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We discuss the possibility of using circularly polarized luminescence (CPL) as a tool to probe individual triplet spin sublevels that are populated nonadiabatically following photoexcitation. This study is motivated by a mechanism proposed for chirality-induced spin selectivity in which coupled electronic-nuclear dynamics may lead to a non-statistical population of the three triplet sublevels in chiral systems. We find that low-temperature CPL should aid in quantifying the exact spin state/s populated through coupled electronic-nuclear motion in chiral molecules. [ABSTRACT FROM AUTHOR]

The article discusses the chiral induced spin selectivity effect (CISS), which is the finding that the motion of an electron within or through chiral systems depends on the spin of that electron. The article explains that while the effect has been observed experimentally, developing a quantitative theoretical description has been challenging. The article also highlights the different types of experimental measurements that have been used to study CISS, including measurements of spin-dependent transmission, tunneling currents, magnetization, and magnetic domains. The article concludes by discussing the potential applications of CISS in spintronics, electrochemistry, and biology, and expresses optimism that further research will reveal the mechanism behind the CISS effect. [Extracted from the article]

Chiral symmetry is ubiquitous in Biology, Physics, and Chemistry. The biomolecules essential for life on Earth—such as deoxyribonucleic acid (DNA), sugars, and proteins—display homochirality that affects their function in biological processes. Ten years ago, it was discovered that electron transfer through chiral molecules depends on the direction of the electron spin, and more recently, it was shown that the charge displacement in chiral molecules creates transient spin polarization. Thus, the properties of ferromagnet/chiral molecule interfaces are affected by spin exchange interactions, via the overlap of the chiral molecule with the ferromagnet's spin wave function. This effect offers a mechanism for homochiral bias in Biology, which was previously unappreciated, and an approach to enantioselective chemistry and chiral separations, which is controlled by the electron spin. [ABSTRACT FROM AUTHOR]

Recent experiments have demonstrated that the electron transmission yield through chiral molecules depends on the electron spin orientation. This phenomenon has been termed the chiral-induced spin selectivity (CISS) effect, and it provides a challenge to theory and promise for organic molecule-based spintronic devices. This article reviews recent developments in our understanding of CISS. Different theoretical models have been used to describe the effect; however, they all presume an unusually large spin-orbit coupling in chiral molecules for the effect to display the magnitudes seen in experiments. A simplified model for an electron's transport through a chiral potential suggests that these large couplings can be manifested. Techniques for measuring spin-selective electron transport through molecules are overviewed, and some examples of recent experiments are described. Finally, we present results obtained by studying several systems, and we describe the possible application of the CISS effect for memory devices. [ABSTRACT FROM AUTHOR]

Central to theories of electron transfer (ET) is the idea that nuclear motion generates a transition state that enables electron flow to proceed, but nuclear motion also induces fluctuations in the donor–acceptor (DA) electronic coupling that is the rate–limiting parameter for nonadiabatic ET The interplay between the DA energy gap and DA coupling fluctuations is particularly noteworthy in biological ET, where flexible protein and mobile water bridges take center stage. Here, we discuss the critical timescales at play for ET reactions in fluctuating media, highlighting issues of the Condon approximation, average medium versus fluctuation–controlled electron tunneling, gated and solvent relaxation controlled electron transfer, and the influence of inelastic tunneling on electronic coupling pathway interferences. Taken together, one may use this framework to establish principles to describe how macromolecular structure and structural fluctuations influence ET reactions. This framework deepens our understanding of ET chemistry in fluctuating media. Moreover, it provides a unifying perspective for biophysical charge–transfer processes and helps to frame new questions associated with energy harvesting and transduction in fluctuating media. [ABSTRACT FROM AUTHOR]

Abstract: Recent advances in the study of protein interfacial electron transfer are described. Special emphasis is given to cytochrome c/self-assembled monolayer/electrode assemblies. Results on the ionic strength dependence of the formal potential, the change of electron transfer mechanism with increase of electron tunneling distance, and the most probable electron tunneling pathway are discussed. [Copyright &y& Elsevier]

The electron-transfer rate constant is measured in two U-shaped donor-bridge-acceptor molecules over a wide range of temperature in acetonitrile and N-methylacetamide (NMA). The electron-transfer rate at high temperature can be well described by a nonadiabatic model of the reaction, but at low temperatures the rate in NMA becomes controlled by the solvent. The results are discussed in terms of theoretical models for the change in reaction mechanism and its dependence on the solute-solvent frictional coupling. [ABSTRACT FROM AUTHOR]

Chirality in life has been preserved throughout evolution. It has been assumed that the main function of chirality is its contribution to structural properties. In the past two decades, however, it has been established that chiral molecules possess unique electronic properties. Electrons that pass through chiral molecules, or even charge displacements within a chiral molecule, do so in a manner that depends on the electron's spin and the molecule's enantiomeric form. This effect, referred to as chiral induced spin selectivity (CISS), has several important implications for the properties of biosystems. Among these implications, CISS facilitates long-range electron transfer, enhances bio-affinities and enantioselectivity, and enables efficient and selective multi-electron redox processes. In this article, we review the CISS effect and some of its manifestations in biological systems. We argue that chirality is preserved so persistently in biology not only because of its structural effect, but also because of its important function in spin polarizing electrons. [ABSTRACT FROM AUTHOR]

This work systematically evaluates the effect of array periodicity on the near infrared transmission characteristics of annular aperture arrays (AAAs) in gold films. Both the experimental and theoretical transmission spectra of AAAs are shown to be sensitive to the period and the arrangement of the apertures within the array. The spectra of square arrays with periods ranging from 1400 to 600 nm show a strong correlation with surface plasmon polariton (SPP)-Bloch modes of the metal/dielectric interfaces. For rectangular AAAs the transmission spectra are significantly attenuated and reveal a polarization sensitivity that arises from the breaking of the symmetry and degeneracy of the SPP-Bloch modes. [ABSTRACT FROM AUTHOR]

Studies the electron transfer through an organized organic monolayer of alkyl chains absorbed on a silicon wafer. Use of the silicon as an electrode in the electrochemical cell; Measurement of the charge transfer efficiency; Suggestion for a mechanism rationalizing all observations.

Covalent bonding interactions determine the energy–momentum (E–k) dispersion (band structure) of solid-state materials. Here, we show that noncovalent interactions can modulate the E–k dispersion near the Fermi level of a low-dimensional nanoscale conductor. We demonstrate that low energy band gaps may be opened in metallic carbon nanotubes through polymer wrapping of the nanotube surface at fixed helical periodicity. Electronic spectral, chiro-optic, potentiometric, electronic device, and work function data corroborate that the magnitude of band gap opening depends on the nature of the polymer electronic structure. Polymer dewrapping reverses the conducting-to- semiconducting phase transition, restoring the native metallic carbon nanotube electronic structure. These results address a long-standing challenge to develop carbon nanotube electronic structures that are not realized through disruption of π conjugation, and establish a roadmap for designing and tuning specialized semiconductors that feature band gaps on the order of a few hundred meV. [ABSTRACT FROM AUTHOR]

Chiral perovskite nanoparticles and films are promising for integration in emerging spintronic and optoelectronic technologies, yet few design rules exist to guide the development of chiral material properties. The chemical space of potential building blocks for these nanostructures is vast, and the mechanisms through which organic ligands can impart chirality to the inorganic perovskite lattice are not well understood. In this work, we investigate how the properties of chiral ammonium ligands, the most common organic ligand type used with perovskites, affect the circular dichroism of strongly quantum confined CsPbBr3 nanocrystals. We show that aromatic ammonium ligands with stronger electron-donating groups lead to higher-intensity circular dichroism associated with the lowest-energy excitonic transition of the perovskite nanocrystal. We argue that this behavior is best explained by a modulation of the exciton wavefunction overlap between the nanocrystal and the organic ligand, as the functional groups on the ligand can shift electron density toward the organic species-perovskite lattice interface to increase the imprinting. [ABSTRACT FROM AUTHOR]

We investigate a spin-boson inspired model of electron transfer, where the diabatic coupling is given by a position-dependent phase, eiWx. We consider both equilibrium and nonequilibrium initial conditions. We show that, for this model, all equilibrium results are completely invariant to the sign of W (to infinite order). However, the nonequilibrium results do depend on the sign of W, suggesting that photo-induced electron transfer dynamics with spin–orbit coupling can exhibit electronic spin polarization (at least for some time). [ABSTRACT FROM AUTHOR]

Biological structures rely on kinetically tuned charge transfer reactions for energy conversion, biocatalysis, and signaling as well as for oxidative damage repair. Unlike man-made electrical circuitry, which uses metals and semiconductors to direct current flow, charge transfer in living systems proceeds via biomolecules that are nominally insulating. Long-distance charge transport, which is observed routinely in nucleic acids, peptides, and proteins, is believed to arise from a sequence of thermally activated hopping steps. However, a growing number of experiments find limited temperature dependence for electron transfer over tens of nanometers. To account for these observations, we propose a temperature-independent mechanism based on the electric potential difference that builds up along the molecule as a precursor of electron transfer. Specifically, the voltage changes the nature of the electronic states away from being sharply localized so that efficient resonant tunneling across long distances becomes possible without thermal assistance. This mechanism is general and is expected to be operative in molecules where the electronic states densely fill a wide energy window (on the scale of electronvolts) above or below the gap between the highest-occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO). We show that this effect can explain the temperature-independent charge transport through DNA and the strongly voltage-dependent currents that are measured through organic semiconductors and peptides. [ABSTRACT FROM AUTHOR]

Conspectus: Molecular spintronics (spin + electronics), which aims to exploit both the spin degree of freedom and the electron charge in molecular devices, has recently received massive attention. Our recent experiments on molecular spintronics employ chiral molecules which have the unexpected property of acting as spin filters, by way of an effect we call “chiral-induced spin selectivity” (CISS). In this Account, we discuss new types of spin-dependent electrochemistry measurements and their use to probe the spin-dependent charge transport properties of nonmagnetic chiral conductive polymers and biomolecules, such as oligopeptides, L/D cysteine, cytochrome c, bacteriorhodopsin (bR), and oligopeptide-CdSe nanoparticles (NPs) hybrid structures. Spin-dependent electrochemical measurements were carried out by employing ferromagnetic electrodes modified with chiral molecules used as the working electrode. Redox probes were used either in solution or when directly attached to the ferromagnetic electrodes. During the electrochemical measurements, the ferromagnetic electrode was magnetized either with its magnetic moment pointing “UP” or “DOWN” using a permanent magnet (H = 0.5 T), placed underneath the chemically modified ferromagnetic electrodes. The spin polarization of the current was found to be in the range of 5–30%, even in the case of small chiral molecules. Chiral films of the l- and d-cysteine tethered with a redox-active dye, toludin blue O, show spin polarizarion that depends on the chirality. Because the nickel electrodes are susceptible to corrosion, we explored the effect of coating them with a thin gold overlayer. The effect of the gold layer on the spin polarization of the electrons ejected from the electrode was investigated. In addition, the role of the structure of the protein on the spin selective transport was also studied as a function of bias voltage and the effect of protein denaturation was revealed. In addition to “dark” measurements, we also describe photoelectrochemical measurements in which light is used to affect the spin selective electron transport through the chiral molecules. We describe how the excitation of a chromophore (such as CdSe nanoparticles), which is attached to a chiral working electrode, can flip the preferred spin orientation of the photocurrent, when measured under the identical conditions. Thus, chirality-induced spin polarization, when combined with light and magnetic field effects, opens new avenues for the study of the spin transport properties of chiral molecules and biomolecules and for creating new types of spintronic devices in which light and molecular chirality provide new functions and properties. [ABSTRACT FROM AUTHOR]

• In situ spectroelectrochemistry is used to compare steel/electrolyte interfaces under CP to those at high-pH. • No protective passive film with high impedance formed under CP conditions. • Anodic excursions can induce unstable passivition on steel surfaces under high CP. In situ spectroelectrochemistry measurements, including electrochemical impedance spectroscopy (EIS) and UV–vis light reflecting spectroscopy, were conducted simultaneously to compare the characteristics at the steel/electrolyte interface under cathodic protection (CP) to that in high-pH alkaline solution. The results show that the electrochemical characteristics and optical light reflectance of the steel/electrolyte interface under CP are significantly different from those with a passive film formed in high-pH alkaline solution. These data indicate that no protective passive film is formed under the CP potential of −1.2V SSC , presumably because of the continuous supply of CP current to the cathodic interface and subsequent cathodic reduction reactions. The essence of the cathodic protection mechanism is to eliminate the anodic and cathodic zones by cathodic polarization, not to produce passive film on the steel surface. Another interesting phenomenon observed in the experiments was for the steel specimen under CP potentials equal to or more negative than −1.2 V SSC , for which the interruption of CP current and anodic excursions could induce passivation on the steel surface for a certain time. Analyses indicate that the occurrence of passivation in this case is related to the high pH environment produced by previous cathodic reactions and the positive potential shift caused by the anodic excursion; whereas the disappearance of passivation correlates with a decreasing pH and the subsequent electrochemical reactions, which could provide some insights for understanding the effect of dynamic stray current on cathodically protected steel. [ABSTRACT FROM AUTHOR]

This work presents new results and summarizes literature results on the chiral induced spin selectivity (CISS) effect observed for amino acids, peptides, and DNA. To facilitate robust comparisons between measurements of different types and by different groups, we propose a convention for describing the spin‐dependent properties of chiral materials and apply it in the discussion. Different phenomena known to affect the sign and magnitude of the spin polarization are described and critically analyzed, including: the molecule's orientation, the molecule's dipole moment direction with respect to the electron propagation direction, the molecular length, the molecule/substrate interface, and the role of the molecule's secondary structure. Lastly, we identify open key questions about spin‐filtering by biomolecules at interfaces. [ABSTRACT FROM AUTHOR]

Controlled reduction of oxygen is important for developing clean energy technologies, such as fuel cells, and is vital to the existence of aerobic organisms. The process starts with oxygen in a triplet ground state and ends with products that are all in singlet states. Hence, spin constraints in the oxygen reduction must be considered. Here, we show that the electron transfer efficiency from chiral electrodes to oxygen (oxygen reduction reaction) is enhanced over that from achiral electrodes. We demonstrate lower overpotentials and higher current densities for chiral catalysts versus achiral ones. This finding holds even for electrodes composed of heavy metals with large spin–orbit coupling. The effect results from the spin selectivity conferred on the electron current by the chiral assemblies, the chiral-induced spin selectivity effect. [ABSTRACT FROM AUTHOR]

This work explores electron transfer through nonbonded contacts in two U-shaped DBA molecules 1DBA and 2DBA by measuring electron-transfer rates in organic solvents of different polarities. These molecules have identical U-shaped norbornylogous frameworks, 12 bonds in length and with diphenyldimethoxynaphthalene (DPMN) donor and dicyanovinyl (DCV) acceptor groups fused at the ends. The U-shaped cavity of each molecule contains an aromatic pendant group of different electronic character, namely p-ethylphenyl, in 1DBA, and p-methoxyphenyl, in 2DBA. Electronic coupling matrix elements, Gibbs free energy, and reorganization energy were calculated from experimental photophysical data for these compounds, and the experimental results were compared with computational values. The magnitude of the electronic coupling for photoinduced charge separation, ∣VCS∣ in 1DBA and 2DBA were found to be 147 and 274 cm-1, respectively, and suggests that the origin of this difference lies in the electronic nature of the pendant aromatic group and charge separation occurs by tunneling through the pendant group, rather than through the bridge. 2DBA, but not 1DBA, displayed charge transfer (CT) fluorescence in nonpolar and weakly polar solvents, and this observation enabled the electronic coupling for charge recombination, ∣VCR∣ in 2DBA to be made, the magnitude of which is ∼ 500 cm-1, significantly larger than that for charge separation. This difference is explained by changes in the geometry of the molecule in the relevant states; because of electrostatic effects, the donor and acceptor chromophores are about 1 Å closer to the pendant group in the charge-separated state than in the locally excited state. Consequently the through-pendant-group electronic coupling is stronger in the charge-separated state—which controls the CT fluorescence process—than in the locally excited state—which controls the charge separation process. The magnitude of ∣VCR∣ for 21DBA is almost 2 orders of magnitude greater than that in DMN-12-DCV, having the same length bridge as for the former molecule, but lacking a pendant group. This result unequivocally demonstrates the operation of the through-pendant-group mechanism of electron transfer in the pendant-containing U-shaped systems of the type 1DBA and 2DBA. [ABSTRACT FROM AUTHOR]

Abstract: The electron transfer reactions of three U-shaped donor-bridge-acceptor molecules with different pendant groups have been studied in different solvents as a function of temperature. Analysis of the electron transfer kinetics in nonpolar and weakly polar solvents provides experimental reaction Gibbs energies that are used to parameterize a molecular solvation model. This solvation model is then used to predict energetic parameters in the electron transfer rate constant expression and allow the electronic coupling between the electron donor and electron acceptor groups to be determined from the rate data. The U-shaped molecules differ by alkylation of the aromatic pendant group, which lies in the ‘line-of-sight’ between the donor and acceptor groups. The findings show that the electronic coupling through the pendant group is similar for these molecules. [Copyright &y& Elsevier]

The electronic coupling matrix elements attending the charge separation reactions of a C-shaped molecule containing an excited pyrene as the electron acceptor and a dimethylaniline as the donor are determined in aromatic, ether, and ester solvents. Band shape analyses of the charge-transfer emission spectra (CT→S[SUB0]) provide values of the reaction free energy the solvent reorganization energy, and the vibrational reorganization energy in each solvent. The free energy for charge separation in benzene and toluene solvents is independenttv determined from the excited state equilibrium established between the locally excited pyrene s[SUB1] state and the charge-transfer state. Analyses of the charge separation kinetics using the spectroscopically determined reorganization energies and reaction free energies indicate that the electronic coupling is solvent independent, despite the presence of a cleft between the donor and acceptor. Hence, solvent molecules are not involved in the coupling pathway. The orientations of the donor and acceptor units, relative to the spacer, are not rigidly constrained, and their torsional motions decrease solvent access to the cleft. Generalized Mulliken-Hush calculations show that rotation of the pyrene group about the bond connecting it to the spacer greatly modulates the magnitude of through-space coupling between the S[SUB1] and CT states. The relationship between the torsional dynamics and the electron-transfer dynamics is discussed. [ABSTRACT FROM AUTHOR]

We show that enantioselective reactions can be induced by the electron spin itself and that it is possible to replace a conventional enantiopure chemical reagent by spin‐polarized electrons that provide the chiral bias for enantioselective reactions. Three examples of enantioselective chemistry resulting from electron‐spin polarization are presented. One demonstrates the enantioselective association of a chiral molecule with an achiral self‐assembled monolayer film that is spin‐polarized, while the other two show that the chiral bias provided by the electron helicity can drive both reduction and oxidation in enantiospecific electrochemical reactions. In each case, the enantioselectivity does not result from enantiospecific interactions of the molecule with the ferromagnetic electrode but from the polarized spin that crosses the interface between the substrate and the molecule. Furthermore, the direction of the electron‐spin polarization defines the handedness of the enantioselectivity. This work demonstrates a new mechanism for realizing enantioselective chemistry. [ABSTRACT FROM AUTHOR]

We show that enantioselective reactions can be induced by the electron spin itself and that it is possible to replace a conventional enantiopure chemical reagent by spin‐polarized electrons that provide the chiral bias for enantioselective reactions. Three examples of enantioselective chemistry resulting from electron‐spin polarization are presented. One demonstrates the enantioselective association of a chiral molecule with an achiral self‐assembled monolayer film that is spin‐polarized, while the other two show that the chiral bias provided by the electron helicity can drive both reduction and oxidation in enantiospecific electrochemical reactions. In each case, the enantioselectivity does not result from enantiospecific interactions of the molecule with the ferromagnetic electrode but from the polarized spin that crosses the interface between the substrate and the molecule. Furthermore, the direction of the electron‐spin polarization defines the handedness of the enantioselectivity. This work demonstrates a new mechanism for realizing enantioselective chemistry. [ABSTRACT FROM AUTHOR]

Electron spin and molecular chirality are emerging as factors that can be used effectively to direct charge flow at the molecular scale. We report order of magnitude effects of molecular chirality on electron-transfer rates between quantum dots (QDs) in chiral QD assemblies. Indeed, both the circular polarization of the light that excites the electron donor and the imprinted chirality of the acceptor QDs affect the dot-to-dot electron-transfer kinetics. We define a polarization for the electron-transfer rate constant and show that it correlates with the strength of the acceptor QD circular dichroism (CD) spectrum. These findings imply that the CD strength of the QD exciton transition(s) may be used as a predictor for the spin-dependent electron transfer, indicating that chiral imprinting of the dots may lie at the origin of this phenomenon. [ABSTRACT FROM AUTHOR]

Scanning tunneling microscope break junction measurements are used to examine how the molecular conductance of nucleic acids depends on the composition of their backbone and the linker group to the electrodes. Molecular conductances of 10 base pair long homoduplexes of DNA, aeg-PNA, γ-PNA, and a heteroduplex of DNA/aeg-PNA with identical nucleobase sequence were measured. The molecular conductance was found to vary by 12 to 13 times with the change in backbone. Computational studies show that the molecular conductance differences between nucleic acids of different backbones correlate with differences in backbone structural flexibility. The molecular conductance was also measured for duplexes connected to the electrode through two different linkers, one directly to the backbone and one directly to the nucleobase stack. While the linker causes an order-of-magnitude increase in the overall conductance for a particular duplex, the differences in the electrical conductance with backbone composition are preserved. The highest molecular conductance value, 0.06G 0, was measured for aeg-PNA duplexes with a base stack linker. These findings reveal an important new strategy for creating longer and more complex electroactive, nucleic acid assemblies. [ABSTRACT FROM AUTHOR]

Noncovalent interactions between molecules are key for many biological processes. Necessarily, when molecules interact, the electronic charge in each of them is redistributed. Here, we show experimentally that, in chiral molecules, charge redistribution is accompanied by spin polarization. We describe how this spin polarization adds an enantioselective term to the forces, so that homochiral interaction energies differ from heterochiral ones. The spin polarization was measured by using a modified Hall effect device. An electric field that is applied along the molecules causes charge redistribution, and for chiral molecules, a Hall voltage is measured that indicates the spin polarization. Based on this observation, we conjecture that the spin polarization enforces symmetry constraints on the biorecognition process between two chiral molecules, and we describe how these constraints can lead to selectivity in the interaction between enantiomers based on their handedness. Model quantum chemistry calculations that rigorously enforce these constraints show that the interaction energy for methyl groups on homochiral molecules differs significantly from that found for heterochiral molecules at van der Waals contact and shorter (i.e., -0.5 kcal/mol at 0.26 nm). [ABSTRACT FROM AUTHOR]

The recently discovered chiral induced spin selectivity (CISS) effect gives rise to a spin selective electron transmission through biomolecules. Here we review the mechanism behind the CISS effect and its implication for processes in Biology. Specifically, three processes are discussed: long-range electron transfer, spin effects on the oxidation of water, and enantioselectivity in bio-recognition events. These phenomena imply that chirality and spin may play several important roles in biology, which have not been considered so far. [ABSTRACT FROM AUTHOR]

This work shows how to create covalently bound nanoparticle dyad assemblies on a colloidal template and studies photoinduced charge transfer in them. New results are reported for how the electron-transfer rate changes with the inter-nanoparticle distance and the energy band offset of the nanoparticles (reaction Gibbs energy). The experimental findings show that the distance dependence is consistent with an electron tunneling mechanism. The dependence of the rate on the energy band offset is found to be consistent with Marcus theory, as long as one performs a sum over final electronic states. These results indicate that our understanding of electron transfer in molecular donor-bridge-acceptor assemblies can be translated to describe nanoparticle-bridge-nanoparticle assemblies. [ABSTRACT FROM AUTHOR]

This work demonstrates that chiral imprinted CdSe quantum dots (QDs) can act as spin selective filters for charge transport. The spin filtering properties of chiral nanoparticles were investigated by magnetic conductive-probe atomic force microscopy (mCP-AFM) measurements and magnetoresistance measurements. The mCP-AFM measurements show that the chirality of the quantum dots and the magnetic orientation of the tip affect the current-voltage curves. Similarly, magnetoresistance measurements demonstrate that the electrical transport through films of chiral quantum dots correlates with the chiroptical properties of the QD. The spin filtering properties of chiral quantum dots may prove useful in future applications, for example, photovoltaics, spintronics, and other spin-driven devices. [ABSTRACT FROM AUTHOR]

Single-stepnonadiabatic electron tunneling models are widely usedto analyze electrochemical rates through self-assembled monolayerfilms (SAMs). For some systems, such as nucleic acids, long-rangecharge transfer can occur in a “hopping” regime thatinvolves multiple charge transfer events and intermediate states.This report describes a three-step kinetic scheme to model chargetransfer in this regime. Some of the features of the three-step modelare probed experimentally by changing the chemical composition ofthe SAM. This work uses the three-step model and a temperature dependenceof the charge transfer rate to extract the charge injection barrierfor a SAM composed of a 10-mer peptide nucleic acid that operatesin the hopping regime. [ABSTRACT FROM AUTHOR]

Core–shell particles composed of a dielectric core and a metallic nanoshell exhibit tunable surface plasmons that may be exploited to enhance the light absorption capability of photoactive materials. This work uses both experimental and theoretical methods to elucidate the mechanism by which SiO 2 @Au@SiO 2 (SGS) core–shell–shell particles improve the light harvesting efficiency of PbS–TiO 2 heterojunction solar cells. The enhanced light absorption by PbS nanoparticles depends on their location in the device and their impact on device morphology. This study demonstrates that SGSs can promote the light harvesting of thin film solar cells in two ways. First, the localized surface plasmon resonance of the SGSs increases light scattering and the local electromagnetic field at the PbS–SGS interface. Second, placing SGSs between the PbS and TiO 2 layers, forms nanodomes on top Au electrode and gives rise to additional light scattering that enhances the light harvesting efficiency. By combining these effects the short circuit current density and the energy conversion efficiency are increased by 29% and 24% respectively compared to a cell without SGSs. [ABSTRACT FROM AUTHOR]

[Display omitted] • Manipulating Co 3 O 4 deposition for best electrocatalytic performance in dopamine sensing. • Doping on super-aligned electrospun carbon nanofiber scaffolds for site activity. • Rapid responses of dopamine reaction at the electrode surface. • Highly sensitive to secreted dopamine secreted from living cells. • Superior stability and reproducibility of as-prepared electrode sensors. A demand exists for the development of miniaturized biosensors with high sensitivity and a wide dynamic range for rapid detecting dopamine (DA) levels. In this work, an electrochemical sensor is created by decorating closely packed cobalt oxide (Co 3 O 4) nanograins on nitrogen-doped electrospun carbon nanofibers (NECNFs) via a facile electrodeposition method. The carbon nanofiber matrix provides both a scaffold with ultrahigh surface area for homogeneous dispersion of cobalt oxide nanostructures and facilitates the electrochemical conductivity for the hybrid electrode. The sensing principle is based on the redox reaction between DA and DA quinone that generates electrical signal, which is detectable via differential pulse voltammetry (DPV) and chronoamperometry (CA). Owing to a high electroactive surface area and facilitating electron transfer between electrode surface and the target molecule, the electrical sensing platform exhibits superior sensitivity and selectivity toward DA, with an excellent limit of detection (9 nM) over a wide range of concentrations (0.01 to 100 µM). Moreover, based on its excellent sensing properties and biocompatibility, the sensor has been used for the real-time monitoring exogeneous DA released from pheochromocytoma (PC12) cells. This work demonstrates promise of a novel sensor technology that may render rapid point-of-care testing of DA towards early clinical diagnosis. [ABSTRACT FROM AUTHOR]

Charge transfer (CT) properties are compared between peptide nucleic acid structures with an aminoethylglycine backbone (aeg-PNA) and those with a y-methylated backbone (γ-PNA). The common aeg-PNA is an achiral molecule with a flexible structure, whereas γ-PNA is a chiral molecule with a significantly more rigid structure than aeg-PNA. Electrochemical measurements show that the CT rate constant through an aeg-PNA bridging unit is twice the CT rate constant through a γ-PNA bridging unit. Theoretical calculations of PNA electronic properties, which are based on a molecular dynamics structural ensemble, reveal that the difference in the CT rate constant results from the difference in the extent of backbone fluctuations of aeg- and γ-PNA. In particular, fluctuations of the backbone affect the local electric field that broadens the energy levels of the PNA nucleobases. The greater flexibility of the aeg-PNA gives rise to more broadening, and a more frequent appearance of high- CT rate conformations than in γ-PNA. [ABSTRACT FROM AUTHOR]

This work illustrates a simple approach for optimizing the lanthanide luminescence in molecular dinuclear lanthanide complexes and identifies a particular multidentate europium complex as the best candidate for further incorporation into polymeric materials. The central phenyl ring in the bis-tridentate model ligands L3-L5, which are substituted with neutral (X = H, L3), electron-withdrawing (X = F, L4), or electron-donating (X = OCH3, L5) groups, separates the 2,6-bis(benzimidazol-2-yl)pyridine binding units of linear oligomeric multi-tridentate ligand strands that are designed for the complexation of luminescent trivalent lanthanides, Ln(III). Reactions of L3-L5 with [Ln(hfac)3(diglyme)] (hfac- is the hexafluoroacetylacetonate anion) produce saturated single-stranded dumbbell-shaped complexes [Ln2(Lk)(hfac)6] (k = 3-5), in which the lanthanide ions of the two nine-coordinate neutral [N3Ln(hfac)3] units are separated by 12-14 Å. The thermodynamic affinities of [Ln(hfac)3] for the tridentate binding sites in L3-L5 are average (6.6 ≤ log(β2,1Y,Lk) ≤ 8.4) but still result in 15-30% dissociation at millimolar concentrations in acetonitrile. In addition to the empirical solubility trend found in organic solvents (L4 > L3 L5), which suggests that the 1,4-difluorophenyl spacer in L4 is preferable, we have developed a novel tool for deciphering the photophysical sensitization processes operating in [Eu2(Lk)(hfac)6]. A simple interpretation of the complete set of rate constants characterizing the energy migration mechanisms provides straightforward objective criteria for the selection of [Eu2(L4)(hfac)6] as the most promising building block. [ABSTRACT FROM AUTHOR]

This work explores the sensitization of luminescent lanthanide Tb3+ and Eu3+ cations by the electronic structure of zinc sulfide (ZnS) semiconductor nanopartides. Excitation spectra collected while monitoring the lanthanide emission bands reveal that the ZnS nanopartides act as an antenna for the sensitization of Tb3+ and Eu3+. The mechanism of lanthanide ion luminescence sensitization is rationalized in terms of an energy and charge transfer between trap sites and is based on a semiemnirical model, proposed by Dorenbos and co-workers (Dorenbos, P. J. Phys.: Condens. Matter 2003, 15, 8417-8434; J. Lumin. 2004, ' 108, 301-305; J. Lumin. 2005, 111, 89-104. Dorenbos, P., van der Kolk, E. Appl Phys. Lett. 2006, 89, 061122-1-061122-3; Opt. Mater. 2008, 30, 1052-10S7. Dorenbos, P. J. Alloys Compd. 2009, 488, 568-573; references 1-6.) to describe the energy level scheme. This model implies that the mechanisms of luminescence sensitization of Tb3+ and Eu3+ in ZnS nanopartides are different; namely, Tb3+acts as a hole trap, whereas Eu3+ acts as an electron trap. Further testing of this model is made by extending the studies from ZnS nanopartides to other II-VI semiconductor materials; namely, CdSe, CdS, and ZnSe. [ABSTRACT FROM AUTHOR]

Abstract: Objectives: The protein components of low-density lipoprotein (LDL), oxidized LDL and proteoglycans such as versican contain tryptophan, an amino acid with characteristic fluorescence features at 308nm excitation wavelength. We hypothesize that intrinsic fluorescence spectroscopy at 308nm excitation wavelength IFS308, a method suitable for clinical use, can identify coronary artery lesions with superficial foam cells (SFCs) and/or proteoglycans. Methods: We subjected 119 human coronary artery specimens to in vitro fluorescence and reflectance spectroscopy. We used 5 basis spectra to model IFS308, and extracted their contributions to each individual IFS308 spectrum. A diagnostic algorithm using the contributions of Total Tryptophan and fibrous cap to IFS308 was built to identify specimens with SFCs and/or proteoglycans in their top 50μm. Results: We detected SFCs and/or proteoglycans, such as versican or the glycosaminoglycan hyaluronan, in 24 fibrous cap atheromas or pathologic intimal thickening (PIT) lesions. An algorithm using the contributions of Total Tryptophan and fibrous cap to IFS308 was able to identify these segments with 92% sensitivity and 80% specificity. Conclusion: We were able to establish a set of characteristic LDL, oxidized LDL, versican and hyaluronan fluorescence spectra, ready to be used for real-time diagnosis. The IFS308 technique detects SFCs and/or proteoglycans in fibrous cap atheromas and PIT lesions. SFCs and proteoglycans are histological markers of vulnerable plaques, and this study is a step further in developing an invasive clinical tool to detect the vulnerable atherosclerotic plaque. [Copyright &y& Elsevier]

We present evidence for a near-resonant mechanism of charge transfer in short peptide nucleic acid (PNA) duplexes obtained through electrochemical, STM break junction (STM-BJ), and computational studies. A seven base pair (7-bp) PNA duplex with the sequence (TA)3-(XY)-(TA)3 was studied, in which XV is a complementary nucleobase pair. The experiments showed that the heterogeneous charge transfer rate constant (k0) and the single-molecule conductance (σ) correlate with the oxidation potential of the purine base in the XV base pair. The electrochemical measurements showed that the enhancement of k0 is independent, within experimental error, of which of the two PNA strands contains the purine base of the XV base pair. 7-bp PNA duplexes with one or two GC base pairs had similar measured k0 and conductance values. While a simple superexchange model, previously used to rationalize charge transfer in single stranded PNA (Paul et al. J. Am. Chem. Soc. 2009, 131, 6498-6507), describes some of the experimental observations, the model does not explain the absence of an enhancement in the experimental k0 and a upon increasing the G content in the duplexes from one to two. Moreover, the superexchange model is not consistent with other studies (Paul et al. J. Phys. Chem. B 2010, 114, 14140), that showed a hopping charge transport mechanism is likely important for PNA duplexes longer than seven base pairs. A quantitative computational analysis shows that a near-resonant charge transfer regime, wherein a mix of superexchange and hopping mechanisms are expected to coexist, can rationalize all of the experimental results. [ABSTRACT FROM AUTHOR]

Self-assembled monolayers of single-stranded (ss) peptide nudeic acids (PNAs) containing seven nucleotides (TTTXTTT), a C-terminus cysteine, and an N-terminus ferrocene redox group were formed on gold electrodes. The PNA monomer group (X) was selected to be either cytosine (C), thymine (T), adenine (A), guanine (G), or a methyl group (Bk). The charge transfer rate through the oligonucleotides was found to correlate with the oxidation potential of X. Kinetic measurements and computational studies of the ss- PNA fragments show that a nucleobase mediated charge transport mechanism in the deep tunneling superexchange regime can explain the observed dependence of the kinetics of charge transfer on the PNA sequence. Theoretical analysis suggests that the charge transport is dominantly hole-mediated and takes place through the filled bndge orbitals. The strongest contribution to conductance comes from the highest filled orbitals (HOMO, HOMO-1, and HOMO-2) of indMdual bases, with a rapid drop off in contributions from lower lying filled orbitals. Our studies further suggest that the linear correlation observed between the experimental charge transfer rates and the oxidation potential of base X arises from weak average interbase couplings and similar stacking geometries for the four TTTXTTT systems. [ABSTRACT FROM AUTHOR]

Upon interaction with anionic phospholipids, particularly mitochondria-specific cardiolipin (CL), cytochrome c (cyt c) loses its tertiary structure and its peroxidase activity dramatically increases. CL-induced peroxidase activity of cyt c has been found to be important for selective CL oxidation in cells undergoing programmed death. During apoptosis, the peroxidase activity and the fraction of CL-bound cyt c markedly increase, suggesting that CL may act as a switch to regulate cyt c's mitochondrial functions. Using cyclic voltammetry and equilibrium redox titrations, we show that the redox potential of cyt c shifts negatively by 350–400 mV upon binding to CL-containing membranes. Consequently, functions of cyt c as an electron transporter and cyt c reduction by Complex III are strongly inhibited. Further, CL/cyt c complexes are not effective in scavenging superoxide anions and are not effectively reduced by ascorbate. Thus, both redox properties and functions of cyt c change upon interaction with CL in the mitochondrial membrane, diminishing cyt c's electron donor/acceptor role and stimulating its peroxidase activity. [ABSTRACT FROM AUTHOR]

U-shaped donor–bridge–acceptor molecules with different electronic couplings have been investigated as a function of temperature in solvents with slow polarization relaxation, in particular, N-methylacetamide (NMA) and N-methylpropionamide (NMP). At high temperature, the electron-transfer rate is well described by a nonadiabatic model; however, the rate at low temperature is controlled by the solvent friction. The change of the electron-transfer mechanism is discussed and compared with theoretical models. [ABSTRACT FROM AUTHOR]

Using nanometer thick tunneling barriers with specifically attached cytochrome c, the electrontransfer rate constant was studied as a function of the SAM composition (alkane versus terthiophene), the ω-terminating group type (pyridine, imidazole, nitrile), and the solution viscosity. At large electrode-reactant separations, the pyridine terminated alkanethiols exhibit an exponential decline of the rate constant with increasing electron-transfer distance. At short separations, a plateau behavior, analogous to systems involving -COOH terminal groups to which cytochrome c can be attached electrostatically, is observed. The dependence of the rate constant in the plateau region on system properties is investigated. The rate constant is insensitive to the mode of attachment to the surface but displays a significant viscosity dependence, change with spacer composition (alkane versus terthiophene), and nature of the solvent (H[sub 2]O versus D[sub 2]O). Based on these findings and others, the conclusion is drawn that the charge-transfer rate constant at short distance is determined by polarization relaxation processes in the structure, rather than the electron tunneling probability or large-amplitude conformational rearrangement (gating). The transition in reaction mechanism with distance reflects a gradual transition between the tunneling and frictional mechanisms. This conclusion is consistent with data from a number of other sources as well. [ABSTRACT FROM AUTHOR]

Reports on a systematic determination of electronic coupling matrix elements in U-shaped molecules. Determination of the electronic coupling through a pendant molecular moiety that resides between the donor and acceptor groups; Quantification of the efficiency of electron tunneling through nonbonded contacts.

Examines the strategy used for the immobilization of cytochrome c on the surface of chemically modified electrodes. Electron-transfer kinetics of protein; Concentration of adsorbed cytochrome c; Use of electrochemical methods and scanning tunneling microscopy.

The article presents a study which examines the evidence for water mediated electron transfer (ET) through bis-amino acid donor-bridge-acceptor oligomers (DBA). It states that water molecules influence electron transport in biomolecules and play a significant role in biologically vital processes in living cells. It explains the importance of water in determining the activation energy for ET reactions.

Investigates the noncovalent engineering of carbon nanotube surfaces by conjugated polymers. Molecular structure of single-walled carbon nanotubes; Variation of the polymer side chain; Introduction of neutral and ionic functional groups into the nanotube surface.