Publications

Protein folding is a complex self-assembly process that enables a newly translated polypeptide to acquire the three-dimensional structure that defines its function. The mechanism of folding corresponds to the path on a funnel-shaped free energy landscape that the polypeptide traverses in order to reach the minimum that corresponds to a native tertiary structure or an ensemble of folded states. To understand protein folding means to characterize the folding transition state, intermediates, and thermodynamics and kinetics. Chemical protein synthesis is complementary to the available molecular biology and biophysical methods to study folding mechanisms. It enables precise modifications to polypeptide backbone and side chains, including single-atom substitutions, chiral editing, fine-tuning stereo-electronic interactions, artificial covalent linking, site-specific labeling with fluorophores, or incorporation of completely artificial building blocks. This chapter describes examples of the application of chemical approaches to the synthesis and modification of proteins in order to obtain unique insights into molecular determinants of protein folding.

Almost all cells in the human body are subjected to mechanical stress. These forces can vary from a few Pascals (shear stress) to some Mega Pascals (on hip cartilage). It is now well known that mechanical forces have a critical effect on cellular physiology. However, although the main biological effects of mechanical forces are well documented, the relation between mechanical stress and physiological phenomena is mainly unknown (mechanotransduction phenomenon). In this chapter, some effects of mechanical stress on bone cells (mesenchymal stem cells, osteoblasts…) are given.

The enormous experimental progress in atomic, molecular, and optical (AMO) physics during the last decades allows us nowadays to isolate single, a few or even many-body ensembles of microscopic particles, and to manipulate their quantum properties at a level of precision, which still seemed unthinkable some years ago. This versatile set of tools has enabled the development of the well-established concept of engineering of many-body Hamiltonians in various physical platforms. These available tools, however, can also be harnessed to extend the scenario of Hamiltonian engineering to a more general Liouvillian setting, which in addition to coherent dynamics also includes controlled dissipation in many-body quantum systems. Here, we review recent theoretical and experimental progress in different directions along these lines, with a particular focus on physical realizations with systems of atoms and ions. This comprises digital quantum simulations in a general open system setting, as well as engineering and understanding new classes of systems far away from thermodynamic equilibrium. In the context of digital quantum simulation, we first outline the basic concepts and illustrate them on the basis of a recent experiment with trapped ions. We also discuss theoretical work proposing an intrinsically scalable simulation architecture for spin models with high-order interactions such as Kitaev's toric code, based on Rydberg atoms stored in optical lattices. We then turn to the digital simulation of dissipative many-body dynamics, pointing out a route for the general quantum state preparation in complex spin models, and discuss a recent experiment demonstrating the basic building blocks of a full-fledged open-system quantum simulator. In view of creating novel classes of out-of-equilibrium systems, we focus on ultracold atoms. We point out how quantum mechanical long-range order can be established via engineered dissipation, and present genuine many-body aspects of this setting: in the context of bosons, we discuss dynamical phase transitions resulting from competing Hamiltonian and dissipative dynamics. In the context of fermions, we present a purely dissipative pairing mechanism, and show how this could pave the way for the quantum simulation of the Fermi-Hubbard model. We also propose and analyze the key properties of dissipatively targeted topological phases of matter.

We study quantum correlations encoded in a three-flavor neutrino system by using complete complementarity relations (CCR). Due to the presence of local coherence in two-flavor subsystems, the CCR has an additional contribution not present in the two flavor mixing case. We investigate such coherence for the three possible bipartite subsystems of the global state both for an electron and a muon neutrino system.

We study the evolution of quantum correlations in a lepton-antineutrino pair, as produced in weak interactions (e.g. pion decay). Assuming an inital state entangled in the spins of the two particles, we show that both chiral and flavor (neutrino) oscillations affect spin correlations. Such corrections are relevant in the non-relativistic regime. In the second part we focused our attention on the weak process n + νe → p + e in which the results found in the previous sections could be observed.

Surface plasmon polaritons (SPPs) result from collective oscillations of free electrons coupled to an electromagnetic field at a plane interface between a metal and a dielectric medium. As photons, SPPs can be considered either as waves or as bosonic particles [1] and they can experience striking quantum interferences such as Hong-Ou-Mandel (HOM) effect [2]. We use in this paper a plasmonic platform (Fig.1) that can convert photons into plasmons, and separate or recombine them on a plasmonic beamsplitter [3]. Single SPPs are excited using single photons created by parametric down conversion into a periodically-poled KTP crystal. The platform is placed in a Mach-Zehnder interferometer in order to vary the path difference between SPPs before impinging on the beamsplitter. The setup allows us to revisit quantum optics experiments using SPP as carriers of the quantum of energy. Using the same device, we can test the wave-particle duality, two-particle (HOM) interference and non-local control of single plasmon interference using the entanglement between a photon and a SPP [4]. In the case of the HOM experiment, we demonstrate that the losses can be used as a new degree of freedom [5]. Playing with the dephasing between transmission and reflection coefficient of the beamsplitter, we can observe a peak instead of the usually expected dip in the HOM interference (Fig.2), i.e. an anti-coalescence effect of SPP. In this talk, we will introduce the plasmonic device main features as well as the different quantum plasmonics experiments that have been performed thanks to the SPP beamsplitter. These results are essential to understand the SPP quantum behavior or to develop hybrid plasmon-photon systems for potential future applications in quantum communication mediated by SPP. [1] JM Elson and R.H. Ritchie, Phys. Rev. B 4, 4129 (1971) [2] J.S. Fakonas et al., Nat. Phot. 8, 317 (2014) [3] M.C. Dheur et al. , Sc. Advances 2, e151574 (2016) [4] M.C. Dheur et al. ArXiv 1610.07493, B. Vest et al. ArXiv 1610.07479 [5] S. Barnett et al., Phys. Rev. A 57, 2134 (1998) Fig.1: Plasmonic platform used for the quantum optics experiment (B). It consists in two SPP launchers (A), a plasmonic beamsplitter, and two slits to convert SPP to photons in the glass substrate. The plasmonic interference can thus be probed using single photon counting modules. Fig2: HOM experiment on a lossy plasmonic beamsplitter, whose complex amplitude reflection and transmission factors are denoted r and t respectively. The usual HOM dip is observed when r = it (left), a peak in the coincidence rate is shown when r = t.

Controlling the fluorescence emission from nanoscale quantum emitters such as single molecules is a key element for a wide range of applications, from efficient analytical sensing to quantum information processing. Enhancing the fluorescence intensity and narrowing the emission directivity are both essential features to achieve a full control of fluorescence, yet this is rarely obtained simultaneously with optical nanoantennas. We report that gold nanoapertures surrounded by periodic corrugations transform standard molecules into bright unidirectional fluorescence sources [1]. We obtain enhancement factors of the fluorescence rate per molecule up to 75 fold simultaneously with a directional emission of the fluorescence into a narrow angular cone into a cone of ±15° in the direction normal to the sample plane. The bright emission and narrow directionality enable the detection of single molecules with a low numerical aperture objective, and improve the effectiveness of fluorescence-based applications. We thoroughly quantify the increased light-matter coupling as well as the radiation pattern intensity. The present demonstration is of high relevance for the development of advanced single molecule sensing, bright single-photon sources for quantum information processing, and light emitting devices. Reference [1] H. Aouani, O. Mahboub, N. Bonod, E. Devaux, E. Popov , H. Rigneault, T.W. Ebbesen, J. Wenger, Nano Letters 11, 637-644 (2011).

Nanoapertures milled in opaque metallic films offer a simple and robust photonic tool to significantly enhance the fluorescence of single molecules. We provide a detailed physical characterization of this phenomenon for apertures milled in gold and aluminum, and discuss its application to biophotonics. For the first time, the most general figures are provided to predict the awaited enhancement factors for almost every kind of fluorescent molecule. This knowledge is essential to discuss the ability to detect low-quantum yield species. We also report the first demonstration of single metal nanoapertures to perform DNA hybridization sensing, and measure similar enhancement factors as for experiments on diffusing molecules.

A nanoscale layer of chromium or titanium is commonly used in plasmonic nanoantennas to firmly adhere a gold film to a glass substrate, yet the influence of this layer on the antenna performance is often ignored. As a result, the need for the use of potentially better materials is not widely recognized. Using a single aperture milled in a gold film with 120 nm diameter as a nanobench for these investigations, we present the first experimental report of the strong dependence of the plasmonic enhancement of single-molecule fluorescence on the nature of the adhesion layer. By combining fluorescence correlation spectroscopy and fluorescence lifetime measurements, we show that this structure is very sensitive to the properties of the adhesion layer, and we detail the respective contributions of excitation and emission gains to the observed enhanced fluorescence. Any increase in the absorption losses due to the adhesion layer permittivity or thickness is shown to lower the gains in both excitation and emission, which we relate to a damping of the energy coupling at the nanoaperture. With this nanobench, we demonstrate the largest enhancement factor reported to date (25×) by using a TiO2 adhesion layer. The experimental data are supported by numerical simulations and argue for a careful consideration of the adhesion layer while designing nanoantennas for high-efficiency single-molecule analysis.

A diffusive process that is reset to its origin at random times, so-called stochastic resetting (SR), is an ubiquitous expedient in many natural systems. Yet, beyond its ability to improve the efficiency of target searching, SR is a true nonequilibrium thermodynamic process that brings forward new and challenging questions.<p>Here, we show how the recent developments of experimental information thermodynamics renew the way to address SR and can lead, beyond a new understanding, to better control on the nonequilibrium nature of SR. This thermodynamically controlled SR is experimentally implemented within a time-dependent optical trapping potential. We show in particular that SR converts heat into work from a single bath continuously and without feedback. This implements a Maxwell's demon that constantly erases information. In our experiments, the erasure takes the form of a protocol that allows us to evaluate the true energetic cost of SR. We show that using an appropriate measure of the available information, this cost can be reduced to a reversible minimum while being bounded by the Landauer limit. We finally reveal that the individual trajectories generated by the demon all break ergodicity and thus demonstrate the nonergodic nature of the demon's modus operandi. Our results offer new approaches to processes, such as SR, where the informational framework provides key experimental tools for their nonequilibrium thermodynamic control.</p>

Tailoring the structure of digital polymers is an efficient strategy for reliable reading of large amounts of data by tandem mass spectrometry. Notably, full sequence coverage of chains containing up to 33 bytes of information is achieved for block-truncated poly(phosphodiester)s designed to undergo controlled fragmentations. However, the previously established reading methodology based on multiple MS stages performed sequentially remains slow and not prone to automation. Here, we report a full gas-phase bottom-up workflow enabling production, separation and sequencing of all sub-sequences of block-truncated poly(phosphodiester)s in a single run. To do so, a multidimensional coupling involving two activation stages in tandem with ion mobility spectrometry has been optimized. Since blocks to be sequenced have their mobility varying in a predictable manner, proper selection of tags used for their identification permits to achieve mobility resolution prior to sequencing. Performing this coupling with MALDI further paves the way to automated imaging-based reading approaches.

Solution-processed semiconducting transition metal dichalcogenides commonly serve as quintessential 2D substrates and templates to develop hybrid structures with novel and/or enhanced properties and performance. However, the effects and control of their ubiquitous and abundant structural defects are still poorly explored and understood. Here, exploiting their highly reactive and defective edges, an unprecedented strategy is introduced for their toposelective functionalization with noble metal nanoparticles through galvanic displacement. Selectively edge-decorated transition metal dichalcogenides nanosheets are successfully produced with gold, palladium, or platinum nanoparticles, showing tunable loading and size. As proof of concept, the hybrid systems are tested for optical and photothermal sensing, as well as electrocatalysis and electronics, demonstrating their enhanced functionality and broad applicability. These findings pave the way for the versatile production of mixed-dimensional multifunctional materials, achieved by harnessing the defective nature of solution-processed transition metal dichalcogenides via molecular chemistry approaches.

In quantum information processing, qudits-quantum systems with d levels-have been a major challenge for their potential to accelerate certain computational tasks. Spin transport measurements on tris(phthalocyaninato)-dinuclear rare-earth(III) molecules offer a promising platform for nuclear spin qudits with increased Hilbert space. However, the absence of radicals in these systems has hindered studies on the coupling between lanthanide ions and conduction electrons.</p><p>In this study, we report the synthesis of (phthalocyaninato)bis(porphyrinato)-dinuclear rare-earth(III) complexes functionalized with thiomethyl groups. The tailored oxidation levels in the neutral complexes facilitated the conversion to air-stable radicals. CASSCF calculations and static magnetic measurements revealed a radical-lanthanide exchange coupling constant, J Rad-Ln = -0.45 cm -1 . Dynamic magnetic measurements demonstrated a shift in the magnetic properties due to exchange interaction, namely from field-induced single-molecule magnets (SMM) to zero-field SMM. The findings of this study, along with the potential of the strong bond between thiomethyl group and gold electrode, highlight the potential of these molecules as novel materials for the implementation of nuclear spin qubits with an increased Hilbert space.

<div><p>Photodetectors are optoelectronic devices that output an electric signal when illuminated, with a wide range of uses in modern technologies, from the fields of biomedical imaging to communications. However, further improving the sensitivity and functionality of these devices to achieve even broader applications would require to further develop devices with selective detection capability over wide ranges of wavelengths. In this study, we present a novel photodetector capable of multiwavelength visible light detection using a blend of organic semiconductors and inorganic perovskites as active material. In this photo-field-effect transistor(photoFET), the photogating effect of CsPbBr3 nanocrystals upon illumination below 520 nm triggers a large shift in threshold voltage while illumination over 600 nm results in an increase in current without threshold voltage shift. As a result, the device exhibits the capability to discriminate red and blue light while being sensitive to the intensity of incident light within the visible spectrum. This innovative device opens the door to the development of a single photodetector devices capable of recognizing multiple wavelengths and show strong promise for increased photosensitivity due to the lack of power losses from filters. Furthermore, the combination of transistor operation and detection functions has strong promise for the development of reconfigurable and neuromorphic circuits.</p></div>

We show that idealized Dicke superradiant decay from a fully inverted state can at all times be described by a positive statistical mixture of coherent spin states (CSS). Since CSS are separable, this implies that no entanglement is involved in Dicke decay. Based on this result, we introduce a new numerical quantum trajectory approach leading to low-entanglement unravelings. This opens up new possibilities for employing matrix product state (MPS) techniques for large-scale numerical simulations with collective decay processes.

Chemodynamic therapy (CDT) is regarded as an emerging strategy with high specificity for tumor therapy by producing highly toxic reactive oxygen species (ROS) in tumor cells by a Fenton or Fenton-like reaction. Excessive ROS can cause mitochondrial damage and induce ferroptosis in cells, leading to the death of cancer cells. However, the generally low efficiency of the Fenton reaction has limited the effectiveness of CDT. Herein, two-dimensional MoS₂ decorated with PB NPs is used as a co-catalyst to promote Fe^III/Fe^II conversion and thus enhance the efficiency of the Fenton reaction. The photothermal properties of both MoS₂ and PB NPs further enhance the Fenton reaction, eventually producing a large amount of ROS. Mitochondrial damage and ferroptosis caused by ROS are evidenced in vitro and in a tumor-bearing mouse model and jointly lead to a decrease in heat shock protein content, further enhancing the photothermal effect of PB NP/MoS₂ nanosystem. This chemodynamic/photothermal synergistic therapy allows achieving good anticancer therapeutic effect. Statement of significance: CDT is a promising cancer treatment that selectively generates toxic ROS to eliminate tumor cells. Nevertheless, its efficacy is often limited by the low efficiency of the Fenton reaction. This study presents a nanocomposite composed of MoS₂ nanosheets decorated with PB NPs, which enhances CDT by improving Fe^III/Fe^II conversion and increasing ROS production. In addition, the photothermal properties of the material further amplify its therapeutic effects. In cell and animal models, this synergistic approach effectively induces mitochondrial damage and ferroptosis, thereby weakening the defenses of the cancer cells. This work provides a significant advancement in CDT, offering a more potent strategy for cancer therapy.

<div><p>Stimuli-responsive organic thin-film transistors (TFTs) such as light-switchable TFTs are key components for multifunctional optoelectronics beyond Moore. However, the modulation of the light-switchable TFTs output developed so far requires the use of ultraviolet (UV) light, despite the latter triggers photooxidation and degradation of the molecular materials and hybrids thereof. Herein, we report an all-visible light-switchable TFT whose current output can be reversibly interconverted between two different states by non-coherent and low-power (&lt; 1 mW cm -2 ) visible light. The lightsensitive material was assembled by blending CdS quantum dots (QDs) coated by photochromic diarylethene (DAE) molecules with a semiconducting p-type poly[2,5-(2-octyldodecyl)-3,6diketopyrrolopyrrole-alt-5,5-(2,5-di(thien-2-yl)thieno[3,2-b]thiophene)] (DPP-DTT). For the first time, triplet energy transfer (TET) at the organic-inorganic interface between photochromic molecules and QDs was exploited to drive light-switchable TFTs devices, enabling DAEs reversible photoisomerization when exposed to 405 nm and 515 nm visible light. Significantly, the conversion efficiency of DAEs via all-visible-light switching is comparable to that achieved under UV light irradiation, while the light switching fatigue resistance of the devices displayed a radical improvement. Our work provides a new pathway to realize all-visible-light activated devices for future design of advanced digital optoelectronics in the context of next-generation data storage technologies and neuromorphic computing.</p></div>

Symmetry is known to strongly influence the course of a chemical reaction. It has also been found to play a key role in vibrational strong coupling (VSC), where it can influence the outcome of chemical reactions or alter chemical equilibria. However, the precise nature of this effect and its extent remains elusive. To further explore the role of vibrational symmetry, we have investigated the equilibrium constants of different charge transfer complexes, in particular of isomers of trimethyl benzene belonging to different point groups from which a general symmetry rule emerges. We describe the strongly coupled system by a direct product of irreducible representations associated with the complexes and the cavity. As a consequence, the coupled vibration is associated with a new irreducible representation that projects differently on the reaction coordinate of the charge transfer complexation, reflecting the changes in the equilibrium constants. This phenomenological symmetry rule points to a general underlying framework for predicting the outcome of chemical reactivity under VSC.

The generation of self-organized phases drives the emergence of states of matter of higher complexity. Herein, we study in situ generated self-assembled systems based on the condensation between different aldehydes and hydrazides in water. The resulting acylhydrazones can self-organize into turbid hydrogels or bigger micro-crystals depending on the component substituents. The generation of the organized phases was investigated by NMR and UV-Vis spectroscopy as well as by microscopy, rheology and solid-state X-ray analyses. Polar substituents like imidazole rings, carboxylic acids and alcohols still lead to hydrogels due to the high propensity of the hydrophobic aromatic cores to self-assemble. The micro-crystalline gels containing acidic and basic groups displayed pH-responsiveness. Such behaviour allowed for adaptive scrambling-sorting transitions and sorting selectivity switching within 1x2 dynamic covalent libraries driven by self-organization in response to environmental conditions. Moreover, the generation of hydrophobic microenvironments in the self-assembled 3D-network promoted selective imine formation made of apolar components as a result of the stabilization and protection of the reversible covalent bond from hydrolysis. Thus, the dynamic systems described here exhibit up to five levels of adaptive behaviours governed by self-organization (see conclusions).

Halide perovskites have been considered as promising thermoelectric materials due to their unusual combination of good charge mobility and ultralow thermal conductivity. Low dimensional halide perovskite derivatives (0D, 1D and 2D) have been predicted to have high thermoelectric figure of merit due to quantum confinement effects, but this class of metal halides has been under-explored experimentally. Here, we investigate the thermoelectric properties of the all-inorganic 0D halide perovskite, Cs 3 Cu 2 I 5 , doped with barium. Ba-doped pellets were fabricated by solid state synthesis. An enhancement of electrical conductivity by &gt;3 orders of magnitude was achieved upon doping and extended X-ray absorption fine structure measurements indicate that Ba substituted Cs on the smaller of the two A-sites. We show that thermal conductivity is in the ultralow regime and decreases with doping, consistent with increased scattering from defects. The positive Seebeck coefficient of +2400 ± 60 mV K -1 for Cs 3 Cu 2(1-x) Ba x I 5 (x = 0.1) confirmed p-type doping. To our knowledge, this is the first study on substitutional doping of a 0D halide perovskite to improve the thermoelectric figure of merit.

The advent of transition metal dichalcogenides (TMDCs) has revolutionized the field of optoelectronics. In this context, recent advances in large-area synthesis of monolayer WS2 opened the door to potential optoelectronic applications, because of its inherently high photoluminescence (PL) yield and superior electron mobility. However, randomly distributed point and line defects are key bottlenecks for efficient charge transport, hindering further development of system-on-chip (SoC) technologies. Herein, we report a molecular welding strategy using benzene-1,4-dithiol (BDT) to simultaneously passivate sulfur vacancies and bridge grain boundary (GB) fissures in monolayer WS2. The GB welding was monitored on the atomic scale by high-angle annular dark-field scanning transmission electron microscopy. This treatment yields uniform PL emission, ~200-fold enhancement in electron mobility, a three-order-of-magnitude increase in both on-state current and Ion/Ioff ratio for transistors across GBs, comparable to intragrain characteristics. Additionally, temperature-dependent PL spectroscopy was employed to identify the defect types and the activation energy of GBs. Our approach, utilizing facile vapor deposition of ad-hoc molecules to repair line defects in 2D crystals, offers a scalable and effective solution to repair extended line defects in two-dimensional (2D) semiconductors, advancing the development of high-performance, uniform 2D optoelectronic systems.

Two toehold‐mediated strand displacement mechanisms—parallel (PTMSD) and series (STMSD)—are explored as strategies for editing digital information stored in synthetic bio‐hybrid polymers. To demonstrate their potential, uniform DNA–poly(phosphodiester) (PPDE) conjugates are synthesized using automated phosphoramidite chemistry and characterized by HPLC and mass spectrometry. In these macromolecules, binary information is encoded exclusively in the synthetic polymer segment, while the DNA single strands (ssDNA) serve as programmable motifs for orthogonal self‐assembly. DNA sequences are optimized using nucleic acid design software, and the synthetic domains are encoded with a previously reported binary alphabet. These bio‐hybrid precursors are then assembled into linear supramolecular architectures via DNA‐directed self‐assembly. The resulting structures incorporated both digitally encoded polymer segments and double‐stranded DNA connectors, as well as accessible ssDNA toeholds that enabled PTMSD and STMSD. Polyacrylamide gel electrophoresis (PAGE) is used to monitor the strand displacement reactions, confirming that PTMSD enables the selective release or erasure of encoded information through dual‐toehold accessibility. Furthermore, STMSD is shown to facilitate stepwise rewriting of information. As a proof‐of‐concept, an English word encoded in the system is successfully edited into its French translation.

Neuromorphic devices are emerging as key components for next-generation computing, driven by the rapid growth of digital technology. To meet growing demand for energy-efficient logic operations, photonic synaptic devices have become a focal point of interest. Here, a novel molybdenum disulfide (MoS 2 )based synaptic memory field-effect transistor (FET) is presented, exploiting the photo-induced ionic gating effect through Janus functionalization with ion-conductive sodium alginate (SA) and ferroelectric poly(vinylidene fluorideco-trifluoroethylene) [P(VDF-TrFE)]. The integration of SA as a dynamic cations reservoir enables ion migration and corresponding modulation of persistent photoconductivity on MoS 2 , emulating synaptic plasticity including sensory, short-term, and long-term memory operation. The SA/MoS 2 FET demonstrates over eight multilevel states adjustable by light irradiation conditions. The device also exhibits excellent visible-range photodetection (455-680 nm), with a high photoresponsivity of 20 kA W -1 and a fast response time of 120 ms under 20 V gate bias and 680 nm LED illumination.

<div><p>The development of sustainable, high-performance gel polymer electrolytes (GPEs) is crucial for next-generation energy storage; however, existing materials often exhibit limited mechanical stability, suboptimal ionic transport, or environmental drawbacks. Here, for the first time gelatin-alginate organohydrogels crosslinked with Cu 2+ and Mn 2+ are used as GPEs for supercapacitors, in combination with Li + incorporation to enhance ionic conductivity and transport. Small-Angle X-ray Scattering (SAXS) reveals that the choice of the crosslinking cation governs the nanoscale organization of the polymer network-reflected in distinct correlation lengths-which in turn critically influences ionic transport, mechanical stability, and electrochemical performance. Cu 2+ -crosslinked gels achieve the highest areal capacitance (591.8 mF cm -2 ), energy density (82.2 µWh cm -2 ), and power density (1957.8 µW cm -2 ), whereas Mn 2+ -crosslinked gels exhibit superior cycling stability (88.3% retention over 5000 cycles). Li + incorporation increases the mechanical flexibility of Mn-based gels-reducing the compressive modulus by over 60%-enhancing ion mobility and charge storage. Conversely, Cu-based gels maintain structural integrity while exhibiting improved conductivity. These findings demonstrate how biopolymer-based GPEs, designed through nanoscale engineering and ion doping, achieve an optimal balance of mechanical robustness and electrochemical performance. By combining scalability and exceptional energy storage capabilities, these materials establish a new paradigm for flexible supercapacitors and sustainable energy technologies.</p></div>

Graphene nanostructures are capable of supporting plasmonic resonances in the visible and infrared parts of the spectrum. Thus, they can be exploited as platforms for Surface-Enhanced Infrared Absorption Spectroscopy (SEIRAS) and Surface-Enhanced Raman Spectroscopy (SERS) studies. One application of SEIRAS and SERS is the study of proteins at very low concentrations, down to the picomolar range. Among the different forms of graphene, graphene nanodots are ideal nanostructures that can be produced on a large scale using established protocols relying on sonication-assisted exfoliation under specific experimental conditions. Their rich surface chemistry facilitates stable and nondenaturing adsorption of membrane proteins, ensuring preservation of their native secondary structure upon immobilization. In this study, we exploited graphene nanodots deposited by drop casting or spray coating onto a silicon wafer as a substrate to study the cytochrome bd-I oxidase fromE. coli, a membrane protein that is present in the respiratory chains of bacteria. The amide I signal was examined to confirm the structural integrity of the protein once immobilized onto the graphene nanodots. SEIRAS and SERS experiments revealed reproducible enhancement of the protein signal, approximately by a factor of 2 and 6-10 compared to other substrates, respectively, enabling analyte detection with a sensitivity down to the nanomolar range. Furthermore, our tailored substrate exhibited high stability of the protein exceeding 6 days, thus underscoring its high potential for biosensing.

In this study, we investigate the relationship between the polymorphism and crystallographic parameters and the charge transport properties achieved through the fabrication of organic field-effect transistors (OFETs) based on a novel molecular semiconductor, i.e., 2,7-bis(7,7-dimethyloctyl)benzo[b]benzo [4,5]thieno [2,3-d]thiophene (ditBuC6-BTBT). Four polymorphs of ditBuC6-BTBT were identified: three observed at room temperature (Forms I, Ia, and II), and one appearing above 100 °C (Form III). While cell parameters were measured for all forms, full crystal structures were determined only for Forms Ia and II. Although a direct correlation between molecular packing and charge transport properties could not be established from the present study, the structural analysis of the polymorphs contributes to a broader understanding of the packing motifs in ditBuC6-BTBT. A meticulous examination of the minute discrepancies in the powder patterns substantiated the existence of both the metastable Form I and Form Ia, which became more difficult to isolate due to unintentional seeding of the thermodynamically stable Form II. Nonequilibrium crystallization techniques utilizing thermal gradient and bar-assisted meniscus shearing methods were explored to enhance control over polymorph selection. The intrinsic charge transport properties ruled by the overlap of the frontier orbitals were studied by computing the transfer integrals. Optimized devices fabricated by depositing thin films by solution shearing and vacuum evaporation led to field-effect mobility in the linear regime of ca. 0.05 cm 2 V -1 s -1 . The observed device performances were interpreted as a result of the combined effects of crystal packing features, ionization potential values, and polymorphic coexistence, highlighting the challenges in deriving clear structure-property correlations and underscoring the complexities in achieving highperformance organic electronics with this material.

Efficient and durable energy storage materials are essential to meet the increasing demand for renewable energy technologies. However, existing materials often encounter trade-offs among energy density, power density, and cycling stability. To overcome these limitations, a 2D imide-linked polyoxometalatecovalent organic framework (i-POCOF) is introduced. This hybrid material combines the redox activity of polyoxometalates (POMs) with the structural adaptability of covalent organic frameworks (COFs). Complementarily, 0D imide-functionalized POM-molecule and 1D POM-polymer systems are investigated, enabling a systematic evaluation of how dimensionality affects their physicochemical properties and electrochemical performance. By increasing dimensionality, the hybrids exhibit improved surface area ranging from 107 m 2 g -1 for 0D to 257 m 2 g -1 for 2D, and optimized porosity (average pore size from 1.9 nm for 0D to 3.7 nm for 2D), resulting in enhanced ion diffusion and charge transport. In particular, 2D i-POCOF exhibits remarkable electrochemical performance, achieving a specific capacitance of 132 F g -1 , energy density of 73.3 Wh kg -1 , and power density of 0.9 kW kg -1 , with only 6% capacitance loss after 5000 cycles. These findings highlight the potential of POM hybrids as high-performance and stable energy storage hybrids, providing a promising pathway to overcome current limitations in electrode materials.

Harnessing the full potential of a gate-modulated planar junction to maximize its on-state current density presents fundamental challenges in nanotechnology, particularly for semiconducting nanowires due to their random orientations and partial coverage. Herein, we developed a straightforward method by combining dual self-alignment with nanosphere lithography to fabricate a nanomesh electrode conformally encapsulated by a polymeric insulator. This honeycomb-like nanostructured electrode is designed to form a vertically stacked electrode pair with the (semi-)conducting materials precisely filling its pores. For a 200 μm × 200 μm transistor area, the channel width-to-length ratio is expected to approach 7.6 × 10 5 , effectively achieving a patterning resolution of 100-200 nm without requiring expensive nanofabrication tools such as photolithography and electron-beam lithography. The resulting field-effect transistors using supramolecular poly(3-hexylthiophene) nanowires as channel active layer exhibited a maximum on-state current density exceeding 2000 mA cm -2 . Additionally, the integration of a light-emitting junction by vacuum-depositing tris(8-hydroxyquinolinato) aluminum atop results in gate-modulated uniform luminance up to 1000 cd m -2 . This approach paves the way for highly integrated applications, such as micro-LED pixel driving, by maximizing the transistor current density based on a given metal-insulatorsemiconductor junction.

Molecular motors can act on their environment through their unique ability to generate non-reciprocal autonomous motions at the nanoscale. Although their operating principles are now understood, artificial molecular motors have yet to demonstrate their general capacity to confer novel properties on (supra)molecular systems and materials. Here we show that amphiphilic light-driven molecular motors can adsorb onto an air‒ water interface and form Langmuir monolayers upon compression. By irradiation with ultraviolet light, the surface pressure isotherms of these films reveal a drastic shift toward a smaller molecular area as a consequence of motor activation. We explain this counterintuitive phenomenon by the rotation-induced supramolecular polymerization of amphiphilic motors through a non-thermal annealing process to escape a kinetically trapped amorphous state. The effect is limited by the maximum torque the molecular motor can deliver (~10 pN nm) and leads to the formation of highly organized patterns. This serendipitous discovery highlights the opportunities offered by molecular motors to control supramolecular polymerization for the design of innovative materials.

Abstract In the brain, both the recording and decaying of memory information following external stimulus spikes are fundamental learning rules that determine human behaviors. The former is essential to acquire new knowledge and update the database, while the latter filters noise and autorefresh cache data to reduce energy consumption. To execute these functions, the brain relies on different neuromorphic transmitters possessing various memory kinetics, which can be classified as nonvolatile and volatile memory. Inspired by the human brain, nonvolatile and volatile memory electronic devices have been employed to realize artificial neural networks and spiking neural networks, respectively, which have emerged as essential tools in machine learning. Molecular switches, capable of responding to electrical, optical, electrochemical, and magnetic stimuli, display a disruptive potential for emulating information storage in memory devices. This Review highlights recent developments on responsive molecules, their interfacing with low‐dimensional nanostructures and nanomaterials, and their integration into electronic devices. By capitalizing on these concepts, a unique account of neurotransmitter‐transfer electronic devices based on responsive molecules with ad hoc memory kinetics is provided. Finally, future directions, challenges, and opportunities are discussed on the use of these devices to engineer more complex logic operations and computing functions at the hardware level.

A key requirement for quantum technologies based on atoms, ions, and molecules, is the ability to realize precise phase- and amplitude-controlled quantum operations via coherent laser pulses. However, for generating pulses on the sub-microsecond timescale, the characteristics of the optical and electronic components can introduce unwanted distortions that have a detrimental effect on the fidelity of quantum operations. In this paper, we present a compact arbitrary waveform generator that integrates a double-pass acousto-optic modulator for user-specified laser amplitude and phase modulations. Additionally, the module integrates an optical heterodyne detector to extract the precise laser pulse shape in real-time. The measured pulse shape is then fed into a digital feedback loop used to estimate the complex-valued transfer function and pre-distorted input pulses. We demonstrate the performance by generating shaped laser pulses suitable for realizing quantum logic gates with durations down to 180\,ns, requiring only a small number of feedback iterations.

The crystal structures of organic semiconductors are critical when they are integrated into optoelectronic devices, such as organic field-e)ect transistors (OFETs). In this study, we introduce a crystal engineering approach that leverages weak, nondirectional dispersion forces and steric e)ects, working together to govern the molecular packing. We investigated how the substitution at the periposition a)ects the crystal structure in a series of oligorylene molecules. Upon elucidation of the crystal structures, we found a distinct di)erence between symmetrical and unsymmetrical derivatives. The unsymmetrical derivatives are prone to forming a sandwich herringbone (SHB) motif, while symmetrical derivatives exhibit a typical herringbone (HB) motif. In most of the rylene derivatives, substitutions at the peri-position triggered an "end-to-face" orientation within the HB structure, rather than an "edge-to-face" orientation, which occurs more often. Results from the Hirschfeld surface analysis provide evidence that the "end-to-face" orientation promotes C-H-π interactions between terminal methyl groups and the π-core of the molecules. While these C-H methyl ---π interactions contribute to the overall stability of the packing structure, they remain ine)ective in enhancing the charge transport properties. In contrast, a particular derivative, tetramethyl perylene (TMP), exhibits a HB structure with an edge-to-face orientation, promoting both C-H---π and π---π interactions. These interactions are crucial for improving the charge carrier mobility, as evidenced by mobility values. For TMP, we could obtain the mobility value of 0.05 cm 2 V -1 s -1 in OFETs, whereas a slightly higher mobility of 0.2 cm 2 V -1 s -1 was observed with Field-Induced Time-Resolved Microwave conductivity (FI-TRMC) technique.

Abstract Recent theoretical studies have highlighted how spatially varying cavity electromagnetic fields enable novel cavity quantum electrodynamics phenomena, such as the Dicke superradiant phase transition. Three-dimensional photonic-crystal cavities, which exhibit discrete in-plane translational symmetry, overcome this limitation, but fabrication challenges have hindered the achievement of strong coupling. Here, we demonstrate multimode ultrastrong coupling between cavity modes of a three-dimensional photonic-crystal cavity at terahertz frequencies and the cyclotron resonance of a Landau-quantized two-dimensional electron gas in gallium arsenide. The multimode coupling depends on the spatial profiles of the cavity modes, resulting in distinct coupling scenarios based on probe polarization. Our results align with an extended multimode Hopfield model that accounts for spatial field variations. Guided by the model, we discuss possible strong ground-state correlations between cavity modes and introduce relevant figures of merit for multimode ultrastrong coupling. Our findings highlight the crucial role of spatial inhomogeneity in multimode ultrastrong coupling.

<div><p>MXenes represent one-of-a-kind materials to devise radically novel technologies and achieve breakthroughs in optoelectronics. To exploit their full potential, precise control over the influence of stoichiometry on optical and thermal properties, as well as device performance, must be achieved. Here, the characteristics of optoelectronic devices based on Ti 3 C 2 T x and Ti 2 CT x thin films are uncovered, highlighting the striking difference in their photothermal responses to laser irradiation under different experimental conditions. Even though their absorption coefficients at 450 nm are comparable, the thermal excitation and relaxation phenomena display markedly different kinetics: Ti 2 CT x devices show a strong asymmetry during the heating-cooling cycle, with the heat dissipation kinetics being three orders of magnitude slower than Ti 3 C 2 T x and strongly influenced by environmental conditions. The findings are expected to stimulate fundamental investigations into the photothermal response of MXenes and open exciting prospects for their use in printed and wearable optoelectronics, including memory devices and neuromorphic computing.</p></div>

High-dimensional quantum computing has generated significant interest due to its potential to address scalability and error correction challenges faced by traditional qubit-based systems. This paper investigates the Average Gate Fidelity (AGF) of single qudit systems under Markovian noise in the Lindblad formalism, extending previous work by developing a comprehensive theoretical framework for the calculation of higher-order correction terms. We derive general expressions for the perturbative expansion of the Average Gate Infidelity (AGI) in terms of the environmental coupling coefficient and validate these with extensive numerical simulations, emphasizing the transition from linear to nonlinear behaviour in the strong coupling regime. Our findings highlight the dependence of AGI on qudit dimensionality, quantum gate choice, and noise strength, providing critical insights for optimising quantum gate design and error correction protocols. Additionally, we utilise our framework to identify universal bounds for the AGI in the strong coupling regime and explore the practical implications for enhancing the performance of near-term qudit architectures. This study offers a robust foundation for future research and development in high-dimensional quantum computing, contributing to the advancement of robust, high-fidelity quantum operations.

<div><p>We present a novel, portable sensor platform that enables concurrent monitoring of surface mass and charge density variations at thin biointerfaces. This platform combines a coplanar-gated field-effect transistor (FET) architecture with grating-coupled surface plasmon resonance (SPR), yielding an integrated disposable sensor chip prepared by nanoimprint and maskless photolithography techniques. The sensor chip design is suitable for scalable production and relies on reduced graphene oxide (rGO), serving as the FET's semiconductor material for the electronic readout, and a metallic gate electrode surface that is corrugated with a multidiffractive structure for optical probing with resonantly excited surface plasmons (SPs). Together with its integration in a compact instrumentation, this results in a form factor optimized solution for dual-mode investigations without compromising the optical or electronic sensor performance. A poly-L-lysine (PLL)-based thin linker layer was deployed at the sensor surface to covalently attach azide-conjugated biomolecules by using incorporated "clickable" dibenzocyclooctyne (DBCO) moieties. Interestingly, the dual-mode measurements allow elucidating the role of the globular nature of the PLL chains when increasing the density of DBCO attached to their backbone, leading to PLL folding and internalization of DBCO moieties, and thus reducing the coupling yield for the used deoxyribonucleic acid (DNA) oligomers. We envision that this platform can be employed to studying a range of other biointerface architectures and biomolecular interaction phenomena, which are inherently tied to mass and charge density variations.</p></div>

Light-matter interactions have generated considerable interest as a means to manipulate material properties. Light-induced superconductivity has been demonstrated using pulsed lasers. An attractive alternative possibility is to exploit strong light-matter interactions arising by coupling phonons to the vacuum electromagnetic field of a cavity mode as has been suggested and theoretically studied. Here we explore this possibility for two very different superconductors, namely YBCO (YBa$_2$Cu$_3$O$_{6+x}$) and Rb$_3$C$_{60}$, coupled to surface plasmon polaritons, using a novel cooperative effect based on the presence of a strongly coupled vibrational environment allowing efficient dressing of the otherwise weakly coupled phonon bands of these compounds. By placing the superconductor-surface plasmon system in a SQUID magnetometer, we find that the superconducting transition temperatures ($T_{c}$) for both compounds are modified in the absence of any external laser field. For YBCO, $T_{c}$ decreases from 92 K to 86 K while for Rb$_3$C$_{60}$, it increases from 30 K to 45 K at normal pressures. In the latter case, a simple theoretical framework is provided to understand these results based on an enhancement of the electron-phonon coupling. This proof-of-principle study opens a new tool box to not only modify superconducting materials but also to understand the mechanistic details of different superconductors.

The solid-state structure and morphology of organic semiconductors (OSCs) are critical in determining the performance of organic electronic devices, as they directly influence charge carrier mobility. Improved molecular packing and ordering are key to achieving better device performance. While halogen bonding (XB) has been extensively used in supramolecular crystal engineering, its potential for organic electronics remains largely untapped. Here, we show that strong and directional XB can significantly enhance the morphology and optoelectronic properties of a pyridine-substituted naphthalene diimide (NDI) derivative. By employing various XB donors with differing interaction strengths and comparing them to a nonbonding reference compound, we achieve a two-orders-of-magnitude improvement in field-effect mobility and I ON -I OFF ratio. Furthermore, the geometric substitution pattern of the XB donors is found to strongly influence molecular packing, crystalline domain formation, and, ultimately, device performance.

The conversion of CO2 and epoxides into cyclic carbonates represents a promising strategy for CO2 utilization and valorization, with applications spanning pharmaceuticals, agrochemicals, polymer manufacturing, and energy storage. This concept article provides a concise perspective on the advancements in CO2 cycloaddition reactions catalyzed by single-atom catalysts (SACs), encompassing photocatalysis, thermocatalysis, and photothermal catalysis. Despite significant progress in the field, challenges such as limited catalytic activity and low stability of SACs under reaction conditions remain significant obstacles to industrial implementation. Mechanistic insights into active species are emphasized to enable the rational design and optimization of catalytic systems. Additionally, key industrial challenges, such as the elimination of co-catalysts, scalability limitations, and the development of cost-effective production methods, are critically examined. By bridging fundamental research and practical applications, this concept article seeks to guide future advancements in the sustainable production of cyclic carbonates through CO2 cycloaddition.

<div><p>Two-dimensional conjugated metal-organic frameworks (2D c-MOFs) have emerged as an intriguing class of quantum materials due to their high crystallinity, persistent spin centers, and tunable structures and topologies. However, it remains unclear how to achieve long spin relaxation time at room temperature in 2D c-MOFs via a bottom-up design strategy. Herein, we design a hexahydroxytrithiatruxene ligand (HHTH) to minimize the influence of nuclear spin on electron spin relaxation while weakening d-π conjugation to construct a "spin docking" for preserving spin centers, which enables the resulting 2D c-MOFs, Ni 3 HHTH 2 , to exhibit quantum coherence and Rabi oscillations at room temperature. Spin dynamics studies not only reveal an unusual temperature-dependent Rabi frequency in Ni 3 HHTH 2 but also indicate that the coordination mode determines the spinlattice relaxation behavior via spin-phonon coupling. These investigations provide a general guideline for the development of highperformance quantum qubits based on 2D spin arrays.</p></div>

Plasmonic metal/semiconductor hetero-nanostructures have attracted tremendous research interests in optoelectronic devices, photocatalysis and photothermal therapy, and related fields. Among various mechanisms of localized surface plasmon resonance (LSPR) induced enhancements, the mechanism of LSPR-induced hot carriers injection has emerged as a particularly powerful and efficient process for modulating charge dynamics, especially in photocatalysis. The efficiency of these hot carrier injections relies on robust metal-semiconductor interfaces, with performance heavily influenced by the composition, crystallinity and atomic structure of the multi-interfaces involved. This perspective explores the mechanisms of LSPR-induced hot carrier injection, highlighting recent advances with emphasis on multi-interfacial engineering to optimize charge dynamics and utilization. These interface-regulated hot carrier processes, combined with enhanced photocatalytic performance, provide with new opportunities for further advanced photocatalysis and a wide range of photoelectric conversion applications.

<div><p>Two-dimensional (2D) polymeric fullerene scaffolds, composed of covalently bonded superatomic C60 nanoclusters, are emerging semiconductors possessing unique hierarchical electronic structures. Hitherto their synthesis has relied on complex and time-consuming reactions, thereby hindering scalable production and limiting the technological relevance. Here, we demonstrate a facile electrochemical exfoliation strategy based on the intercalation and expansion of a layered fullerene superlattice, to produce large size (~52.5 µm 2 ) and monolayer thick 2D polymeric C60 with high yield (~83%). In-situ reduction of solvated protons (H + ) weakens the interlayer interactions thereby promoting the rapid and uniform intercalation of tetra-n-butylammonium (TBA + ), ensuring gram-scale throughput and high structural integrity of exfoliated 2D polymeric C60. As a proof of concept, the solution-processed 2D polymeric C60 nanosheets have been integrated into thin-film photodetectors, exhibiting a broad spectral photoresponse ranging from 405 nm to 1200 nm, with a peak photocurrent at 850 nm and a stable response time. This efficient and scalable exfoliation method holds great promise for the advancement of multifunctional composites and optoelectronic devices based on 2D polymeric C60.</p></div>

Despite advances in the field of 2D polymerization, the synthesis of high-quality, micrometre-thick films of oriented 2D covalent organic frameworks (COFs) remains challenging. Conventional approaches focusing on thermodynamic control of the polymerization pathway face a detrimental trade-off between orientation and thickness. Here we describe a straightforward method for preparing imine-linked 2D COF films with a near-perfect face-on orientation by leveraging kinetically trapped amorphous 3D covalent adaptable network (CAN) intermediates. These off-pathway intermediates are generated as coatings through solution casting, during which the CANs spontaneously align to relax tensile stresses induced by solvent evaporation. A subsequent lift-off process, followed by an amorphous-to-crystalline transformation under solvothermal conditions, converts the 3D-oriented polymer networks into thermodynamically stable, porous and free-standing 2D COF films. This versatile kinetic trapping strategy is suitable for a range of building blocks and network topologies, constituting a convenient synthetic tool for accessing high-quality, robust, large-area 2D COF films with a strongly aligned polycrystalline structure.

A reliable method for the efficient chemical synthesis and poly(ethylene glycol) PEG-like modification of fluorogenic RNA aptamers is reported. The 43-mer version of Mango-II RNA (MangoII-v1), which binds tightly and specifically to the green fluorophore TO1-Biotin (TO1-B), was synthesized by automated phosphoramidite chemistry using 2′-O-[(triisopropylsilyl)oxy]methyl] (2′-O-TOM)-protected ribonucleosides. Solid-phase phosphoramidite chemistry was also used as a single tool to prepare MangoII-v1 modified with a PEG-like oligophosphate synthetic segment (MangoII-v1-P). After cleavage from the resin, deprotection, and purification, the capacity to activate the fluorescence of TO1-B and the degradation behavior of the chemically synthesized RNAs MangoII-v1 and MangoII-v1-P, were deeply investigated in comparison with those of the enzymatically synthesized 48 nucleotides long RNA MangoII. Interestingly, the chemically synthesized MangoII-v1 RNA aptamer demonstrated great activity toward its target, compared to the enzymatically synthesized analogue. Moreover, it was found to be highly stable, retaining its structural integrity and bioactivity, even after seven days of incubation in 20% fetal bovine serum. MangoII-v1-P also showed a high affinity for TO1-B and excellent degradation resistance.

<div>Rationale:<p>To increase the confidentiality level of molecular tags, binary information can be hidden in sequence-defined oligomers using isobaric monomers including a photo-sensitive one, which mass can be modified upon light irradiation. Reading such secured data requires light edition prior to MS/MS sequencing, which was investigated here in a single gas-phase workflow. Methods: Oligo (phosphodiester)s made of units with either light-sensitive ortho-or light-inert para-nitrobenzyl side-group were electrosprayed as deprotonated oligomers and sampled in an ion trap instrument equipped with various light sources. Nanosecond-pulsed laser (266 or 365 nm) and CW laser (375 nm) irradiations were compared for their efficiency to induce photocleavage of all o-nitrobenzyl moieties in laser-induced dissociation and to produce sufficient amounts of edited oligomers to achieve full coverage of their sequence in collision-induced dissociation. Results: While cleavage of photo-sensitive moieties was never fully achieved with the pulsed laser, photo-cleavage of all onitrobenzyl side-groups readily occurred with the CW laser, as monitored by successive losses of o-nitrobenzaldehyde from the irradiated chains. Time required for maximal production of edited oligomers increased with their number of reactive units but shorter irradiation steps were found sufficient to produce enough secondary precursors to achieve full sequence coverage in MS/ MS. Conclusions: Laser-induced modification of light-sensitive units allowed monotonic sequences of two isobaric monomers to be turned into MS/MS readable sequences. This gas-phase experiment enables a much higher throughput compared with the 1-h irradiation requested for the oligomer edition when performed in solution.</p></div>

Abstract Aqueous microdroplets have been reported to dramatically increase the rate of chemical reactions. Proposed mechanisms for this acceleration include confinement effects upon droplet evaporation, and Brønsted acid or electric field catalysis at the air‐water interface. However, computational investigations indicate that the operation of these mechanisms is reaction‐dependent, with conclusive evidence for a role for electric field catalysis still lacking. Here, we present a computational investigation of the reported abiotic phosphorylation of ribose and the subsequent formation of ribonucleosides, focusing on acidity and oriented external electric field (OEEF) effects. The most plausible reaction mechanism identified involves the protonation of ribose, followed by carbocation formation and an S N 2 substitution step. Without an OEEF, all considered pathways are thermally inaccessible. However, in the presence of a significant OEEF, the S N 2‐based pathway, leading to the β ‐ribonucleoside isomer, becomes highly stabilized, reducing the energetic span to a thermally accessible 12–13 kcal/mol. Surprisingly, the OEEF‐mediated reaction closely mirrors the enzymatic mechanism of phosphorolysis via S N 2 substitution, including a pronounced anomeric selectivity. Our results support the hypothesis that some reactions in aqueous microdroplets are accelerated by electric fields and provide further evidence for the importance of electrostatic catalysis in biological systems, particularly for phosphorylase enzymes.

Biology has mastered energy transduction, converting energy between various forms, and employing it to drive its vital processes. Central to this is the ability to use chemical energy for the active transport of substances, pumping ions and molecules across hydrophobic lipid membranes between aqueous (sub)cellular compartments. Biology employs information ratchet mechanisms, where kinetic asymmetry in the fuel‐to‐waste (i. e., substrate‐to‐product) conversion results in catalysis‐driven active transport. Here, we report an artificial system for catalysis‐driven active transport across a hydrophobic phase, pumping a maleic acid cargo between aqueous compartments. We employ two strategies to differentiate the conditions in either compartment, showing that active transport can be driven either by adding fuel to a single compartment, or by differentiating the rates of activation and/or hydrolysis when fuel is present in both compartments. We characterize the nonequilibrium system through complete kinetic analysis. Finally, we quantify the energy transduction achieved by the catalysis‐driven active transport and establish the emergence of positive and negative feedback mechanisms within the system.

The dynamics of many-body quantum states in open systems is commonly numerically simulated by unraveling the density matrix into pure-state trajectories. In this work, we introduce a new unraveling strategy that can adaptively minimize the averaged entanglement in the trajectory states. This enables a more efficient classical representation of trajectories using matrix product decompositions. Our new approach is denoted non-unitarity maximizing unraveling (NUMU). It relies on the idea that adaptively maximizing the averaged non-unitarity of a set of Kraus operators leads to a more efficient trajectory entanglement destruction. Compared to other adaptive entanglement lowering algorithms, NUMU is computationally inexpensive. We demonstrate its utility in large-scale simulations with random quantum circuits. NUMU lowers runtimes in practical calculations, and it also provides new insight on the question of classical simulability of quantum dynamics. We show that for the quantum circuits considered here, unraveling methods are much less efficient than full matrix product density operator simulations, hinting to a still large potential for finding more advanced adaptive unraveling schemes.

Orientation and steric hindrance decrease the efficiency for an antibody to attach to its specific receptor. Giving flexibility to a dendronized peptide through a small PEG fragment increases the peptides affinity to cellular receptors.

Abstract The controlled formation of a functional adlayer at the catalyst‐water interface is a highly challenging yet potentially powerful strategy to accelerate proton transfer and deprotonation for ultimately improving the performance of proton‐exchange membrane water electrolysis (PEMWE). In this study, the synthesis of robust vinylene‐linked covalent organic frameworks (COFs) possessing high proton conductivities is reported, which are subsequently hybridized with ruthenium dioxide yielding high‐performance anodic catalysts for the acidic oxygen evolution reaction (OER). In situ spectroscopic measurements corroborated by theoretical calculations reveal that the assembled hydrogen bonds formed between COFs and adsorbed oxo‐intermediates effectively orient interfacial water molecules, stabilizing the transition states for intermediate formation of OER. This determines a decrease in the energy barriers of proton transfer and deprotonation, resulting in exceptional acidic OER performance. When integrated into a PEMWE device, the system achieves a record current density of 1.0 A cm −2 at only 1.54 V cell voltage, with a long‐term stability exceeding 180 h at industrial‐level 200 mA cm −2 . The approach relying on the self‐assembly of an oriented hydrogen‐bonded adlayer highlights the disruptive potential of COFs with customizable structures and multifunctional sites for advancing PEMWE technologies.

A dual relay catalytic protocol, built on reversible dehydrogenation of amines by Rh catalysis and C–H functionalisation of transient imines by Pd catalysis, is reported to enable regioselective arylation of amines at their unactivated β-C(sp3)–H bond. Notably, the new strategy is applicable to secondary anilines and N-PMP-protected primary aliphatic amines of intermediate steric demands, which is in contrast to the existing strategies that involve either free-amine-directed C–H activation for highly sterically hindered secondary aliphatic amines or steric-controlled migrative cross-coupling for unhindered N-Boc protected secondary aliphatic amines. Regioselectivity of the reaction is imposed by the electronic effects of transient imine intermediates rather than by the steric effects between specific starting materials and catalysts, thereby opening the uncharted scope of amines. In a broader sense, this study demonstrates new opportunities in dual relay catalysis involving hydrogen borrowing chemistry, previously explored in the functionalisation of alcohols, to execute otherwise challenging transformations for amines, commonly present in natural products, pharmaceuticals, biologically active molecules, and functional materials.

The neutral, dizwitterionic dicarboxylate 1,4‐bis(carboxylatomethyl)piperazine (cmpip) is used in the solvohydrothermal synthesis of three uranyl ion complexes. Both [(UO 2 ) 2 Cl 2 (pda)(cmpip) 2 ]·2H 2 O ( 1 ) and [(UO 2 ) 2 Cl 2 (chdc)(cmpip) 2 ] ( 2 ) are mixed‐ligand complexes involving additional dianionic dicarboxylates, 1,4‐phenylenediacetate (pda 2− ), or trans ‐1,4‐cyclohexanedicarboxylate (chdc 2− ), respectively, which crystallize as two‐stranded, ladder‐like monoperiodic coordination polymers. The chains in 1 and 2 are arranged into thick layers, adjacent chains being associated through strong NH…O reciprocal hydrogen bonding of cmpip ligands. The complex [UO 2 (cmpip) 2 (H 2 O)](NO 3 )Cl·2H 2 O ( 3 ) involves only cmpip as a carboxylate donor, and it crystallizes as a diperiodic assembly with the sql topology. The four cmpip ligands bound to uranyl are located on the same side of it so as to form a deep cavity, resulting in the heavily puckered geometry of the layers. The cmpip ligands in 3 are involved in extended hydrogen bonding with other cmpip ligands and chlorine and nitrate anions. Compound 2 is nonemissive, but 1 and 3 have a photoluminescence quantum yield of 7% in the solid state, with an emission spectrum showing the usual vibronic fine structure.

<div><p>Many high-performance perovskite solar cells (PSCs) rely heavily on halogenated antisolvent methods, hampering their potential commercialization. In this work, the industry-compatible dimethyl sulfide (DMS) solvent, which coordinates strongly with the metal cation, is used in a bathing approach to investigate the crystallization of triple halide perovskites. The resulting thin films are more uniform exhibiting preferential crystal growth in the (001) direction (perpendicular to the substrate) and large grains of 444 ± 122 nm compared to 421 ± 147 nm for the reference films. Moreover, the electron diffusion length and lifetimes are enhanced from 1 to 3 mm and from 551 to 1050 ns, respectively, compared to the reference film. The champion solar cell based on our approach exhibits a power conversion efficiency (PCE) of 20.6%, comparable to the conventional lab-scale counterpart at 21.4%.</p><p>Additionally, the long-term stability of our devices shows that 88% (similar to the reference at 93%) of the initial performance is retained after 60 days at room temperature with 60% relative humidity.</p></div> <div>Broader context<p>Improvement of the limiting factors including scalable and high-quality lm deposition is crucial for the commercial application of perovskite solar cells. Here, the antisolvent bathing (ASB) method with the high coordination dimethyl sulde solvent has been explored as a promising candidates due to the efficient extraction of the precursor solvents lingering in the perovskite lm. Using the ASB approach and 5 min annealing at 80 °C, highly crystalline lms with an average grain size of 444 nm are observed. Furthermore, a photovoltaic performance at 20.6% is achieved together with a stability of 88% of the initial PCE, even aer 60 hours of aging under ambient environmental conditions such as room temperature, and 60% relative humidity.</p></div>

<div><p>Molecular recognition and detection of small bioactive molecules, like neurotransmitters, remain a challenge for chemists, whereas nature found an elegant solution in the form of protein receptors. Here, we introduce a concept of a dynamic artificial receptor that synergically combines molecular recognition with dynamic imine bond formation inside a lipid nanoreactor, inducing a fluorescence response. The designed supramolecular system combines a lipophilic recognition ligand derived from a boronic acid, a fluorescent aldehyde based on push-pull styryl pyridine and a phenol-based catalyst. The recognition ligand specifically captures dopamine inside lipid nanodroplets and thus triggers imine bond formation with the aldehyde, producing the emission color change. The rational design of the fluorescent aldehyde, the catalyst, and the recognition ligand allows dramatic acceleration of the imine bond formation required for rapid sensing of dopamine. The nanoprobe enables dopamine detection with micromolar sensitivity and singe-nanoprobe imaging of dopamine gradients through its robust two-color ratiometric response. It displays remarkable selectivity without the interference of competing biogenic primary amines and biological media: blood serum, plasma, urine and cell lysate. The proposed concept of a dynamic artificial receptor offers a solution to the long-standing problem of molecular recognition and sensing of small molecules in complex biological media.</p></div>

Abstract Biomolecular machines autonomously convert energy into functions, driving systems away from thermodynamic equilibrium. This energy conversion is achieved by leveraging complex, kinetically asymmetric chemical reaction networks that are challenging to characterize precisely. In contrast, all known synthetic molecular systems in which kinetic asymmetry has been quantified are well described by simple single‐cycle networks. Here, we report on a unique light‐driven [2]rotaxane that enables the autonomous operation of a synthetic molecular machine with a multi‐cycle chemical reaction network. Unlike all prior systems, the present one exploits a photoactive macrocycle, which features a different photoreactivity depending on the binding sites at which it resides. Furthermore, E to Z isomerization reverses the relative affinity of the macrocycle for two binding sites on the axle, resulting in a multi‐cycle network. Building on the most recent theoretical advancements, this work quantifies kinetic asymmetry in a multi‐cycle network for the first time. Our findings represent the simplest rotaxane capable of autonomous shuttling developed so far and offer a general strategy to generate and quantify kinetic asymmetry beyond single‐cycle systems.

SNAr reactions were remarkably accelerated using a pre-targeting and activating unit based on dynamic covalent chemistry (DCvC). A Cys attack at the C-F bond on the aromatic ring of salicylaldehyde derivatives was only observed upon iminium formation with a neighboring Lys residue of model small peptides. Such self-activation was ascribed to the stronger electron-withdrawing capability of the iminium bond with respect to that of the parent aldehyde that stabilized the transition state of the reaction, together with the higher preorganization of the reactive groups in the cationic aldiminium species. This approach was further applied for the functionalization of two antibodies. In both cases, the presence of the aldehyde group in close proximity to the reactive C-F bond resulted in a noteworthy increase in bioconjugation yields, with excellent chemoselectivity. Whereas the modification of an IgG1 antibody led to stochastic product distributions, microenvironment-selectivity was noted when employing IgG4, in line with the lower number of Lys residues in the hinge region of the latter. Additionally, the post-functionalization of the modified antibodies was attained through the dynamic covalent exchange of the tethered iminium derivative with hydrazides, representing an unprecedented "tag and modify" selective bioconjugation strategy based on DCvC. TCEP A1 (i) (iii) (vi) DAR 4 HIC red-IgG4 ADC-I4 VcMMAE-ADC-I4 C) A) 84 K 12 na C-C 4 sa C-C B)

Two-dimensional (2D) materials are promising candidates for solar-driven desalination. However, conventional photothermal 2D materials like transition metal carbides and nitrides (MXenes) as well as transition metal dichalcogenides (TMDs) suffer from major limitations such as their complex synthesis and low photothermal conversion efficiency. In contrast, metal phosphorus trichalcogenides (MPCh3) do not display the same drawbacks and possess widely tunable bandgaps (1.2–3.5 eV), making them ideal candidates for solar desalination. Moreover, their properties and applications related to light–matter interactions can be further enhanced by coupling with other low-dimensional nanostructures, tailoring hybrid van der Waals heterostructures of mixed dimensionality. Herein, we report the synthesis of FePS3 nanosheets/carbon nanodots (CNDs) 2D/0D nanoheterojunctions and their photothermal response when integrated into a 3D photothermal evaporator. These nanoheterojunctions exhibited high photothermal conversion performance, with an average absorbance of 90.6% from the UV to the NIR and a temperature increase of 42 °C over the blank control under 1 sun illumination for 300 s. A high water evaporation rate of 1.68 kg m–2 h–1 was observed under the same condition. Photothermal conversion and water evaporation experiments, along with femtosecond transient absorption spectroscopy (fs-TAS), photoluminescence (PL) analysis, and finite-difference time-domain (FDTD) simulations, revealed that the incorporation of CNDs and formation of the nanoheterojunction synergistically enhance localized heating and light absorption, improve trapping efficiency, and optimize nonradiative transition pathways. This study demonstrates the disruptive potential of the rational design of high-performance 2D material hybrids through MPCh3-based nano

We report the carbonization of metal-organic framework-5 (MOF-5) at various temperatures to investigate the correlation between physicochemical properties and electrochemical performance in zinc-ion energy storage. The sample carbonized at 1000 °C exhibits the highest specific capacitance (268.93 F g^-1 ), energy density (166.9 W h kg^-1 ), and power density (9234 W kg^-1 ), attributed to increased porosity, enhanced graphitization, and reduced charge transfer resistance. This simultaneous achievement of high energy and power densities underscores the potential of carbonized MOF-5 (CMOF-5) as a high-performance nanostructured electrode material for advanced energy storage devices.

Data show that the presence of women in quantum science is affected by a number of detriments and their percentage decreases even further for higher positions. Beyond data, from our shared personal experiences as female tenured quantum physics professors, we believe that the current model of scientific leadership, funding, and authority fails to represent many of us. It is time for a real change that calls for a different kind of force and for the participation of everyone. Women for quantum calls for a joint effort and aims with this initiative to contribute to such a transformation.

Four distinct zeolitic imidazolate frameworks (ZIFs) are prepared using zinc and cobalt ions with 2-aminobenzimidazole and 2-methylimidazole as linkers to explore their electrochemical properties as platforms for aldehyde detection.

Two-dimensional van der Waals heterostructures with exotic quantum phenomena have garnered a huge surge in the field of optoelectronic devices. Herein, we report spectroscopic evidence of efficient interfacial charge transfers at the interface of a novel 2D/2D V₄C₃T<i>_<i>x</i></i> MXene/protonated g-C₃N₄ (PCN) heterostructured thin film, demonstrating robust photosensitivity and a large exciton activation energy of 139.5 meV. Through temperature-dependent photoluminescence (PL) and timeresolved PL spectroscopy, we unravel the photophysical mechanism driving efficient charge transfer and photosensitivity inV₄C₃T<i>_<i>x</i></i>/PCN heterostructures. These heterostructures exhibit superior photosensitivity to white and UV light compared with either PCN or V₄C₃T<i>_<i>x</i></i> pristine materials. Additionally, we observed significant PL quenching with unusual negative thermal quenching and extended charge carrier lifetime in the V₄C₃T<i>_<i>x</i></i>/ PCN heterostructures across a broad temperature range of 70-370 K. Notably, at the elevated temperature of 370 K, the carrier lifetime was enhanced by more than 2-fold, making the heterostructures promising for optoelectronic applications. This work provides critical insight into the charge transfer mechanism between V₄C₃T<i>_<i>x</i></i> MXene and PCN, opening a new avenue for rationally designing g-C₃N₄-based heterostructures for highly photosensitive optoelectronic devices.

Circularly polarized luminescence (CPL) can be induced by doping an achiral fluorescent dye into a chiral polymer matrix. Here, we demonstrate the supramolecular self-assembly of chiral poly(L-lactic acid) (PLLA) with the fluorescent dye, 9,10-bis(phenylethynyl)anthracene (BPEA), forming microspheres that generate CPL. As the BPEA concentration increases, the fluorescent colour shifts from blue to green and red, suggesting the formation of BPEA dimers and J-aggregates. The highest luminescent dissymmetry factor (g_lum) of 3.1 × 10⁻² was obtained from the microsphere suspension at the BPEA/PLLA ratio of 0.1.

sp$^2$-carbon-linked covalent organic frameworks (sp$^2$c-COFs) are crystalline porous polymers with repeat organic units linked by sp$^2$ carbons, and have attracted increasing interest due to their robust skeleton and tunable semiconducting properties. Single-crystalline sp$^2$c-COFs with well-defined structures can represent an ideal platform for investigating fundamental physics properties and device performance. However, the robust olefin bonds inhibit the reversible-reaction-based crystal self-correction, thus yielding polycrystalline or amorphous polymers. Here we report an imine-to-olefin transformation strategy to form single-crystal sp$^2$c-COFs. The isolated single crystals display rectangular nanotube-like domains with sizes up to approximately 24 μm × 0.8 μm × 0.8 μm, and permanent pore distribution around 1.1 nm. The highly conjugated olefin linkage endows the crystals with enhanced electronic connectivity which determines a remarkable room-temperature metal-free ferromagnetism (8.6 × 10$^{-3}$ emu g$^{-1}$). Our protocol is robust and generally applicable for the synthesis of single-crystalline sp$^2$c-COFs for future spin-electron devices.

Thermal fluctuations pose a significant challenge to the signal stability of nanomaterial-based piezoresistive pressure sensors, limiting their effectiveness in applications such as electronic skin and robotics. Conventional temperature compensation strategies often rely on additional thermal sensors or complex calibration algorithms. Here, a flexible pressure sensor is reported featuring a nonlinear conductive graphene composite layer within a bilayer architecture, enabling bias voltage-controlled sensitivity without structural redesign. The sensor achieves ultra-high sensitivity (742.3 kPa^-1), a broad linear sensing range of up to 800 kPa (R² = 0.99913), and excellent long-term durability over 10 000 cycles. Crucially, the unique nonlinear characteristics enable the bias voltage to function as an internal remote control for correcting temperature drifts between 25 and 60 °C, as demonstrated by precise manipulation in robotic grippers under varying temperature conditions. This work offers a universal strategy for building environmentally adaptive sensors, advancing the development of robust and high-precision wearable electronics.

A series of novel conjugated semiconducting polymers based on the unsubstituted thiazolo[5,4-d]thiazole (TzTz) unit is synthesized using atom-economic and environmentally friendly direct (hetero)arylation polymerization (DHAP). The versatility of the proposed polymerization conditions, employing a non-chlorinated and moderately toxic solvent and cooperative palladium/copper bimetallic catalytic system, is demonstrated through the use of seven comonomers with varying electron-withdrawing strength: 2,2′-bithiophene (BT), 6,7-difluoroquinoxaline (Qx), thieno[3,4-c]pyrrole-4,6(5H)-dione (TPD), 5,6-difluorobenzo[c][1,2,5]thiadiazole (BTD), isoindigo (IID), para-azaquinodimethane (AQM) and 2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione (DPP). The resulting TzTz-based copolymers exhibit optical bandgaps between 1.5 and 2.0 eV with HOMO/LUMO energy levels spanning from -5.2/-3.3 eV to -5.4/-3.9 eV. They all show satisfactory thermal stability for electronic applications (Td = 300-360 °C). Notably, TzTz-based copolymers are observed they generally exhibit improved backbone planarity and deeper LUMO levels than their thiophene derivatives. A synthesis tool to finely lower the LUMO levels of next-generation A-A' copolymers in view of increasing the performance and air-stability of doped organic electronics is believed to be provided by this work.

Iron is essential for bacterial growth, and Pseudomonas aeruginosa synthesizes the siderophores pyochelin (PCH) and pyoverdine to acquire it. PCH contains a thiazolidine ring that aids in iron chelation but is prone to hydrolysis, leading to the formation of 2-(2-hydroxylphenyl)-thiazole-4-carbaldehyde (IQS). Using mass spectrometry, we demonstrated that PCH undergoes hydrolysis and oxidation in solution, resulting in the formation of aeruginoic acid (AA). This study used proteomic analyses and fluorescent reporters to show that AA, dihydroaeruginoic acid (DHA), and PCH induce the expression of femA, a gene encoding the ferri-mycobactin outer membrane transporter in P. aeruginosa. Notably, the induction by AA and DHA was observed only in strains unable to produce pyoverdine, suggesting their weaker iron-chelating ability compared to that of pyoverdine. 55Fe uptake assays demonstrated that both AA-Fe and DHA-Fe complexes are transported via FemA; however, no uptake was observed for PCH-Fe through this transporter. Structural studies revealed that FemA is able to bind AA2-Fe or DHA2-Fe complexes. Key interactions are conserved between FemA and these two complexes, with specificity primarily driven by one of the two siderophore molecules. Interestingly, although no iron uptake was noted for PCH through FemA, the transporter also binds PCH-Fe in a similar manner. These findings show that under moderate iron deficiency, when only PCH is produced by P. aeruginosa, degradation products AA and DHA enhance iron uptake by inducing femA expression and facilitating iron transport through FemA. This provides new insights into the pathogen’s strategies for iron homeostasis.

We report the synthesis of a new functional molecule, a quater-tiophene based surfactant, which can both adsorb at the water / gas interface (surface active molecule) and aggregates through pi-pi stacking interactions. We assess then the ability of this molecule to create these functionalities at interfaces. This interfacial functional aggregation, characterized here in situ for the first time, is probed thanks to Langmuir trough experiments and spectrometric ellipsometry. These results open some new routes for the design of new water based opto-electronic devices.

Isomer discrimination is of paramount importance across various sectors, including pharmaceuticals, agriculture, and the food industry, owing to their unique physicochemical characteristics. Because of their extremely similar characteristics, traditional analytical methods fail or encounter severe limitations in isomer discrimination. To overcome this grand challenge, a novel sensing strategy is proposed based on surface-enhanced Raman scattering (SERS) substrates (i.e., plasmonic platforms) combined with machine learning algorithms. These plasmonic platforms exhibit exceptional signal uniformity across wide regions and sensitivity, enabling the discrimination of structural isomers (hydroquinone, resorcinol, pyrocatechol), geometric isomers ((Z/E)-stilbene, (Z/E)-resveratrol), and optical isomers (R/S-ibuprofen). Notably, for the analysis of optical isomers, 1-naphthalenethiol is employed as a probe to facilitate specific isomer orientation on the surface of the plasmonic platform through, for the first time, π–π interactions. The integration of machine learning methodologies, such as Partial Least Squares Regression and Artificial Neural Networks, significantly enhances both quantitative analysis and classification accuracy, achieving detection limits as low as 2 × 10⁻⁸ m. Validation with commercially available ibuprofen samples shows excellent agreement with traditional circular dichroism results, highlighting the method's robustness and precision. The strategy provides a versatile, ultrasensitive, and reliable solution for isomer discrimination, with broad applications in pharmaceuticals, environmental monitoring, and clinical diagnostics.

Dirac particles have two intrinsic degrees-of-freedom, helicity and chirality. While helicity is conserved in time, chirality is not constant under time evolution for massive particles, yielding the phenomenon of chiral oscillations. So far, chiral oscillations have been mainly described in the framework of single particle relativistic quantum mechanics. In this paper, we present a quantum field theory approach to chiral oscillations in analogy with the one used to describe flavor mixing and oscillations. By taking the expectation value of chiral charges, we obtain the same chiral oscillation formula derived via standard relativistic quantum mechanics. We find that chiral charges are diagonalized by a Bogoliubov transformation: this implies that the vacuum for particles with definite chirality is orthogonal to the one for those with definite energy. In the case of neutrinos, our results can be further extended to include also flavor oscillations.