quantum dots mediated by hole transfer competing with other carrier dynamics.

Triplet generation by quantum dots (QDs)-sensitized molecules emerges great potential in many applications. However, the mechanism of triplet energy transfer (TET) is still fuzzy especially due to the complicated energy level alignment of QDs and molecules or trap states in QDs. Here, CdSe QDs and 5-tetracene carboxylic acid (TCA) molecules are selected as the triplet donor and acceptor, respectively, to form a TET system. By tuning the band gap of CdSe, the CdSe-TCA complex is exactly designed to present a Type-II like alignment of relative energetics. Coupling the transient absorption and time-resolved fluorescence spectra, all carrier dynamics is distinctly elucidated. Quantitative analysis demonstrates that hole transfer persisting for ∼ 2 ps outcompetes all other carrier dynamics such as electron trapping (∼100 ps level), charge recombination (∼ 5 ns) and the so-called "back transfer charge recombination" (∼50 ns), and thus leads to a hole-transfer-mediated TET process. The low TET yield (∼34.0%) ascribed to electron behavior can be further improved if electron trapping and charge recombination are efficiently suppressed. The observation on distinguishable carrier dynamics attributed to legitimate design of energy level alignment facilitates a better understanding of the TET mechanism from QDs to molecules as well as further development of photoelectronic devices based on such TET systems.

A promoted charge separation/transfer and surface plasmon resonance effect synergistically enhanced photocatalytic performance in Cu nanoparticles and single-atom Cu supported attapulgite/polymer carbon nitride photocatalyst

The Cu nanoparticles and single-atom Cu-supported attapulgite/polymer carbon nitride (PCN) photocatalyst was successfully synthesized via a calcination process. The C≡N triple bond defect structure was successfully introduced into PCN structure through the composite process of modified attapulgite and PCN, suppressing the recombination of photogenerated electrons, narrowed the bandgap, and improved the efficiency of photocatalytic. The photoluminescence spectra, time-resolved fluorescence spectra, and ultraviolet-visible diffuse reflectance spectra together with theoretical calculation revealed that the doping of single-atom Cu further promoted the separation of photogenerated carriers and reduced the bandgap. The surface plasmon resonance effect produced by Cu nanoparticles and the promoted charge separation and transfer effect of single-atom Cu synergistically enhance the photocatalytic performance, and the degradation rate toward methylene blue dye was 7.7 times higher than that of PCN. Compared with the traditional single-method modified PCN catalyst, the catalyst prepared by this cocktail-like multi-composite strategy has the characteristics of high charge separation efficiency, high catalytic efficiency, and high stability.

Deciphering the non-covalent binding patterns of three whey proteins with rosmarinic acid by multi-spectroscopic, molecular docking and molecular dynamics simulation approaches

Binding of rosmarinic acid (RA) with three whey proteins, β-lactoglobulin (β-LG), α-lactalbumin (α-LA) and bovine serum album (BSA) was deciphered in the present study. Steady and time-resolved fluorescence spectra revealed the occurrence of fluorescence quenching via static type with binding constant sequence of BSA > α-LA > β-LG. Thermodynamic parameters indicated the dominated driving force of hydrophobic effect. Synchronous and three-dimensional fluorescence spectra confirmed the alteration in hydrophobic microenvironment of TRP. DSC and FT-IR spectra indicated the RA was successfully encapsulated in the complex. No obvious impact of RA binding on the secondary structure of whey proteins was observed by CD spectra. Molecular docking indicated that RA bound in calyx of β-LG, cleft entrance between α-helical and β-sheet-rich domains of α-LA and Sudlow's site I of BSA with binding affinity of BSA > α-LA > β-LG on basis of hydrophobic force and hydrogen bonds. Molecular dynamics simulation was conducted and RMSF calculations revealed that the fluctuation of interacting residues between RA and proteins becomes restricted to a certain extent. More hydrogen bonds were involved in binding between β-LG and RA. Molecular Mechanics Generalized Born Surface Area (MMGBSA) calculations suggested that β-LG/RA complex was more stable with major contribution from electrostatic interactions. Data may provide useful information for further investigation about fabrication of RA protecting system and development of whey protein-RA functional materials. • Binding constant with RA was in the sequence of BSA > α-LA > β-LG. • The dominated driving force for binding of RA with whey proteins was hydrophobic effect. • DSC and FT-IR spectra indicated that RA was successfully encapsulated in protein after complexation. • RA bound in calyx of β-LG, cleft entrance between α-helical and β-sheet-rich domains of α-LA and Sudlow's site I of BSA. • Molecular dynamics simulation indicated that β-LG/RA complex was more stable than α-LA/RA and BSA/RA.

Tris(trifluoromethyl)germyl biphenyl conjugated molecular system with ferrocenyl substituent: Confirmation of photoinduced intramolecular charge transfer to the germanium center

Unsymmetrical 4,4′-biphenyl derivative with tris(trifluoromethyl)germylethynyl ‒CC‒Ge(CF3)3 and ferrocenylethynyl Fc‒CC‒ substitutes have been prepared (21), its properties have been studied and compared with those full non-fluorinated analogue of trimethylgermylethynyl ‒CC‒Ge(CH3)3 compound (20). UV-visible, absorption, steady state, and time-resolved fluorescence spectra in solution for these germanium and a number of similar compounds (15-17, 22) have been investigated. The process of photoinduced electron transfer from the π-conjugated system to the germanium center is confirmed for 21, as well as for the first time discovered earlier [19] in the 4-biphenyl ‒CC‒Ge(CF3)3 molecule (9). It was found that the lifetime of the radical-ion pair 21 in the excited state (kCR2 = 1.2 × 105 s-1) is approximately an order of magnitude longer than for 9, which can be explained by the stabilizing effect of the electron donor Fc‒CC‒ group. Density-functional theory (DFT) computations was used to calculate the optimized geometry of 21 in excited state, and two main bands in the emission spectrum at laser excitation (340 and 386 nm) an excellent fit to the experimental data. An additional data on the nature of the (CF3)3Ge group, including geometry, electronegativity, and contributions 4d AOs of germanium into lowest unoccupied molecular orbital (LUMO) in a wide range of fluorinated and non-fluorinated compounds were also calculated. The molecular structure of compound 21 was determined by X-ray structural analysis. In the crystal lattice of 21, numerous intermolecular F‧‧‧F interactions shortened in comparison with the van der Waals radii were detected, which leads to the formation of quasi-two-dimensional fluorinated layers in crystals.

Accelerated charge transfer of g-C3N4/BiVO4 Z-scheme 2D heterojunctions by controllably introducing phosphate bridges and Ag nanocluster co-catalysts for selective CO2 photoreduction to CO

Artificial Z-scheme heterojunctions by mimicking photosynthesis have been widely investigated for photoreduction of CO2, yet the activity is hindered by the weak interfacial interactions and insufficient CO2 activation sites. Here, a cascade Z-scheme g-C3N4/BiVO4 (CN/BVO) heterojunction has been tailored by the dual modification of phosphates and Ag nanoclusters for CO2 reduction in pure water, in which phosphates are modified in the interface of CN/BVO by a facile impregnation method, while Ag nanoclusters are anchored on the surface of CN by a light induced in-situ deposition strategy under a low-temperature environment created by liquid N2. The optimal Ag-CN/PO-BVO heterojunction delivers a ca.48 μmol g−1h−1 CO generation rate with 97 % selectivity, which exhibits a 24-fold increment in CO production rate compared with that of pristine BVO. The improved photoactivity is mainly ascribed to the accelerated Z-scheme charge transfer from the built PO-bridged dimension-matched 2D interfaces and from the introduced Ag nanoclusters with preferable catalytic functions for CO2 reduction mainly by means of the time-resolved surface photovoltage responses and fluorescence spectra. Moreover, temperature-programmed desorption curves and in-situ DRIFTS results demonstrate that the introduced Ag is favorable for CO2 activation and CO desorption with COOH intermediates, responsible for the high CO selectivity.

Efficient degradation of organic dyes and reduced Cr(VI) in environmental water purification by in-situ deposition of silver nanoparticles on polydopamine-modified M-ATP/PCN

This paper presents the synthesis of Ag@PDA/M-ATP/PCN photocatalysts for the removal of heavy metals and organic dyes via the in-situ reduction method. According to the photoluminescence (PL) spectra, time-resolved fluorescence spectra, UV–vis absorption spectra, transient photocurrent response spectra, and the EIS results, the composite of M-ATP, PDA coating, and single-atom Ag doping further promotes the separation of the photogenerated carriers, reduces the band-gap, improves the photocatalytic performance, and promotes the synergistic effect of charge separation and transfer to enhance the photocatalytic performance. The catalysts prepared by this composite strategy exhibit high charge separation efficiency, higher catalytic efficiency, and better stability than the conventional single-method modified polymeric carbon nitride catalysts.

Full relaxation dynamics recovery from ultrafast fluorescence experiments by means of the stochastic model: Does the solvent response dynamics depend on the fluorophore nature?

• The model of non-stationary charge-transfer dye fluorescence spectrum is presented. • The solvation dynamics depend on fluorophore. • The contribution of intramolecular vibrations in FLUPS is separated. • The solvent relaxation function of hexane is determined. An approach to analysing time-resolved fluorescence spectra has been developed for dyes with non-parabolic free energy curves of the excited and ground states. It incorporates the description of the solvent relaxation and redistribution/relaxation of intramolecular high-frequency vibrations proceeding in parallel with the pumping. The approach has been applied to simulate spectra of covalently linked perylene-dimethylaniline (PD) in a series of solvents of different polarity. The developed approach combined with the achieved temporal resolution of the modern fluorescence upconversion spectroscopy is shown to provide a possibility to disentangle the relaxation of high-frequency vibrations and the dynamics of the solvent. In this compound the reorganization of both intramolecular vibrations and the solvent strongly affects the absorption and fluorescence spectra so that their influence on spectral dynamics is highly entangled. The comparison of fluorescence spectral dynamics of two dyes, coumarin 153 and PD, shows that the solvation dynamics depend on the fluorophore. The fitting of simulated fluorescence spectral dynamics of PD to the experimental data enables us to determine the solvent relaxation function of hexane.