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1.
Proc Natl Acad Sci U S A ; 118(42)2021 Oct 19.
Artigo em Inglês | MEDLINE | ID: mdl-34625473
2.
Inorg Chem ; 2021 Sep 29.
Artigo em Inglês | MEDLINE | ID: mdl-34585577

RESUMO

A new series of strongly coupled oscillators based upon (porphinato)Pd, (porphinato)Pt, and bis(terpyridyl)ruthenium(II) building blocks is described. These RuPPd, RuPPt, RuPPdRu, and RuPPtRu chromophores feature bis(terpyridyl)Ru(II) moieties connected to the (porphinato)metal unit via an ethyne linker that bridges the 4'-terpyridyl and porphyrin macrocycle meso-carbon positions. Pump-probe transient optical data demonstrate sub-picosecond excited singlet-to-triplet-state relaxation. The relaxed lowest-energy triplet (T1) excited states of these chromophores feature absorption manifolds that span the 800-1200 nm spectral region, microsecond triplet-state lifetimes, and large absorptive extinction coefficients [ε(T1 → Tn) > 4 × 104 M-1 cm-1]. Dynamic hyperpolarizability (ßλ) values were determined from hyper-Rayleigh light scattering (HRS) measurements carried out at several incident irradiation wavelengths over the 800-1500 nm spectral region. Relative to benchmark RuPZn and RuPZnRu chromophores which showed large ßHRS values over the 1200-1600 nm range, RuPPd, RuPPt, RuPPdRu, and RuPPtRu displayed large ßHRS values over the 850-1200 nm region. Generalized Thomas-Kuhn sum (TKS) rules and experimental hyperpolarizability values were utilized to determine excited state-to-excited state transition dipole terms from experimental electronic absorption data and thus assessed frequency-dependent ßλ values, including two- and three-level contributions for both ßzzz and ßxzx tensor components to the RuPPd, RuPPt, RuPPdRu, and RuPPtRu hyperpolarizability spectra. These analyses qualitatively rationalize how the ßzzz and ßxzx tensor elements influence the observed irradiation wavelength-dependent hyperpolarizability magnitudes. The TKS analysis suggests that supermolecules related to RuPPd, RuPPt, RuPPdRu, and RuPPtRu will likely feature intricate dependences of experimentally determined ßHRS values as a function of irradiation wavelength that derive from substantial singlet-triplet mixing, and complex interactions among multiple different ß tensor components that modulate the long wavelength regime of the nonlinear optical response.

3.
J Chem Phys ; 155(5): 055102, 2021 Aug 07.
Artigo em Inglês | MEDLINE | ID: mdl-34364335

RESUMO

Ratcheted multi-step hopping electron transfer systems can plausibly produce directional charge transport over very large distances without requiring a source-drain voltage bias. We examine molecular strategies to realize ratcheted charge transport based on multi-step charge hopping, and we illustrate two ratcheting mechanisms with examples based on DNA structures. The charge transport times and currents that may be generated in these assemblies are also estimated using kinetic simulations. The first ratcheting mechanism described for nanoscale systems requires local electric fields on the 109 V/m scale to realize nearly 100% population transport. The second ratcheting mechanism for even larger systems, based on electrochemical gating, is estimated to generate currents as large as 0.1 pA for DNA structures that are a few µm in length with a gate voltage of about 5 V, a magnitude comparable to currents measured in DNA wires at the nanoscale when a source-drain voltage bias of similar magnitude is applied, suggesting an approach to considerably extend the distance range over which DNA charge transport devices may operate.


Assuntos
DNA/química , Nanoestruturas/química , Condutividade Elétrica , Eletroquímica , Cinética , Eletricidade Estática
4.
J Phys Chem B ; 125(28): 7763-7773, 2021 07 22.
Artigo em Inglês | MEDLINE | ID: mdl-34235935

RESUMO

Electron transport through aromatic species (especially tryptophan and tyrosine) plays a central role in water splitting, redox signaling, oxidative damage protection, and bioenergetics. The cytochrome c peroxidase (CcP)-cytochrome c (Cc) complex (CcP:Cc) is used widely to study interprotein electron transfer (ET) mechanisms. Tryptophan 191 (Trp191) of CcP supports hole hopping charge recombination in the CcP:Cc complex. Experimental studies find that when Trp191 is substituted by tyrosine, phenylalanine, or redox-active aniline derivatives bound in the W191G cavity, enzymatic activity and charge recombination rates both decrease. Theoretical analysis of these CcP:Cc complexes finds that the ET kinetics depend strongly on the chemistry of the modified Trp site. The computed electronic couplings in the W191F and W191G species are orders of magnitude smaller than in the native protein, due largely to the absence of a hopping intermediate and the large tunneling distance. Small molecules bound in the W191G cavity are weakly coupled electronically to the Cc heme, and the structural disorder of the guest molecule in the binding pocket may contribute further to the lack of enzymatic activity. The couplings in W191Y are not substantially weakened compared to the native species, but the redox potential difference for tyrosine vs tryptophan oxidation accounts for the slower rate in the Tyr mutant. Thus, theoretical analysis explains why only the native Trp supports rapid hole hopping in the CcP:Cc complex. Favorable free energies and electronic couplings are essential for establishing an efficient hole hopping relay in this protein-protein complex.


Assuntos
Citocromo-c Peroxidase , Citocromo-c Peroxidase/genética , Citocromo-c Peroxidase/metabolismo , Citocromos c/genética , Citocromos c/metabolismo , Transporte de Elétrons , Cinética , Oxirredução
5.
J Biol Chem ; 297(1): 100857, 2021 07.
Artigo em Inglês | MEDLINE | ID: mdl-34097877

RESUMO

The hexameric low-pH stress response enzyme oxalate decarboxylase catalyzes the decarboxylation of the oxalate mono-anion in the soil bacterium Bacillus subtilis. A single protein subunit contains two Mn-binding cupin domains, and catalysis depends on Mn(III) at the N-terminal site. The present study suggests a mechanistic function for the C-terminal Mn as an electron hole donor for the N-terminal Mn. The resulting spatial separation of the radical intermediates directs the chemistry toward decarboxylation of the substrate. A π-stacked tryptophan pair (W96/W274) links two neighboring protein subunits together, thus reducing the Mn-to-Mn distance from 25.9 Å (intrasubunit) to 21.5 Å (intersubunit). Here, we used theoretical analysis of electron hole-hopping paths through redox-active sites in the enzyme combined with site-directed mutagenesis and X-ray crystallography to demonstrate that this tryptophan pair supports effective electron hole hopping between the C-terminal Mn of one subunit and the N-terminal Mn of the other subunit through two short hops of ∼8.5 Å. Replacement of W96, W274, or both with phenylalanine led to a large reduction in catalytic efficiency, whereas replacement with tyrosine led to recovery of most of this activity. W96F and W96Y mutants share the wildtype tertiary structure. Two additional hole-hopping networks were identified leading from the Mn ions to the protein surface, potentially protecting the enzyme from high Mn oxidation states during turnover. Our findings strongly suggest that multistep hole-hopping transport between the two Mn ions is required for enzymatic function, adding to the growing examples of proteins that employ aromatic residues as hopping stations.


Assuntos
Bacillus subtilis/ultraestrutura , Carboxiliases/química , Elétrons , Oxigênio/metabolismo , Bacillus subtilis/química , Bacillus subtilis/genética , Sítios de Ligação/genética , Carboxiliases/genética , Carboxiliases/ultraestrutura , Catálise , Domínio Catalítico/genética , Cristalografia por Raios X , Cinética , Manganês/química , Oxigênio/química , Triptofano/química , Triptofano/genética
6.
Biochemistry ; 60(17): 1368-1378, 2021 05 04.
Artigo em Inglês | MEDLINE | ID: mdl-33870693

RESUMO

The flow of charge through molecules is central to the function of supramolecular machines, and charge transport in nucleic acids is implicated in molecular signaling and DNA repair. We examine the transport of electrons through nucleic acids to understand the interplay of resonant and nonresonant charge carrier transport mechanisms. This study reports STM break junction measurements of peptide nucleic acids (PNAs) with a G-block structure and contrasts the findings with previous results for DNA duplexes. The conductance of G-block PNA duplexes is much higher than that of the corresponding DNA duplexes of the same sequence; however, they do not display the strong even-odd dependence conductance oscillations found in G-block DNA. Theoretical analysis finds that the conductance oscillation magnitude in PNA is suppressed because of the increased level of electronic coupling interaction between G-blocks in PNA and the stronger PNA-electrode interaction compared to that in DNA duplexes. The strong interactions in the G-block PNA duplexes produce molecular conductances as high as 3% G0, where G0 is the quantum of conductance, for 5 nm duplexes.


Assuntos
DNA/metabolismo , Modelos Biológicos , Transporte Biológico , Ácidos Nucleicos Peptídicos/metabolismo
7.
J Phys Chem A ; 2021 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-33449684

RESUMO

Quantum coherence effects on charge transfer and spin dynamics in a system having two degenerate electron acceptors are studied using a zinc 5,10,15-tri(n-pentyl)-20-phenylporphyrin (ZnP) electron donor covalently linked to either one or two naphthalene-1,8:4,5-bis(dicarboximide) (NDI) electron acceptors using an anthracene (An) spacer, ZnP-An-NDI (1) and ZnP-An-NDI2 (2), respectively. Following photoexcitation of 1 and 2 in toluene at 295 K, femtosecond transient absorption spectroscopy shows that the electron transfer (ET) rate constant for 2 is about three times larger than that of 1, which can be accounted for by the statistical nature of incoherent ET as well as the electron couplings for the charge separation reactions. In contrast, the rate constant for charge recombination (CR) of 1 is about 25% faster than that of 2. Using femtosecond transient infrared spectroscopy and theoretical analysis, we find that the electron on NDI2•- in 2 localizes onto one of the two NDIs prior to CR, thus precluding electronically coherent CR from NDI2•-. Conversely, CR in both 1 and 2 is spin coherent as indicated by the observation of a resonance in the 3*ZnP yield following CR as a function of applied magnetic field, giving spin-spin exchange interaction energies of 2J = 210 and 236 mT, respectively, where the line width of the resonance for 2 is greater than 1. These data show that while CR is a spin-coherent process, incoherent hopping of the electron between the two NDIs in 2, consistent with the lack of delocalization noted above, results in greater spin decoherence in 2 relative to 1.

8.
J Phys Chem B ; 125(1): 17-23, 2021 01 14.
Artigo em Inglês | MEDLINE | ID: mdl-33371674

RESUMO

Experimental evidence suggests that DNA-mediated redox signaling between high-potential [Fe4S4] proteins is relevant to DNA replication and repair processes, and protein-mediated charge transfer (CT) between [Fe4S4] clusters and nucleic acids is a fundamental process of the signaling and repair mechanisms. We analyzed the dominant CT pathways in the base excision repair glycosylase MutY using molecular dynamics simulations and hole hopping pathway analysis. We find that the adenine nucleobase of the mismatched A·oxoG DNA base pair facilitates [Fe4S4]-DNA CT prior to adenine excision by MutY. We also find that the R153L mutation in MutY (linked to colorectal adenomatous polyposis) influences the dominant [Fe4S4]-DNA CT pathways and appreciably decreases their effective CT rates.


Assuntos
DNA Glicosilases , Dano ao DNA , DNA Glicosilases/genética , DNA Glicosilases/metabolismo , Reparo do DNA , Guanina , Mutação , N-Glicosil Hidrolases/metabolismo
9.
Chem Sci ; 11(27): 7076-7085, 2020 Jul 21.
Artigo em Inglês | MEDLINE | ID: mdl-33250976

RESUMO

Growing experimental evidence indicates that iron-sulfur proteins play key roles in DNA repair and replication. In particular, charge transport between [Fe4S4] clusters, mediated by proteins and DNA, may convey signals to coordinate enzyme action. Human primase is a well studied [Fe4S4] protein, and its p58c domain (which contains an [Fe4S4] cluster) plays a role in the initiation of DNA replication. The Y345C mutation in p58c is linked to gastric tumors and may influence the protein-mediated charge transport. The complexity of protein-DNA systems, and the intricate electronic structure of [Fe4S4] clusters, have impeded progress into understanding functional charge transport in these systems. In this study, we built force fields to describe the high potential [Fe4S4] cluster in both oxidation states. The parameterization is compatible with AMBER force fields and enabled well-balanced molecular dynamics simulations of the p58c-RNA/DNA complex relevant to the initiation of DNA replication. Using the molecular mechanics Poisson-Boltzmann and surface area solvation method on the molecular dynamics trajectories, we find that the p58c mutation induces a modest change in the p58c-duplex binding free energy in agreement with recent experiments. Through kinetic modeling and analysis, we identify key features of the main charge transport pathways in p58c. In particular, we find that the Y345C mutation partially changes the composition and frequency of the most efficient (and potentially relevant to the biological function) charge transport pathways between the [Fe4S4] cluster and the duplex. Moreover, our approach sets the stage for a deeper understanding of functional charge transfer in [Fe4S4] protein-DNA complexes.

10.
Matter ; 3(1): 166-179, 2020 Jul 01.
Artigo em Inglês | MEDLINE | ID: mdl-33103114

RESUMO

Water molecules can mediate charge transfer in biological and chemical reactions by forming electronic coupling pathways. Understanding the mechanism requires a molecular-level electrical characterization of water. Here, we describe the measurement of single water molecular conductance at room temperature, characterize the structure of water molecules using infrared spectroscopy, and perform theoretical studies to assist in the interpretation of the experimental data. The study reveals two distinct states of water, corresponding to a parallel and perpendicular orientation of the molecules. Water molecules switch from parallel to perpendicular orientations on applying an electric field, producing switching from high to low conductance states, thus enabling the determination of single water molecular dipole moments. The work further shows that water-water interactions affect the atomic scale configuration and conductance of water molecules. These findings demonstrate the importance of the discrete nature of water molecules in electron transfer and set limits on water-mediated electron transfer rates.

11.
J Phys Chem B ; 124(29): 6376-6388, 2020 07 23.
Artigo em Inglês | MEDLINE | ID: mdl-32600048

RESUMO

The development of light-harvesting devices based on molecular materials depends critically on the ability to focus the electronic oscillator strength of molecules into the UV-vis spectral window. Typical molecular chromophores have only about 1% of their total electronic oscillator strength in this spectral region and thus perform at a small fraction of their possible effectiveness. This theoretical study finds that the electronic oscillator strength of polyenes in the UV-vis region may be enhanced by 1 order of magnitude using electrostatic fields, motivating specific experimental studies of oscillator strength focusing. We find scaling relationships between the polyene length, the intensity of the applied field, and the field-induced increase in oscillator strength that are useful for the implementation of light-harvesting strategies based on polyenes.

12.
J Phys Chem B ; 124(17): 3441-3446, 2020 04 30.
Artigo em Inglês | MEDLINE | ID: mdl-32349484
13.
J Phys Chem B ; 124(16): 3428-3435, 2020 04 23.
Artigo em Inglês | MEDLINE | ID: mdl-32272019

RESUMO

The extent of electronic wave function delocalization for the charge carrier (electron or hole) in double helical DNA plays an important role in determining the DNA charge transfer mechanism and kinetics. The size of the charge carrier's wave function delocalization is regulated by the solvation induced localization and the quantum delocalization among the π stacked base pairs at any instant of time. Using a newly developed localized orbital scaling correction (LOSC) density functional theory method, we accurately characterized the quantum delocalization of the hole wave function in double helical B-DNA. This approach can be used to diagnose the extent of delocalization in fluctuating DNA structures. Our studies indicate that the hole state tends to delocalize among 4 guanine-cytosine (GC) base pairs and among 3 adenine-thymine (AT) base pairs when these adjacent bases fluctuate into degeneracy. The relatively small delocalization in AT base pairs is caused by the weaker π-π interaction. This extent of delocalization has significant implications for assessing the role of coherent, incoherent, or flickering coherent carrier transport in DNA.


Assuntos
Guanina , Timina , Pareamento de Bases , Citosina , DNA/genética , Teoria Quântica
14.
Sens Actuators B Chem ; 3102020 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-32296265

RESUMO

Photosensitive proteins are naturally evolved photosensors that often respond to light signals of specific wavelengths. However, their poor stability under ambient conditions hinders their applications in non-biological settings. In this proof-of-principle study, we grafted the blue light using flavin (BLUF) protein reconstructed with flavin adenine dinucleotide (FAD) or roseoflavin (RoF) onto pristine graphene, and achieved selective sensitivity at 450 nm or 500 nm, respectively. We improved the thermal and operational stability substantially via structure-guided cross-linking, achieving 6-month stability under ambient condition and normal operation at temperatures up to 200 °C. Furthermore, the device exhibited rare negative photoconductivity behavior. The origins of this negative photoconductivity behavior were elucidated via a combination of experimental and theoretical analysis. In the photoelectric conversion studies, holes from photoexcited flavin migrated to graphene and recombined with electrons. The device allows facile modulation and detection of charge transfer, and provides a versatile platform for future studies of photoinduced charge transfer in biosensors as well as the development of stable wavelength-selective biophotosensors.

15.
Phys Chem Chem Phys ; 22(17): 9664-9676, 2020 May 06.
Artigo em Inglês | MEDLINE | ID: mdl-32329504

RESUMO

Electron transfer (ET) in donor-bridge-acceptor (DBA) compounds depends strongly on the structural and electronic properties of the bridge. Among the bridges that support donor-acceptor conjugation, alkyne bridges have attractive and unique properties: they are compact, possess linear structure permitting access to high symmetry DBA molecules, and allow torsional motion of D and A, especially for longer bridges. We report conformation dependent electron transfer dynamics in a set of novel DBA compounds featuring butadiyne (C4) bridge, N-isopropyl-1,8-napthalimide (NAP) acceptors, and donors that span a range of reduction potentials (trimethyl silane (Si-C4-NAP), phenyl (Ph-C4-NAP), and dimethyl aniline (D-C4-NAP)). Transient mid-IR absorption spectra of the C[triple bond, length as m-dash]C bridge stretching modes, transient spectra in the visible range, and TD-DFT calculations were used to decipher the ET mechanisms. We found that the electronic excited state energies and, especially, the transition dipoles (S0 → Sn) depend strongly on the dihedral angle (θ) between D and A and the frontier orbital symmetry, offering an opportunity to photo-select particular excited states with specific ranges of dihedral angles by exciting at chosen wavelengths. For example, excitation of D-C4-NAP at 400 nm predominantly prepares an S1 excited state in the planar conformations (θ ∼ 0) but selects an S2 state with θ ∼ 90°, indicating the dominant role of the molecular symmetry in the photophysics. Moreover, the symmetry of the frontier orbitals of such DBA compounds not only defines the photo-selection outcome, but also determines the rate of the S2 → S1 charge separation reaction. Unprecedented variation of the S2-S1 electronic coupling with θ by over four orders of magnitude results in slow ET at θ ca. 0° and 90° but extremely fast ET at θ of 20-60°. The unique features of high-symmetry alkyne bridged DBA structures enable frequency dependent ET rate selection and make this family of compounds promising targets for the vibrational excitation control of ET kinetics.

16.
J Phys Chem B ; 123(49): 10456-10462, 2019 12 12.
Artigo em Inglês | MEDLINE | ID: mdl-31710233

RESUMO

We examine the relative magnitudes of electronic coupling HDA in two face-to-face rigid and diastereomeric (porphinato)zinc(II)-quinone (PZn-Q) assemblies, 1ß-ZnA and 1ß-ZnB, in which the six quinonyl carbon atoms lie in virtually identical arrangements relative to the PZn plane at sub-van der Waals donor-acceptor (D-A) interplanar separations. Steady-state and time-resolved transient optical data and computational studies show that minor differences in relative D-A cofacial orientation give rise to disparate HDA magnitudes for both photoinduced charge separation (CS) and thermal charge recombination (CR). Time-dependent density functional theory (TDDFT) computations illuminate the nature of direct charge transfer states and the electronic structural factors that give rise to these differential HDAs. These data show more extensive mixing of locally excited (LE) and CS states in 1ß-ZnA relative to 1ß-ZnB and that these HDA differences track the magnitudes of electronic coupling matrix elements determined from steady-state electronic spectral data and thermal CR rate constants measured via pump-probe spectroscopy. Collectively, this work shows that electron transfer dynamics may be manipulated in cofacial D-A systems, even at sub-van der Waals contact, provided that conformational rigidity precludes structural fluctuations that modulate D-A interactions on the charge transfer time scale.


Assuntos
Benzoquinonas/química , Teoria da Densidade Funcional , Elétrons , Porfirinas/química , Fatores de Tempo
17.
Inorg Chem ; 58(22): 15487-15497, 2019 Nov 18.
Artigo em Inglês | MEDLINE | ID: mdl-31697481

RESUMO

Donor-bridge-acceptor (D-B-A) systems with a polarizable bridge can afford rapid photoinduced electron transfer dynamics that may be susceptible to rate modulation by infrared excitation. We describe the synthesis, characterization, and electronic structure of a class of readily assembled D-B-A structures linked by a cobalt cyclam bridge. The reaction between [Co(cyclam)Cl2]Cl and 4-ethynyl-N-isopropyl-1,8-naphthalimide (HC2NAPiPr) yields [Co(cyclam)(C2NAPiPr)Cl]Cl (1), which reacts with LiC2Y at -78 °C to afford [Co(cyclam)(C2NAPiPr)(C2D)]Cl with D as C6H4-4-NMe2 (2a), NAPiPr (2b), Ph (2c), and C6H4-4-N(4-MeOPh)2 (2d). Molecular structures of 1 and 2a were established using single-crystal X-ray diffraction, while the redox properties and fluorescence profiles of compounds 1 and 2 were examined using voltammetric and steady-state emission techniques, respectively. The electronic structures and photophysical properties of these compounds were studied using density functional theory and time-dependent density functional theory methods. The excited-state dynamics of compounds 1, 2a, and 2d were explored using femtosecond transient absorption spectroscopy with 400 nm excitation and detection in both the visible and mid-IR spectral regions. Formation of a long-lived excited state was complete within 20 ps of excitation in all three compounds. Ultrafast spectral changes observed in 2a and 2d within the first 20 ps indicated the formation of a charge separated state (CS state, D+-B-A-) with characteristic times of less than 0.1 and 0.25 ps, respectively. The CS state undergoes rapid charge recombination (8 ps in 2a and 4 ps in 2d). The CS dynamics is facilitated by the Co center, which mixes the bright NAP-centered electronic state with a pure CS state. The mixing strength depends on the donor energetics and conformation, which significantly influences the charge transfer dynamics in 2a and 2d.

18.
Chem Commun (Camb) ; 55(79): 11823-11832, 2019 Oct 01.
Artigo em Inglês | MEDLINE | ID: mdl-31515543

RESUMO

Electron bifurcation moves electrons from a two-electron donor to reduce two spatially separated one-electron acceptors. If one of the electrons reduces a high-potential (lower energy) acceptor, then the other electron may proceed "uphill" to reduce a low-potential (higher energy) acceptor. This mechanism is now considered the third mode of energy transduction in biology, and offers promise for the development of novel bioinspired energy conversion strategies. Nature uses electron bifurcation to realize highly sought-after reactions: reversible CO2 reduction, nitrogen fixation, and hydrogen production. In this review, we summarize the current understanding of electron bifurcation, including both recent progress and outstanding questions in understanding and developing artificial electron bifurcation systems.

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