State Electron Transfer Research Articles

A Diode-Like Dye-Cu Anisotropic Junction in a Coordination Polymer as a Logic State Ratchet for Intratumor Redox Photomodulation.

Redox logic materials offer new avenues to modulate intracellular pathologic redox environment area-specifically, but the unambiguity of redox logic states and their unidirectional and repetitive switchability are challenging to realize. By merging a bistable diisophthalic phenazine dye ligand with CuII salt, a multistable coordination polymer (CP) was constructed, of which the dye-Cu anisotropic junction achieved the diode-like unidirectional electron transfer and logic state ratchet for the first time. Radical cationic CP maintained OFF status with low toxicity in healthy tissues, but was reduced to the neutral SERVO state by the overexpressed glutathione (GSH) in hypoxic tumors. After photoirradiation, the stabilized charge-separated ON status promoted photo-Fenton reaction for reactive oxygen species (ROS) signal transduction, and simultaneously recovered the initial state for catalytic signal amplification of ROS, furnishing intratumor redox photomodulation for therapy.

A Diode‐Like Dye‐Cu Anisotropic Junction in a Coordination Polymer as a Logic State Ratchet for Intratumor Redox Photomodulation

AbstractRedox logic materials offer new avenues to modulate intracellular pathologic redox environment area‐specifically, but the unambiguity of redox logic states and their unidirectional and repetitive switchability are challenging to realize. By merging a bistable diisophthalic phenazine dye ligand with CuII salt, a multistable coordination polymer (CP) was constructed, of which the dye‐Cu anisotropic junction achieved the diode‐like unidirectional electron transfer and logic state ratchet for the first time. Radical cationic CP maintained OFF status with low toxicity in healthy tissues, but was reduced to the neutral SERVO state by the overexpressed glutathione (GSH) in hypoxic tumors. After photoirradiation, the stabilized charge‐separated ON status promoted photo‐Fenton reaction for reactive oxygen species (ROS) signal transduction, and simultaneously recovered the initial state for catalytic signal amplification of ROS, furnishing intratumor redox photomodulation for therapy.

Photophysical Properties of Bright Luminescent Polyethyleneimine@Carbon Nanodots and Their Application in White Light-Emitting Diodes

Highly fluorescent carbon nanodots (CNDs) have broad application prospects in optoelectronics, energy, biological imaging, and other fields because of their good solubility in water, adjustable photoluminescence (PL), low toxicity, good biocompatibility, and stable chemical properties. In this paper, polyethyleneimine@CNDs (PEI@CNDs) with unique excitation- and concentration-dependent PL properties were synthesized by a one-pot hydrothermal approach. The morphology, structure, surface chemistry, photophysical properties, and stability of the PEI@CNDs were well probed. The PEI@CNDs solution at low concentration displayed blue PL with a quantum yield of 50.6%. As the concentrations of the PEI@CNDs increase, the PL colors changed from blue, cyan, and green, to greenish-yellow. At low concentration, the excitation-independent and excitation-dependent PL property is mainly caused by carbon core and surface state emission. However, at higher concentration, the quenched blue emission and enhanced green emission were found. This is mainly attributed to the aggregate-related inner filter effect, electron transfer, and surface states. Mixing 10.0 mg/mL of PEI@CNDs with polyvinyl alcohol can be used to construct composite films, which were combined with the blue light-emitting diode to construct white light-emitting diodes with white and warm white emissions.

Bimolecular Excited-State Proton-Coupled Electron Transfer within Encounter Complexes.

Bimolecular excited-state proton-coupled electron transfer (PCET*) was observed for reaction of the triplet MLCT state of [(dpab)2Ru(4,4'-dhbpy)]2+ (dpab = 4,4'-di(n-propyl)amido-2,2'-bipyridine, 4,4'-dhbpy = 4,4'-dihydroxy-2,2'-bipyridine) with N-methyl-4,4'-bipyridinium (MQ+) and N-benzyl-4,4'-bipyridinium (BMQ+) in dry acetonitrile solutions. The PCET* reaction products, the oxidized and deprotonated Ru complex, and the reduced protonated MQ+ can be distinguished from the excited state electron transfer (ET*) and the excited state proton transfer (PT*) products by the difference in the visible absorption spectrum of the species emerging from the encounter complex. The observed behavior differs from that of reaction of the MLCT state of [(bpy)2Ru(4,4'-dhbpy)]2+ (bpy = 2,2'-bipyridine) with MQ+, where initial ET* is followed by diffusion-limited proton transfer from the coordinated 4,4'-dhbpy to MQ0. The difference in observed behavior can be rationalized based on changes in the free energies of ET* and PT*. Substitution of bpy with dpab results in the ET* process becoming significantly more endergonic and the PT* reaction becoming somewhat less endergonic.

How Pendant Groups Dictate Energy and Electron Transfer in Perovskite–Rhodamine Light Harvesting Assemblies

Energy and electron transfer processes allow for efficient manipulation of excited states within light harvesting assemblies for photocatalytic and optoelectronic applications. We have now successfully probed the influence of acceptor pendant group functionalization on the energy and electron transfer between CsPbBr3 perovskite nanocrystals and three rhodamine-based acceptor molecules. The three acceptors─rhodamine B (RhB), rhodamine isothiocyanate (RhB-NCS), and rose Bengal (RoseB)─contain an increasing degree of pendant group functionalization that affects their native excited state properties. When interacting with CsPbBr3 as an energy donor, photoluminescence excitation spectroscopy reveals that singlet energy transfer occurs with all three acceptors. However, the acceptor functionalization directly influences several key parameters that dictate the excited state interactions. For example, RoseB binds to the nanocrystal surface with an apparent association constant (Kapp = 9.4 × 106 M-1) 200 times greater than RhB (Kapp = 0.05 × 106 M-1), thus influencing the rate of energy transfer. Femtosecond transient absorption reveals the observed rate constant of singlet energy transfer (kEnT) is an order-of-magnitude greater for RoseB (kEnT = 1 × 1011 s-1) than for RhB and RhB-NCS. In addition to energy transfer, each acceptor had a subpopulation of molecules (∼30%) that underwent electron transfer as a competing pathway. Thus, the structural influence of acceptor moieties must be considered for both excited state energy and electron transfer in nanocrystal-molecular hybrids. The competition between electron and energy transfer further highlights the complexity of excited state interactions in nanocrystal-molecular complexes and the need for careful spectroscopic analysis to elucidate competitive pathways.

A fluorescent pH switch probe for the ‘turn-on’ dual-channel discriminative detection of magnesium and zinc ions

A coumarin-based fluorescent probe is presented for the multi-channel reversible “ Turn-on ” detection of Mg 2+ ion (at 483 nm) and Zn 2+ ion (at 560 nm) as well as a base (450 nm) at different wavelengths with large Stokes shifts. • A coumarin-based probe HL is utilized for the dual channel ‘turn-on’ detection of Mg 2+ and Zn 2+ ions. • HL detects Mg 2+ and Zn 2+ ions at two different wavelengths with large Stokes shifts. • HL detects both metal ions by the inhibition of C=N bond rotation, PET and ESIPT while promoting CHEF. • Probe HL also functioned as a reversible fluorescent pH switch. • HL was utilized for the detection of Mg 2+ and Zn 2+ ions in human breast cancer cells. • Low-cost detection methods, paper-strips and polymer films, were used for the sensing of Mg 2+ and Zn 2+ ions. A coumarin-based fluorescent probe, HL (( E )-8-((benzo[d]thiazol-2-ylimino)methyl)-7-hydroxy-4-methyl-2H-chromen-2-one), is presented for the dual-channel “ Turn-on ” detection of Mg 2+ (at 483 nm) and Zn 2+ (at 560 nm) ions at two different wavelengths with large Stokes shifts. HL exhibits impressive detection limits and binding constants with both Mg 2+ and Zn 2+ ions. HL detected these ions by the inhibition of -C=N bond rotation and suppression of photoinduced electron transfer (PET) and excited state intramolecular proton transfer (ESIPT) while promoting chelation enhanced fluorescence (CHEF). For the detection of Mg 2+ and Zn 2+ ions, reversibility was achieved by using ATP. HL is not only sensitive and selective for the detection of Mg 2+ and Zn 2+ ions but also showed considerable reversible “ Turn-on-Turn-off ” fluorescent pH switch behavior. The DFT studies assisted in understanding the binding of Mg 2+ and Zn 2+ ions by the probe. HL was utilized to detect Mg 2+ and Zn 2+ ions in the human breast cancer cell line by fluorescence cell imaging studies while several low-cost detection methods were also illustrated.

Restriction of photoinduced electron transfer as a mechanism for the aggregation-induced emission of a trityl-functionalised maleimide fluorophore.

The restriction of intramolecular motion (RIM) and restricted access to a conical intersection (RACI) have been accepted as general working mechanisms for aggregation-induced emission (AIE) phenomena. However, as the family of AIE molecules grows, the RIM and RACl mechanisms cannot be used to fully understand some AIE phenomena. Herein, the restriction of the photoinduced electron transfer (RPET) state is proposed to rationalize the AIE phenomena of trityl-functionalised maleimide molecule based on density functional theory calculations. The "state-crossing from a locally excited to an electron transfer state" (SLEET) model was employed to predict the ON/OFF molecular PET in solution and solid states. According to the SLEET model, we showed that a non-emissive electron transfer excited state leads to the fluorescence quenching of trityl-functionalised maleimide in solution. However, due to the reduced polarity of the environment in aggregates, the electron transfer state is thermodynamically inaccessible, and a low-lying locally excited state exhibits intense emission. These findings provide a theoretical foundation to understand the working mechanisms of AIE molecules and the design of new AIEgens. We expect that the RPET mechanism can be used to screen potential AIEgens using the SLEET model.

Thermopressure Coupling Effect Mimicking Natural Graphite Formation to Enhance the Storage K-Ion Performance of Carbonaceous Heterostructures.

Borrowing from natural mechanisms for material design can lead to functional mimicry and improvement. Inspired by graphite formation, a thermopressure coupling strategy under micropressure (<400 Pa) is applied to prepare carbon anodes. A thermopressure response is discovered based on the cellulose precursor. Here, homologous graphene quantum dot/hard carbon (GQD/HC) heterostructures are synthesized. Under 181.4 Pa and 1,200 °C, the product shows a capacity of 310 mAh g-1, while the capacity of the direct carbonization product is only 120 mAh g-1. Prominently, the GQD/HC heterostructure displays marked mechanical strength and flexibility. The experimental and theoretical results illustrate the ion and electron transfer, coordination environment, and electronic states in the GQD/HC heterostructure and elaborate on the origin of the enhanced performance. The thermopressure coupling under micropressure mimics graphite formation, but the heterostructure has better properties than traditional carbon materials. Additionally, micropressure injects new vitality into material research.

Ultrafast charge transfer dynamics of Rhodamine B with graphene oxide.

Graphene and its derivatives, due to their two-dimensional carbon nanostructures, have provided new opportunities to fortify organic dye-based photovoltaic and photocatalytic assemblies. In this article, we employed organic dyes Rhodamine B (RdB) and graphene oxide (GO) [or reduced graphene oxide (RGO)] to assemble the composite materials RdB-GO and RdB-RGO. It was found that both GO and RGO could strongly quench the fluorescence (FL) intensity of RdB. The mechanisms of FL quenching in both RdB-GO and RdB-RGO have been investigated by using femtosecond fluorescence up-conversion and transient absorption spectroscopy. When RdB was anchored on the GO (or RGO) surface, the solvent relaxation component 3.1ps of pure RdB disappeared; instead, the ultrafast excited state electron transfer process (1-2ps) in RdB-GO and RdB-RGO was found and originated from the LUMO of RdB to the conduction band of GO (or RGO). We further reveal that the energy level change caused by GO reduction makes the energy levels of RGO closer to those of RdB, resulting in the electron transfer being more effective in RdB-RGO. Therefore, the RdB-RGO composite materials may have higher application values for dye-sensitized solar cells.

Photoinduced Electron Transfer from the Tryptophan Triplet State in Zn-Azurin.

Tryptophan is one of few residues that participates in biological electron transfer reactions. Upon substitution of the native Cu2+ center with Zn2+ in the blue-copper protein azurin, a long-lived tryptophan neutral radical can be photogenerated. We report the following quantum yield values for Zn-substituted azurin in the presence of the electron acceptor Cu(II)-azurin: formation of the tryptophan neutral radical (Φrad), electron transfer (ΦET), fluorescence (Φfluo), and phosphorescence (Φphos), as well as the efficiency of proton transfer of the cation radical (ΦPT). Increasing the concentration of the electron acceptor increased Φrad and ΦET values and decreased Φphos without affecting Φfluo. At all concentrations of the acceptor, the value of ΦPT was nearly unity. These observations indicate that the phosphorescent triplet state is the parent state of electron transfer and that nearly all electron transfer events lead to proton loss. Similar results regarding the parent state were obtained with a different electron acceptor, [Co(NH3)5Cl]2+; however, Stern-Volmer graphs revealed that [Co(NH3)5Cl]2+ was a more effective phosphorescence quencher (K SV = 230 000 M-1) compared to Cu(II)-azurin (K SV = 88 000 M-1). Competition experiments in the presence of both [Co(NH3)5Cl]2+ and Cu(II)-azurin suggested that [Co(NH3)5Cl]2+ is the preferred electron acceptor. Implications of these results in terms of quenching mechanisms are discussed.

Fatty acid oxidation: a neglected factor in understanding the adjustment of mitochondrial function to cold temperatures.

For ectothermic species, adaptation to thermal changes is of critical importance. Mitochondrial oxidative phosphorylation (OXPHOS), which leverages multiple electron pathways to produce energy needed for survival, is among the crucial metabolic processes impacted by temperature. Our aim in this study was to identify how changes in temperature affect the less-studied electron transferring flavoprotein pathway, fed by fatty acid substrates. We used the planarian Dugesia tigrina, acclimated for 4weeks at 10°C (cold acclimated) or 20°C (normothermic). Respirometry experiments were conducted at an assay temperature of either 10 or 20°C to study specific states of the OXPHOS process using the fatty acid substrates palmitoylcarnitine (long chain), octanoylcarnitine (medium chain) or acetylcarnitine (short chain). Following cold acclimation, octanoylcarnitine exhibited increases in both the OXPHOS and electron transfer (ET, non-coupled) states, indicating that the pathway involved in medium-chain length fatty acids adjusts to cold temperatures. Acetylcarnitine only showed an increase in the OXPHOS state as a result of cold acclimation, but not in the ET state, indicative of a change in phosphorylation system capacity rather than fatty acid β-oxidation. Palmitoylcarnitine oxidation was unaffected. Our results show that cold acclimation in D. tigrina caused a specific adjustment in the capacity to metabolize medium-chain fatty acids rather than an adjustment in the activity of the enzymes carnitine-acylcarnitine translocase, carnitine acyltransferase and carnitine palmitoyltransferase-2. Here, we provide novel evidence of the alterations in fatty acid β-oxidation during cold acclimation in D. tigrina.

Photoinduced Intervalence Charge Transfers: Spectroscopic Tools to Study Fundamental Phenomena and Applications.

The exploitation of excited state chemistry for solar energy conversion or photocatalysis has been continuously increasing, and the needs of a transition to a sustainable human development indicate this trend will continue. In this scenario, the study of mixed valence systems in the excited state offers a unique opportunity to explore excited state electron transfer reactivity, and, in a broader sense, excited state chemistry. This Concept article analyzes recent contributions in the field of photoinduced mixed valence systems, i. e. those where the mixed valence core is absent in the ground state but created upon light absorption. The focus is on the utilization of photoinduced intervalence charge transfer bands, detected via transient absorption spectroscopy, as key tools to study fundamental phenomena like donor/acceptor inversion, hole delocalization, coexistence of excited states and excited state nature, together with applications in molecular electronics.

Brighten Triplet Excitons of Carbon Nanodots for Multicolor Phosphorescence Films.

Triplet excitons usually do not emit light under ambient conditions due to the spin-forbidden transition rule, thus they are called dark excitons. Herein, triplet excitons in carbon nanodots (CNDs) are brightened by embedding the CNDs into poly(vinyl alcohol) (PVA) films; flexible multicolor phosphorescence films are thus demonstrated. PVA chains can isolate the CNDs, and excited state electron or energy transfer induced triplet exciton quenching is thus reduced; while the formed hydrogen bonds between the CNDs and PVA can restrict vibration/rotation of the CNDs, thus further protecting the triplet excitons from nonradiative recombination. The lifetimes of the flexible multicolor phosphorescence films can reach 567, 1387, 726, and 311 ms, and the longest-lasting phosphorescence film can be observed by naked eyes for nearly 15 s even after bending 5000 times. The phosphorescence films can be processed into various patterns, and a dynamic optical signature concept has been proposed and demonstrated based on the phosphorescence films.

Quantum Chemical Characterization and Design of Quantum Dots for Sensing Applications.

The ability to tune the optoelectronic properties of quantum dots (QDs) makes them ideally suited for the use as fluorescence sensing probes. The vast structural diversity in terms of the composition and size of QDs can make designing a QD for a specific sensing application a challenging process. Quantum chemical calculations have the potential to aid this process through the characterization of the properties of QDs, leading to their in silico design. This is explored in the context of QDs for the fluorescence sensing of dopamine based upon density functional theory and time-dependent density functional theory (TDDFT) calculations. The excited states of hydrogenated carbon, silicon, and germanium QDs are characterized through TDDFT calculations. Analysis of the molecular orbital diagrams for the isolated molecules and calculations of the excited states of the dopamine-functionalized quantum dots establish the possibility of a photoinduced electron-transfer process by determining the relative energies of the electronic states formed from a local excitation on the QD and the lowest QD → dopamine electron-transfer state. The results suggest that the Si165H100 and Ge84H64 QDs have the potential to act as fluorescent markers that could distinguish between the oxidized and reduced forms of dopamine, where the fluorescence would be quenched for the oxidized form. The work contributes to a better understanding of the optical and electronic behavior of QD-based sensors and illustrates how quantum chemical calculations can be used to inform the design of QDs for specific fluorescent sensing applications.

Simple Models of Charge-Transfer Reactivity

Abstract: Finite-difference expressions for the chemical potential (negative electronegativity) and hardness (inverse softness) descriptors of molecular and donor-acceptor systems are summarized and chemically “biased” (informed) and “unbiased” (uninformed) estimates of charge-transfer (CT) descriptors in A(acid)⎯B(base) systems are reexamined. The former recognizes the chemical characteristics of reactants and the chemical-potential discontinuity, while in the latter no prior knowledge of such kind is used. The biased chemical potential and fragment hardness descriptors are interpreted in terms of the frontier-electron orbitals, and the equivalence of predictions in both treatments is demonstrated using the electronegativity-equalization principle. Two-state description of CT involves a statistical mixture of initial state |NCT = 0〉 = |A0, B0〉 of the polarized (mutually closed) reactants in R+ = (A+|B+), and one of admissible final states for the full electron transfer, |NCT| = 1, in the forward B0→A0 or reverse A0→B0 directions, leading to ion-pairs |B0→A0〉 = |NCT = 1〉 = |A−1, B+1〉 and |A0→B0〉 = |NCT = −1〉 = |A+1, B−1〉. Parabolic interpolation between energies of the integral-N states identifies the process activation and reaction energies predicts the equilibrium amount of CT and stabilization energy it generates.

Solvated Nuclear-Electronic Orbital Structure and Dynamics.

Nonadiabatic dynamical processes such as proton-coupled electron transfer and excited state intramolecular proton transfer have been the subject of much research. One of the promising theoretical methods to describe these processes is the nuclear-electronic orbital (NEO) approach. This approach inherently accounts for nuclear quantum effects within quantum chemistry calculations, and it has recently been extended to directly simulate nonadiabatic processes with the development of real-time NEO methods. These processes can also be significantly dependent on the surrounding chemical environment, however, and capturing the effects of the environment is often necessary for analyzing experimentally relevant systems. This work couples the NEO density functional theory and real-time time-dependent density functional theory approaches with solvation through the polarizable continuum model. The effects of this coupling are investigated for ground state properties, solvent-dependent vibrational frequencies, and direct excited state intramolecular proton transfer dynamics.

TiO2–rGO nanocomposites with high rGO content and luminescence quenching through green redox synthesis

We developed TiO2–rGO nanocomposites with high exfoliated rGO content upto 47.1% (TG4) by weight hitherto not reported, through green redox synthesis. Progressive reduction of TiO2 nanocrystal size and their in situ intercalation occurred on increasing rGO via one pot synthesis, not reported previously and forming highly stable Ti–O–C bonds. With increase in rGO content, the exfoliation in the nanocomposite was also limited to single-few layered graphene oxide sheets through use of ascorbic acid avoiding restacking, and thereby the recombination of photogenerated carriers. TG4 showed 50% photoluminescence (PL) quenching indicating long-lived electron transfer state with rGO and apparent rate of nonradiative excited state decay of 1.15 × 108 s−1. Details of lattice orientation, Raman spectra, electronic states and PL lifetime decay are discussed to elucidate effective charge carrier separation in the nanocomposite. Near complete photodegradation of Alizarin Yellow GG azo dye, an industrial pollutant, could be obtained under direct sunlight using TG4 as catalyst.

Theoretical Investigations on the Detecting Mechanism of a Typical 2,4,6-Trinitrophenol Fluorescence Sensor and Its Design Strategy.

Fluorescence sensors based on small organic molecules are drawing increasing attention. In this contribution, the underlying detection mechanism of a typical fluorescence sensor for 2,4,6-trinitrophenol (TNP) based on fluorescence quenching is comprehensively investigated. The TNP molecule is proved to plant an intermolecular electron transfer state (dark state) below the bright state. Strong π-π interaction is observed between the sensor and TNP, which provides considerable orbital overlaps between the sensor and analyte. Electron transfer from the sensor to analyte is facilitated by such a strong interaction, which quenches the sensor's fluorescence. The design strategy for such TNP sensors is proposed based on the detection mechanism, and a series of new sensors is designed, which is likely to have better sensitivity than the original sensor.

Theoretical investigation of [Ru(bpy)2(HAT)]2+ (HAT = 1,4,5,8,9,12-hexaazatriphenylene; bpy = 2,2′-bipyridine): Photophysics and reactions in excited state

In this article, Density Functional Theory based calculations, including dispersion corrections, PBE0(D3BJ)/Def2-TZVP(-f), were performed to elucidate the photophysics of the [Ru(bpy)2(HAT)]2+ complex in water. In addition, the thermodynamics of the charge and electron transfer excited state reactions of this complex with oxygen, nitric oxide and Guanosine-5′-monophosphate nucleotide (GMP) were investigated. The first singlet excite state, S1, strongly couples with the second and third triplet excited states (T2 and T3) giving rise to a high intersystem crossing rate of 6.26 × 1011 s−1 which is ∼106 greater than the fluorescence rate decay. The thermodynamics of the excited reactions revealed that all electron transfer reactions investigated are highly favorable, due mainly to the high stability of the triply charged radical cation 2PS•3+ species formed after the electron has been transferred. Excited state electron transfer from the GMP nucleotide to the complex is also highly favorable (ΔGsol = −92.6 kcal/mol), showing that this complex can be involved in the photooxidation of DNA, in line with experimental findings. Therefore, the calculations allow to conclude that the [Ru(bpy)2(HAT)]2+ complex can act in Photodynamic therapy through both mechanisms type I and II, through electron transfer from and to the complex and triplet–triplet energy transfer, generating ROS, RNOS and through DNA photooxidation. In addition, the work also opens a perspective of using this complex for the in-situ generation of the singlet nitroxyl (1NO−) species, which can have important applications for the generation of HNO and may have, therefore, important impact for physiological studies involving HNO.

Reversibly switchable methanofullerene by photoexcitation and reduction.

A cyclopropanated derivative of the trifluoromethylated fullerene Cs-C70(CF3)8 demonstrates reversible switching behavior triggered by excited state electron transfer or by negative charging. The switching between the state with connected 62-electron π-system and the state with disjoint 28- and 32-electron conjugated caps is effected by opening/closure of the cyclopropanated bond. A pronounced alteration of the electronic properties upon seemingly minor changes in a large fullerene molecule is an attractive feature for the organic electronic devices where similar fullerene compounds are commonly utilized as electron acceptor materials.