Harmonizing Energies: The Interplay Between a Nonplanar SalEn-Type Molecule and a TEMPO Moiety in a New Hybrid Energy-Storing Redox-Conducting Polymer.

Redox-conducting polymers based on SalEn-type complexes have attracted considerable attention due to their potential applications in electrochemical devices. However, their charge transfer mechanisms, physical and electrochemical properties remain unclear, hindering their rational design and optimization. This study aims to establish the influence of monomer geometry on the polymer's properties by investigating the properties of novel nonplanar SalEn-type complexes, poly[N,N'-bis(salicylidene)propylene-2-(hydroxy)diaminonickel(II)], and its analog with 2,2,6,6-tetramethylpiperidinyl-N-oxyl (TEMPO)-substituted bridge (MTS). To elucidate the charge transfer mechanism, operando UV-Vis spectroelectrochemical analysis, electrochemical impedance spectroscopy, and electron paramagnetic resonance are employed. Introducing TEMPO into the bridge moiety enhanced the specific capacity of the poly(MTS) material to 95 mA h g-1, attributed to TEMPO's and conductive backbone's charge storage capabilities. Replacement of the ethylenediimino-bridge with a 1,3-propylenediimino- bridge induced significant changes in the complex geometry and material's morphology, electrochemical, and spectral properties. At nearly the same potential, polaron and bipolaron particles emerged, suggesting intriguing features at the overlap point of the electroactivity potentials ranges of polaron-bipolaron and TEMPO, such as a disruption in the connection between TEMPO and the conjugation chain or intramolecular charge transfer. These results offer valuable insights for optimizing strategies to create organic materials with tailored properties for use in catalysis and battery applications.

Coherent-Error Threshold for Surface Codes from Majorana Delocalization.

Statistical mechanics mappings provide key insights on quantum error correction. However, existing mappings assume incoherent noise, thus ignoring coherent errors due to, e.g., spurious gate rotations. We map the surface code with coherent errors, taken as X or Z rotations (replacing bit or phase flips), to a two-dimensional (2D) Ising model with complex couplings, and further to a 2D Majorana scattering network. Our mappings reveal both commonalities and qualitative differences in correcting coherent and incoherent errors. For both, the error-correcting phase maps, as we explicitly show by linking 2D networks to 1D fermions, to a Z_{2}-nontrivial 2D insulator. However, beyond a rotation angle ϕ_{th}, instead of a Z_{2}-trivial insulator as for incoherent errors, coherent errors map to a Majorana metal. This ϕ_{th} is the theoretically achievable storage threshold. We numerically find ϕ_{th}≈0.14π. The corresponding bit-flip rate sin^{2}(ϕ_{th})≈0.18 exceeds the known incoherent threshold p_{th}≈0.11.

Spectral Signatures of a Negative Polaron in a Doped Polymer Semiconductor: Energy Levels and Hubbard U Interactions.

The modern picture of negative charge carriers on conjugated polymers invokes the formation of a singly occupied (spin-up/spin-down) level within the polymer gap and a corresponding unoccupied level above the polymer conduction band edge. The energy splitting between these sublevels is related to on-site Coulomb interactions between electrons, commonly termed Hubbard U. However, spectral evidence for both sublevels and experimental access to the U value is still missing. Here, we provide evidence by n-doping the polymer P(NDI2OD-T2) with [RhCp*Cp]2, [N-DMBI]2, and cesium. Changes in the electronic structure after doping are studied with ultraviolet photoelectron and low-energy inverse photoemission spectroscopies (UPS, LEIPES). UPS data show an additional density of states (DOS) in the former empty polymer gap while LEIPES data show an additional DOS above the conduction band edge. These DOS are assigned to the singly occupied and unoccupied sublevels, allowing determination of a U value of ∼1 eV.

Activation energy for pore opening in lipid membranes under an electric field.

The standard model of pore formation was introduced more than fifty years ago, and it has been since, despite some refinements, the cornerstone for interpreting experiments related to pores in membranes. A central prediction of the model concerning pore opening under an electric field is that the activation barrier for pore formation is lowered proportionally to the square of the electric potential. However, this has only been scarcely and inconclusively confronted to experiments. In this paper, we study the electropermeability of model lipid membranes composed of 1-palmitoyl-2-oleoyl-glycero-3-phosphocholine (POPC) containing different fractions of POPC-OOH, the hydroperoxidized form of POPC, in the range 0 to 100 mol %. By measuring ion currents across a 50-µm-diameter black lipid membrane (BLM) with picoampere and millisecond resolution, we detect hydroperoxidation-induced changes to the intrinsic bilayer electropermeability and to the probability of opening angstrom-size or larger pores. Our results over the full range of lipid compositions show that the energy barrier to pore formation is lowered linearly by the absolute value of the electric field, in contradiction with the predictions of the standard model.

Environmentally Friendly Improvement of Plasmonic Nanostructure Functionality towards Magnetic Resonance Applications.

Plasmonic nanostructures have attracted a broad research interest due to their application perspectives in various fields such as biosensing, catalysis, photovoltaics, and biomedicine. Their synthesis by pulsed laser ablation in pure water enables eliminating various side effects originating from chemical contamination. Another advantage of pulsed laser ablation in liquids (PLAL) is the possibility to controllably produce plasmonic nanoparticles (NPs) in combination with other plasmonic or magnetic materials, thus enhancing their functionality. However, the PLAL technique is still challenging in respect of merging metallic and semiconductor specific features in nanosized objects that could significantly broaden application areas of plasmonic nanostructures. In this work, we performed synthesis of hybrid AuSi NPs with novel modalities by ultrashort laser ablation of bulk gold in water containing silicon NPs. The Au/Si atomic ratio in the nanohybrids was finely varied from 0.5 to 3.5 when changing the initial Si NPs concentration in water from 70 µg/mL to 10 µg/mL, respectively, without requiring any complex chemical procedures. It has been found that the laser-fluence-insensitive silicon content depends on the mass of nanohybrids. A high concentration of paramagnetic defects (2.2·× 1018 spin/g) in polycrystalline plasmonic NPs has been achieved. Our findings can open further prospects for plasmonic nanostructures as contrast agents in optical and magnetic resonance imaging techniques, biosensing, and cancer theranostics.

Photogeneration of Spin Quintet Triplet-Triplet Excitations in DNA-Assembled Pentacene Stacks.

Singlet fission (SF), an exciton-doubling process observed in certain molecular semiconductors where two triplet excitons are generated from one singlet exciton, requires correctly tuned intermolecular coupling to allow separation of the two triplets to different molecular units. We explore this using DNA-encoded assembly of SF-capable pentacenes into discrete π-stacked constructs of defined size and geometry. Precise structural control is achieved via a combination of the DNA duplex formation between complementary single-stranded DNA and the local molecular geometry that directs the SF chromophores into a stable and predictable slip-stacked configuration, as confirmed by molecular dynamics (MD) modeling. Transient electron spin resonance spectroscopy revealed that within these DNA-assembled pentacene stacks, SF evolves via a bound triplet pair quintet state, which subsequently converts into free triplets. SF evolution via a long-lived quintet state sets specific requirements on intermolecular coupling, rendering the quintet spectrum and its zero-field-splitting parameters highly sensitive to intermolecular geometry. We have found that the experimental spectra and zero-field-splitting parameters are consistent with a slight systematic strain relative to the MD-optimized geometry. Thus, the transient electron spin resonance analysis is a powerful tool to test and refine the MD-derived structure models. DNA-encoded assembly of coupled semiconductor molecules allows controlled construction of electronically functional structures, but brings with it significant dynamic and polar disorders. Our findings here of efficient SF through quintet states demonstrate that these conditions still allow efficient and controlled semiconductor operation and point toward future opportunities for constructing functional optoelectronic systems.

Resolving Isomeric Posttranslational Modifications Using a Biological Nanopore as a Sensor of Molecular Shape.

The chemical nature and precise position of posttranslational modifications (PTMs) in proteins or peptides are crucial for various severe diseases, such as cancer. State-of-the-art PTM diagnosis is based on elaborate and costly mass-spectrometry or immunoassay-based approaches, which are limited in selectivity and specificity. Here, we demonstrate the use of a protein nanopore to differentiate peptides─derived from human histone H4 protein─of identical mass according to the positions of acetylated and methylated lysine residues. Unlike sequencing by stepwise threading, our method detects PTMs and their positions by sensing the shape of a fully entrapped peptide, thus eliminating the need for controlled translocation. Molecular dynamics simulations show that the sensitivity to molecular shape derives from a highly nonuniform electric field along the pore. This molecular shape-sensing principle offers a path to versatile, label-free, and high-throughput characterizations of protein isoforms.

A chip-based array for high-resolution fluorescence characterization of free-standing horizontal lipid membranes under voltage clamp.

Optical techniques, such as fluorescence microscopy, are of great value in characterizing the structural dynamics of membranes and membrane proteins. A particular challenge is to combine high-resolution optical measurements with high-resolution voltage clamp electrical recordings providing direct information on e.g. single ion channel gating and/or membrane capacitance. Here, we report on a novel chip-based array device which facilitates optical access with water or oil-immersion objectives of high numerical aperture to horizontal free-standing lipid membranes while controlling membrane voltage and recording currents using individual micropatterned Ag/AgCl-electrodes. Wide-field and confocal imaging, as well as time-resolved single photon counting on free-standing membranes spanning sub-nanoliter cavities are demonstrated while electrical signals, including single channel activity, are simultaneously acquired. This optically addressable microelectrode cavity array will allow combined electrical-optical studies of membranes and membrane proteins to be performed as a routine experiment.

Sachdev-Ye-Kitaev Circuits for Braiding and Charging Majorana Zero Modes.

The Sachdev-Ye-Kitaev (SYK) model is an all-to-all interacting Majorana fermion model for many-body quantum chaos and the holographic correspondence. Here we construct fermionic all-to-all Floquet quantum circuits of random four-body gates designed to capture key features of SYK dynamics. Our circuits can be built using local ingredients in Majorana devices, namely, charging-mediated interactions and braiding Majorana zero modes. This offers an analog-digital route to SYK quantum simulations that reconciles all-to-all interactions with the topological protection of Majorana zero modes, a key feature missing in existing proposals for analog SYK simulation. We also describe how dynamical, including out-of-time-ordered, correlation functions can be measured in such analog-digital implementations by employing foreseen capabilities in Majorana devices.

Deoxyribonucleic Acid Encoded and Size-Defined π-Stacking of Perylene Diimides.

Natural photosystems use protein scaffolds to control intermolecular interactions that enable exciton flow, charge generation, and long-range charge separation. In contrast, there is limited structural control in current organic electronic devices such as OLEDs and solar cells. We report here the DNA-encoded assembly of π-conjugated perylene diimides (PDIs) with deterministic control over the number of electronically coupled molecules. The PDIs are integrated within DNA chains using phosphoramidite coupling chemistry, allowing selection of the DNA sequence to either side, and specification of intermolecular DNA hybridization. In this way, we have developed a "toolbox" for construction of any stacking sequence of these semiconducting molecules. We have discovered that we need to use a full hierarchy of interactions: DNA guides the semiconductors into specified close proximity, hydrophobic-hydrophilic differentiation drives aggregation of the semiconductor moieties, and local geometry and electrostatic interactions define intermolecular positioning. As a result, the PDIs pack to give substantial intermolecular π wave function overlap, leading to an evolution of singlet excited states from localized excitons in the PDI monomer to excimers with wave functions delocalized over all five PDIs in the pentamer. This is accompanied by a change in the dominant triplet forming mechanism from localized spin-orbit charge transfer mediated intersystem crossing for the monomer toward a delocalized excimer process for the pentamer. Our modular DNA-based assembly reveals real opportunities for the rapid development of bespoke semiconductor architectures with molecule-by-molecule precision.

Spin-spin interactions and spin delocalisation in a doped organic semiconductor probed by EPR spectroscopy.

The enhancement and control of the electrical conductivity of organic semiconductors is fundamental for their use in optoelectronic applications and can be achieved by molecular doping, which introduces additional charge carriers through electron transfer between a dopant molecule and the organic semiconductor. Here, we use Electron Paramagnetic Resonance (EPR) spectroscopy to characterise the unpaired spins associated with the charges generated by molecular doping of the prototypical organic semiconductor poly(3-hexylthiophene) (P3HT) with 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) and tris(pentafluorophenyl)borane (BCF). The EPR results reveal the P3HT radical cation as the only paramagnetic species in BCF-doped P3HT films and show evidence for increased mobility of the detected spins at high doping concentrations as well as formation of antiferromagnetically coupled spin pairs leading to decreased spin concentrations at low temperatures. The EPR signature for F4TCNQ-doped P3HT is found to be determined by spin exchange between P3HT radical cations and F4TCNQ radical anions. Results from continuous-wave and pulse EPR measurements suggest the presence of the unpaired spin on P3HT in a multitude of environments, ranging from free P3HT radical cations with similar properties to those observed in BCF-doped P3HT, to pairs of dipolar and exchange-coupled spins on P3HT and the dopant anion. Characterisation of the proton hyperfine interactions by ENDOR allowed quantification of the extent of spin delocalisation and revealed reduced delocalisation in the F4TCNQ-doped P3HT films.

Pore-forming toxins as tools for polymer analytics: From sizing to sequencing.

We report here on the nanopore resistive pulse sensing (Np-RPS) method, involving pore-forming toxins as tools for polymer analytics at single molecule level. Np-RPS is an electrical method for the label-free detection of single molecules. A molecule interacting with the pore causes a change of the electrical resistance of the pore, called a resistive pulse, associated with a measurable transient current blockade. The features of the blockades, in particular their depth and duration, contain information on the molecular properties of the analyte. We first revisit the history of Np-RPS, then we discuss the effect of the configuration of the molecule/nanopore interaction on the molecular information that can be extracted from the signal, illustrated in two different regimes that either favor molecular sequencing or molecular sizing. Specifically, we focus on the sizing regime and on the use of two different pore-forming toxins, staphylococcal α-hemolysin (αHL) and aerolysin (AeL) nanopores, for the characterization of water-soluble polymers (poly-(ethylene glycol), (PEG)), homopeptides, and heteropeptides. We discuss how nanopore sizing of polymers could be envisioned as a new approach for peptide/protein sequencing.

Singlet exciton fission in a modified acene with improved stability and high photoluminescence yield.

We report a fully efficient singlet exciton fission material with high ambient chemical stability. 10,21-Bis(triisopropylsilylethynyl)tetrabenzo[a,c,l,n]pentacene (TTBP) combines an acene core with triphenylene wings that protect the formal pentacene from chemical degradation. The electronic energy levels position singlet exciton fission to be endothermic, similar to tetracene despite the triphenylenes. TTBP exhibits rapid early time singlet fission with quantitative yield of triplet pairs within 100 ps followed by thermally activated separation to free triplet excitons over 65 ns. TTBP exhibits high photoluminescence quantum efficiency, close to 100% when dilute and 20% for solid films, arising from triplet-triplet annihilation. In using such a system for exciton multiplication in a solar cell, maximum thermodynamic performance requires radiative decay of the triplet population, observed here as emission from the singlet formed by recombination of triplet pairs. Combining chemical stabilisation with efficient endothermic fission provides a promising avenue towards singlet fission materials for use in photovoltaics.

Electrophysiology on Channel-Forming Proteins in Artificial Lipid Bilayers: Next-Generation Instrumentation for Multiple Recordings in Parallel.

Artificial lipid bilayers have been used for several decades to study channel-forming pores and ion channels in membranes. Until recently, the classical two-chamber setups have been primarily used for studying the biophysical properties of pore forming proteins. Within the last 10 years, instruments for automated lipid bilayer measurements have been developed and are now commercially available. This chapter focuses on protein purification and reconstitution of channel-forming proteins into lipid bilayers using a classic setup and on the commercially available systems, the Orbit mini and Orbit 16.

An Organic Borate Salt with Superior p-Doping Capability for Organic Semiconductors.

Molecular doping allows enhancement and precise control of electrical properties of organic semiconductors, and is thus of central technological relevance for organic (opto-) electronics. Beyond single-component molecular electron acceptors and donors, organic salts have recently emerged as a promising class of dopants. However, the pertinent fundamental understanding of doping mechanisms and doping capabilities is limited. Here, the unique capabilities of the salt consisting of a borinium cation (Mes2B+; Mes: mesitylene) and the tetrakis(penta-fluorophenyl)borate anion [B(C6F5)4]- is demonstrated as p-type dopant for polymer semiconductors. With a range of experimental methods, the doping mechanism is identified to comprise electron transfer from the polymer to Mes2B+, and the positive charge on the polymer is stabilized by [B(C6F5)4]-. Notably, the former salt cation leaves during processing and is not present in films. The anion [B(C6F5)4]- even enables the stabilization of polarons and bipolarons in poly(3-hexylthiophene), not yet achieved with other molecular dopants. From doping studies with high ionization energy polymer semiconductors, the effective electron affinity of Mes2B+[B(C6F5)4]- is estimated to be an impressive 5.9 eV. This significantly extends the parameter space for doping of polymer semiconductors.

Supersymmetry in the Standard Sachdev-Ye-Kitaev Model.

Supersymmetry is a powerful concept in quantum many-body physics. It helps to illuminate ground-state properties of complex quantum systems and gives relations between correlation functions. In this Letter, we show that the Sachdev-Ye-Kitaev model, in its simplest form of Majorana fermions with random four-body interactions, is supersymmetric. In contrast to existing explicitly supersymmetric extensions of the model, the supersymmetry we find requires no relations between couplings. The type of supersymmetry and the structure of the supercharges are entirely set by the number of interacting Majorana modes and are thus fundamentally linked to the model's Altland-Zirnbauer classification. The supersymmetry we uncover has a natural interpretation in terms of a one-dimensional topological phase supporting Sachdev-Ye-Kitaev boundary physics and has consequences away from the ground state, including in q-body dynamical correlation functions.

Quantitative Analysis of Doping-Induced Polarons and Charge-Transfer Complexes of Poly(3-hexylthiophene) in Solution.

The mechanism and the nature of the species formed by molecular doping of the model polymer poly(3-hexylthiophene) (P3HT) in its regioregular (rre-) and regiorandom (rra-) forms in solution are investigated for three different dopants: the prototypical π-electron acceptor 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ), the strong Lewis acid tris(pentafluorophenyl)borane (BCF), and the strongly oxidizing complex molybdenum tris[1-(methoxycarbonyl)-2-(trifluoromethyl)ethane-1,2-dithiolene] (Mo(tfd-CO2Me)3). In a combined optical and electron paramagnetic resonance study, we show that the doping of rreP3HT in solution occurs by integer charge transfer, resulting in formation of P3HT radical cations (polarons) for all of the dopants considered here. Remarkably, despite the different chemical nature of the dopants and dopant-polymer interaction, the formed polarons exhibit essentially identical optical absorption spectra. The situation is very different for the doping of rraP3HT, where we observe formation of a charge-transfer complex with F4TCNQ and of a "localized" P3HT polaron on nonaggregated chains upon doping with BCF, while there is no indication of dopant-induced species in the case of Mo(tfd-CO2Me)3. We estimate the ionization efficiency of the respective dopants for the two polymers in solution and report the molar extinction coefficient spectra of the three different species. Finally, we observe increased spin delocalization in regioregular compared to regiorandom P3HT by electron nuclear double resonance, suggesting that the ability of the charge to delocalize on aggregates of planarized polymer backbones plays a significant role in determining the doping mechanism.

Single-Step Formation of a Low Work Function Cathode Interlayer and n-type Bulk Doping from Semiconducting Polymer/Polyethylenimine Blend Solution.

The use of polyethylenimine (PEI) as a thin interlayer between cathodes and organic semiconductors in order to reduce interfacial Ohmic losses has become an important approach in organic electronics. It has also been shown that such interlayers can form spontaneously because of vertical phase separation when spin-coating a blended solution of PEI and the semiconductor. Furthermore, bulk doping of semiconducting polymers by PEI has been claimed. However, to our knowledge, a clear delineation of interfacial from bulk effects has not been published. Here, we report a study on thin films formed by spin-coating blended solutions of PEI and poly{[N,N'-bis(2-octyldodecyl)naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5'-(2,2'-bithiophene)} [P(NDI2OD-T2)] on indium tin oxide. We observed the vertical phase separation in such films, where PEI accumulates at the bottom and the top, sandwiching the semiconductor layer. The PEI interlayer on ITO reduces the electron injection barrier to the minimum value determined by Fermi level pinning, which, in turn, reduces the contact resistance by 5 orders of magnitude. Although we find no evidence for doping-induced polarons in P(NDI2OD-T2) upon mixing with PEI from optical absorption, more sensitive electron paramagnetic resonance measurements provide evidence for doping and an increased carrier density, at a very low level. This, in conjunction with an increased charge carrier mobility due to trap filling, results in an increase in the mixed polymer conductivity by 4 orders of magnitude relative to pure P(NDI2OD-T2). Consequently, both interfacial and bulk effects occur with notable magnitude in thin films formed from blended semiconductor polymer/PEI solution. Thus, this facile one-step procedure to form PEI interlayers must be applied with attention, as modification of the bulk semiconductor polymer (here doping) may occur simultaneously and might go un-noticed if not examined carefully.