Electrical Double Layer Spillover Drives Coupled Electron- and Phase-Transfer Reactions at Electrode/Toluene/Water Three-Phase Interfaces.

A mechanism for the concerted pathway of coupled electron- and phase-transfer reactions (CEPhT) is proposed. CEPhT at three-phase interfaces formed by a solid electrode, an insulating organic solvent, and an aqueous electrolyte is driven by electric double layer (EDL) spillover, with significant electrostatic potential gradients extending a few nanometers into the insulating phase. This EDL spillover phenomenon is studied using scanning electrochemical cell microscopy to interrogate the oxidation of ferrocene in toluene to ferrocenium in water, (Fc) → (Fc) + e.

Electron Transfer Drives the Photosensitized Polymerization of Contrast Agents by Flavoprotein Tags for Correlative Microscopy.

Singlet oxygen generation has long been considered the key feature that allows genetically encoded fluorescent tags to produce polymeric contrast agents for electron microscopy. Optimization of the singlet oxygen sensitization quantum yield has not included the effects of electron-rich monomers on the sensitizer's photocycle. We report that at monomer concentrations employed for staining, quenching by electron transfer is the primary deactivation pathway for photoexcitations.

Electrostatic modulation of multiple binding events between loquacious-PD and double-stranded RNA.

Electrostatics can alter the RNA-binding properties of proteins that display structure selectivity without sequence specificity. Loquacious-PD relies on this broad scope response to mediate the interaction of endonucleases with double stranded RNAs. Multimodal spectroscopic probes with perturbations reveal an efficient and stable binding mechanism that disfavors high protein density complexes and is sensitive to local electrostatics.

Dynamic Response of Surface-Bound Peptides to a pH Perturbation Under Controlled Electrostatic Conditions.

The dynamic conformations of a thin peptide film covalently-linked to the surface of a transparent electrode are characterized over the course of a perturbation to their local pH by a photoacid under a controlled electrostatic potential. The local environment at this functionalized electrified interface is probed by the ultrafast fluorescence intensity and transient anisotropy of chromophores sparsely attached to the peptide side chains. A partition of chromophores into two sub-populations is observed, one buried in the peptide layer and another that is solvent exposed, and their relative contributions to the observed fluorescence signal are affected by both pH and voltage stimuli.

Photoactivation Properties of Self-n-Doped Perylene Diimides: Concentration-dependent Radical Anion and Dianion Formation.

Perylene diimides (PDIs) have garnered attention as organic photocatalysts in recent years for their ability to drive challenging synthetic transformations, such as aryl halide reduction and olefin iodoperfluoroalkylation. Previous work in this area employs spectator pendant groups attached to the imide nitrogen positions of PDIs that are only added to impart solubility. In this work, we employ electron-rich ammonium iodide or ammonium hydroxide pendant groups capable of self-n-doping the PDI core to form radical anions ( ) and dianions ( ).

Selectively Altering the Reactivity of Transient Organic Radical Ions via Their Solvation Environment.

Photoexcitation of the charge transfer band of electron donor-acceptor complexes composed of toluene and 1,2,4,5-tetracyanobenzene yields organic radical ion pairs whose ultrafast reactive dynamics are determined by equilibrium solvent properties. A comparative study of ultrafast reaction rates in a series of alkane alcohols identified their dependence on the local polarizability and hydrogen bond donating/accepting character of the solvent. Because of the rapid and efficient equilibration of these radical ion pairs into solvent-separated species, simple modifications to bulk conditions can be used as a means to selectively alter their decay rates.

Loquacious-PD regulates the terminus-dependent molecular recognition of Dicer-2 toward double-stranded RNA.

Dicer-2 cleaves double-stranded RNA into siRNAs in a terminus-dependent manner as part of 's RNA interference pathway. Using ultrafast fluorescence, we probe the local environment of chromophores at the dsRNA terminus upon binding by Dicer-2 and interrogate the effects of Loquacious-PD, an accessory protein. We find substrate-selective modes of molecular recognition that distinguish between blunt and 3'overhang termini, but whose differences are greatly reduced by Loquacious-PD.

Efficient and effective single-step screening of individual samples for SARS-CoV-2 RNA using multi-dimensional pooling and Bayesian inference.

Rapid and widespread implementation of infectious disease surveillance is a critical component in the response to novel health threats. Molecular assays are the preferred method to detect a broad range of viral pathogens with high sensitivity and specificity. The implementation of molecular assay testing in a rapidly evolving public health emergency, such as the ongoing COVID-19 pandemic, can be hindered by resource availability or technical constraints.

Measuring the Multiscale Dynamics, Structure, and Function of Biomolecules at Interfaces.

The individual and collective structure and properties of biomolecules can change dramatically when they are localized at an interface. However, the small spatial extent of interfacial regions poses challenges to the detailed characterization of multiscale processes that dictate the structure and function of large biological units such as peptides, proteins, or nucleic acids. This Perspective surveys a broad set of tools that provide new opportunities to probe complex, dynamic interfaces across the vast range of temporal regimes that connect molecular-scale events to macroscopic observables.

Transient kinetic studies of the antiviral Dicer-2 reveal roles of ATP in self-nonself discrimination.

Some RIG-I-like receptors (RLRs) discriminate viral and cellular dsRNA by their termini, and Dicer-2 (dmDcr-2) differentially processes dsRNA with blunt or 2 nucleotide 3'-overhanging termini. We investigated the transient kinetic mechanism of the dmDcr-2 reaction using a rapid reaction stopped-flow technique and time-resolved fluorescence spectroscopy. Indeed, we found that ATP binding to dmDcr-2's helicase domain impacts association and dissociation kinetics of dsRNA in a termini-dependent manner, revealing termini-dependent discrimination of dsRNA on a biologically relevant time scale (seconds).

Multimodal spectroscopic investigation of the conformation and local environment of biomolecules at an electrified interface.

The complex and dynamic interfacial regions between biological samples and electronic components pose many challenges for characterization, including their evolution over multiple temporal and spatial scales. Spectroscopic probes of buried interfaces employing mid-infrared plasmon resonances and time-resolved fluorescence detection in the visible range are used to study the properties of polypeptides adsorbed at the surface of a working electrode. Information from these complementary spectroscopic probes reveals the interplay of solvation, electric fields, and ion concentration on their resulting macromolecular conformations.

Role of Polar Protic Solvents in the Dissociation and Reactivity of Photogenerated Radical Ion Pairs.

The UV photolysis of bimolecular charge transfer complexes is employed to yield reactive radical ions in their solvent-equilibrated electronic ground state. In polar protic media, noncovalent complexes of 1,2,4,5-tetracyanobenzene and toluene undergo efficient, ultrafast dissociation to ion pairs and equilibrate with their solvent environment before the resulting radical ions engage in electron transfer and proton abstraction on subnanosecond time scales. Solvent molecules play a critical role in these reactive pathways and in the dissociation and relaxation processes that precede them.

Efficient Charge Transport in Disordered Conjugated Polymer Microstructures.

A new class of conjugated polymers with high charge mobilities exhibits the apparently conflicting morphological features of increased order at the molecular scale while lacking long-range order and crystallinity. To exploit their unique properties, mechanistic insights for charge transport events taking place from the molecular to the device scale must be uncovered. Thus, a central contributor to the continued progress in conjugated optoelectronic materials will be the development of advanced characterization tools, particularly those targeted to measuring the charge-transfer processes in heterogeneous, anisotropic, and hierarchically structured materials.

Resolving ultrafast exciton migration in organic solids at the nanoscale.

Effectiveness of molecular-based light harvesting relies on transport of excitons to charge-transfer sites. Measuring exciton migration, however, has been challenging because of the mismatch between nanoscale migration lengths and the diffraction limit. Instead of using bulk substrate quenching methods, here we define quenching boundaries all-optically with sub-diffraction resolution, thus characterizing spatiotemporal exciton migration on its native nanometre and picosecond scales.

Resolving and Controlling Photoinduced Ultrafast Solvation in the Solid State.

Solid-state solvation (SSS) is a solid-state analogue of solvent-solute interactions in the liquid state. Although it could enable exceptionally fine control over the energetic properties of solid-state devices, its molecular mechanisms have remained largely unexplored. We use ultrafast transient absorption and optical Kerr effect spectroscopies to independently track and correlate both the excited-state dynamics of an organic emitter and the polarization anisotropy relaxation of a small polar dopant embedded in an amorphous polystyrene matrix.

Uncovering Single-Molecule Photophysical Heterogeneity of Bright, Thermally Activated Delayed Fluorescence Emitters Dispersed in Glassy Hosts.

Recently developed all-organic emitters used in display applications achieve high brightness by harvesting triplet populations via thermally activated delayed fluorescence. The photophysical properties of these emitters therefore involve new inherent complexities and are strongly affected by interactions with their host material in the solid state. Ensemble measurements occlude the molecular details of how host-guest interactions determine fundamental properties such as the essential balance of singlet oscillator strength and triplet harvesting.

Percolation, Tie-Molecules, and the Microstructural Determinants of Charge Transport in Semicrystalline Conjugated Polymers.

Semiconducting polymers play an important role in a wide range of optical and electronic material applications. It is widely accepted that the polymer ordering impacts charge transport in such devices. However, the connection between molecular ordering and device performance is difficult to predict due to the current need for a mathematical theory of the physics that dictate charge transport in semiconducting polymers.

Manipulating Excited-State Dynamics of Individual Light-Harvesting Chromophores through Restricted Motions in a Hydrated Nanoscale Protein Cavity.

Manipulating the photophysical properties of light-absorbing units is a crucial element in the design of biomimetic light-harvesting systems. Using a highly tunable synthetic platform combined with transient absorption and time-resolved fluorescence measurements and molecular dynamics simulations, we interrogate isolated chromophores covalently linked to different positions in the interior of the hydrated nanoscale cavity of a supramolecular protein assembly. We find that, following photoexcitation, the time scales over which these chromophores are solvated, undergo conformational rearrangements, and return to the ground state are highly sensitive to their position within this cavity and are significantly slower than in a bulk aqueous solution.

Chain conformations dictate multiscale charge transport phenomena in disordered semiconducting polymers.

Existing models for the electronic properties of conjugated polymers do not capture the spatial arrangement of the disordered macromolecular chains over which charge transport occurs. Here, we present an analytical and computational description in which the morphology of individual polymer chains is dictated by well-known statistical models and the electronic coupling between units is determined using Marcus theory. The multiscale transport of charges in these materials (high mobility at short length scales, low mobility at long length scales) is naturally described with our framework.

A general relationship between disorder, aggregation and charge transport in conjugated polymers.

Conjugated polymer chains have many degrees of conformational freedom and interact weakly with each other, resulting in complex microstructures in the solid state. Understanding charge transport in such systems, which have amorphous and ordered phases exhibiting varying degrees of order, has proved difficult owing to the contribution of electronic processes at various length scales. The growing technological appeal of these semiconductors makes such fundamental knowledge extremely important for materials and process design.

Low-temperature processed Ga-doped ZnO coatings from colloidal inks.

We present a new colloidal synthesis of gallium-doped zinc oxide nanocrystals that are transparent in the visible and absorb in the near-infrared. Thermal decomposition of zinc stearate and gallium nitrate after hot injection of the precursors in a mixture of organic amines leads to nanocrystals with tunable properties according to gallium amount. Substitutional Ga(3+) ions trigger a plasmonic resonance in the infrared region resulting from an increase in the free electrons concentration.

Controlled conjugated backbone twisting for an increased open-circuit voltage while having a high short-circuit current in poly(hexylthiophene) derivatives.

Conjugated polymers with nearly planar backbones have been the most commonly investigated materials for organic-based electronic devices. More twisted polymer backbones have been shown to achieve larger open-circuit voltages in solar cells, though with decreased short-circuit current densities. We systematically impose twists within a family of poly(hexylthiophene)s and examine their influence on the performance of polymer:fullerene bulk heterojunction (BHJ) solar cells.

Light trapping in thin-film silicon solar cells with submicron surface texture.

The influence of nano textured front contacts on the optical wave propagation within microcrystalline thin-film silicon solar cell was investigated. Periodic triangular gratings were integrated in solar cells and the influence of the profile dimensions on the quantum efficiency and the short circuit current was studied. A Finite Difference Time Domain approach was used to rigorously solve the Maxwell's equations in two dimensions.