Molecular Interface Research Articles

A Chemist's View on Electronic and Steric Effects of Surface Ligands on Plasmonic Metal Nanostructures.

ConspectusPlasmonic metal nanostructures have been extensively developed over the past few decades because of their ability to confine light within the surfaces and manipulate strong light-matter interactions. The light energy stored by plasmonic nanomaterials in the form of surface plasmons can be utilized to initiate chemical reactions, so-called plasmon-induced catalysis, which stresses the importance of understanding the surface chemistry of the plasmonic materials. Nevertheless, only physical interpretation of plasmonic behaviors has been a dominant theme, largely excluding chemical intuitions that facilitate understanding of plasmonic systems from molecular perspectives. To overcome and address the lack of this complementary understanding based on molecular viewpoints, in this Account we provide a new concept encompassing the well-developed physics of plasmonics and the corresponding surface chemistry while reviewing and discussing related references. Inspired by Roald Hoffmann's descriptions of solid-state surfaces based on the molecular orbital picture, we treat molecular interfaces of plasmonic metal nanostructures as a series of metal-ligand complexes. Accordingly, the effects of the surface ligands can be described by bisecting them into electronic and steric contributions to the systems. By exploration of the quality of orbital overlaps and the symmetry of the plasmonic systems, electronic effects of surface ligands on localized surface plasmon resonances (LSPRs), surface diffusion rates, and hot-carrier transfer mechanisms are investigated. Specifically, the propensity of ligands to donate electrons in a σ-bonding manner can change the LSPR by shifting the density of states near the Fermi level, whereas other types of ligands donating or accepting electrons in a π-bonding manner modulate surface diffusion rates by affecting the metal-metal bond strength. In addition, the formation of metal-ligand bonds facilitates direct hot-carrier transfer by forming a sort of molecular orbital between a plasmonic structure and ligands. Furthermore, effects of steric environments are discussed in terms of ligand-ligand and ligand-surface nonbonding interactions. The steric hindrance allows for controlling the accessibility of the surrounding chemical species toward the metal surface by modulating the packing density of ligands and generating repulsive interactions with the surface atoms. This unconventional approach of considering the plasmonic system as a delocalized molecular entity could establish a basis for integrating chemical intuition with physical phenomena. Our chemist's outlook on a molecular interface of the plasmonic surface can provide insights and avenues for the design and development of more exquisite plasmonic catalysts with regio- and enantioselectivities as well as advanced sensors with unprecedented chemical controllability and specificity.

Adsorption Structures Affecting the Electronic Properties and Photoinduced Charge Transfer at Perylene-Based Molecular Interfaces.

Perylene-based organic semiconductors are widely used in organic electronic devices. Here, we studied the ultrafast excited state dynamics after optical excitation at interfaces between the electron donor (D) diindenoperylene (DIP) and the electron acceptor (A) dicyano-perylene-bis(dicarboximide) (PDIR-CN2 ) using femtosecond time-resolved second harmonic generation (SHG) in combination with large scale quantum chemical calculations. Thereby, we varied in bilayer structures of DIP and PDIR-CN2 the interfacial molecular geometry. For an interfacial configuration which contains a edge-on geometry but also additional face-on domains an optically induced charge transfer (CT) is observed, which leads to a pronounced increase of the SHG signal intensity due to electric field induced second harmonic generation. The interfacial CT state decays within 7.5±0.7 ps, while the creation of hot CT states leads to a faster decay (5.3±0.2 ps). For the bilayer structures with mainly edge-on geometries interfacial CT formation is suppressed since π-π overlap perpendicular to the interface is missing. Our combined experimental and theoretical study provides important insights into D/A charge transfer properties, which is needed for the understanding of the interfacial photophysics of these molecules.

Symbiont-host interactome mapping reveals effector-targeted modulation of hormone networks and activation of growth promotion

Plants have benefited from interactions with symbionts for coping with challenging environments since the colonisation of land. The mechanisms of symbiont-mediated beneficial effects and similarities and differences to pathogen strategies are mostly unknown. Here, we use 106 (effector-) proteins, secreted by the symbiont Serendipita indica (Si) to modulate host physiology, to map interactions with Arabidopsis thaliana host proteins. Using integrative network analysis, we show significant convergence on target-proteins shared with pathogens and exclusive targeting of Arabidopsis proteins in the phytohormone signalling network. Functional in planta screening and phenotyping of Si effectors and interacting proteins reveals previously unknown hormone functions of Arabidopsis proteins and direct beneficial activities mediated by effectors in Arabidopsis. Thus, symbionts and pathogens target a shared molecular microbe-host interface. At the same time Si effectors specifically target the plant hormone network and constitute a powerful resource for elucidating the signalling network function and boosting plant productivity.

Determination of HER2 binding domain in antigen-antibody complexes based on chemical crosslinking mass spectrometry

Chemical crosslinking (XL) of non-covalent antigen-antibody complexes followed by mass spectrometric identification (MS) of inter-protein crosslinks can provide spatial constraints between relevant residues, which are valuable structural information associated with the molecular binding interface. To highlight the potential of XL/MS in the biopharmaceutical industry, we herein developed and validated an XL/MS workflow that employed a zero-length linker, 1,1′‑carbonyldiimidazole (CDI), and a widely used medium-length linker, disuccinimidyl sulfoxide (DSSO), for fast, accurate determination of antigen domains targeted by therapeutic antibodies. To avoid false identification, system suitability samples and negative samples were designed for all experiments, and all tandem mass spectra were manually examined. To validate the proposed XL/MS workflow, two complexes involving human epidermal growth factor receptor 2 Fc fusion protein (HER2Fc) with known crystal structures, including HER2Fc-pertuzumab and HER2Fc-trastuzumab, have been subjected to CDI and DSSO crosslinking. Crosslinks established by CDI and DSSO between HER2Fc and pertuzumab accurately revealed their interaction interface. CDI crosslinking contributes more than DSSO because of its short spacer arm and high reactivity towards hydroxyl groups, demonstrating its capacity in protein interaction analysis. The correct binding domain cannot be revealed solely based on DSSO in the HER2Fc-trastuzumab complex, because domain proximity revealed by this 7-atom spacer linker cannot be directly translated as binding interfaces. As the first successful XL/MS application in early-stage therapeutic antibody discovery, we analyzed the molecular binding interface between HER2Fc and H-mab, an innovant drug candidate whose paratopes have not been studied yet. We predict that H-mab probably targets HER2 Domain I. The proposed XL/MS workflow can serve as an accurate, fast, and low-cost method to study the interaction between antibodies and large multi-domain antigens. SignificanceThis article described a fast, low-consumption approach based on chemical crosslinking mass spectrometry (XL/MS) using two linkers for binding domain determination in multidomain antigen-antibody complexes. Our results highlighted the higher importance of zero-length crosslinks established by CDI than 7-atom DSSO crosslinks, as residue proximity revealed by zero-length crosslinks is closely related to epitope-paratope interaction surfaces. Furthermore, the higher reactivity of CDI towards hydroxyl groups broadens the ranges of possible crosslinks, despite the necessity of delicate operation in CDI crosslinking. We suggest that all established CDI and DSSO crosslinks should be comprehensively considered for correct binding domain analysis because predictions solely based on DSSO might be ambiguous. We have determined the binding interface in the HER2-H-mab using CDI and DSSO, which is the first successful application of XL/MS in real-world early-stage biopharmaceutical development.

Hexagonal Hybrid Bismuthene by Molecular Interface Engineering.

High-quality devices based on layered heterostructures are typically built from materials obtained by complex solid-state physical approaches or laborious mechanical exfoliation and transfer. Meanwhile, wet-chemically synthesized materials commonly suffer from surface residuals and intrinsic defects. Here, we synthesize using an unprecedented colloidal photocatalyzed, one-pot redox reaction a few-layers bismuth hybrid of "electronic grade" structural quality. Intriguingly, the material presents a sulfur-alkyl-functionalized reconstructed surface that prevents it from oxidation and leads to a tuned electronic structure that results from the altered arrangement of the surface. The metallic behavior of the hybrid is supported by ab initio predictions and room temperature transport measurements of individual nanoflakes. Our findings indicate how surface reconstructions in two-dimensional (2D) systems can promote unexpected properties that can pave the way to new functionalities and devices. Moreover, this scalable synthetic process opens new avenues for applications in plasmonics or electronic (and spintronic) device fabrication. Beyond electronics, this 2D hybrid material may be of interest in organic catalysis, biomedicine, or energy storage and conversion.

Deterioration Effects of Oxidative Aging on Graphene-Asphalt Nanocomposite Interfaces: Multiscale Modeling.

The purpose of this study is to explore the mechanism of interfacial degradation of graphene-asphalt nanocomposites by oxidative aging and to explain the principle of reduced cracking resistance. In this study, density functional theory (DFT), molecular dynamics (MD) simulation, atomic force microscopy (AFM), Fourier transform infrared (FTIR) spectroscopy, and linear amplitude scanning test (LAS) were used to quantify the effect of oxidative aging on the interfacial degradation of graphene-asphalt nanocomposites with different scales, and the coupling mechanism between scales was systematically analyzed. The results show that interfacial degradation is a complex multiscale coupling behavior. Oxidative aging reduced the fatigue life (Nf) of graphene-asphalt nanocomposites by 8.6% due to a 63.9% reduction in shear barriers and a 14.2% reduction in energy barriers at the molecular interface. Furthermore, oxidative aging enhanced the intermolecular interactions and compatibility of the graphene-asphalt molecules. The interfacial interaction of aged graphene-asphalt nanocomposites is mainly van der Waals force. Graphene-aged aromatics and graphene-aged saturates were the most compatible interfaces, and there was typical benzene ring stacking between graphene and aged aromatic 2. Aged aromatics and aged saturates are the main promoters of interfacial strength and stress transfer, while aged asphaltenes and aged resins sometimes play a weakening role, as verified by the AFM. In addition, DFT calculations show that there is no chemical reaction between graphene and aged asphalt molecules, which is consistent with the FTIR results. This study provides a theoretical basis for the development of targeted antiaging and anticracking technologies for asphalt-based materials.

Degradation of fiber/matrix interface under various environmental and loading conditions: Insights from molecular simulations

Fiber-reinforced polymer composites have been increasingly applied as reinforcing and load-bearing components in building constructions and civil infrastructures. Long-term exposure to changing environmental and loading conditions leads to composite degradation, which is highly related to degraded structure and properties of fiber/matrix interface and consequent interfacial debonding between fiber and matrix at nanoscale. By simulating interfacial structure and interactions with atomistic precision, molecular simulation allows for a high fidelity to interfacial variations as affected by environmental and loading conditions. In this paper, molecular investigations of interfacial degradation between fiber and matrix under various environmental and loading conditions are reviewed. Model construction of interfaces formed by different fibers and matrixes and simulation of various environmental and loading conditions are firstly introduced. Afterwards, mechanical and adhesion properties of molecular interfaces obtained from deformation simulations are presented. Meanwhile, interfacial degradations under various environmental and loading conditions are discussed and underlying mechanisms are revealed. Further discussions on modeling and simulation of molecular interface are proposed for future investigations. Overall, this work reviews previous molecular investigations of interfacial degradation of composites under different environmental and loading conditions, which contributes to evaluation of interfacial behaviors of composite materials during long-term service life.

Structural basis of DNA binding by the WhiB-like transcription factor WhiB3 in Mycobacterium tuberculosis

Mycobacterium tuberculosis (Mtb) WhiB3 is an iron-sulfur cluster-containing transcription factor belonging to a subclass of the WhiB-Like (Wbl) family that is widely distributed in the phylum Actinobacteria. WhiB3 plays a crucial role in the survival and pathogenesis of Mtb. It binds to the conserved region 4 of the principal sigma factor (σA4) in the RNA polymerase holoenzyme to regulate gene expression like other known Wbl proteins in Mtb. However, the structural basis of how WhiB3 coordinates with σA4 to bind DNA and regulate transcription is unclear. Here we determined crystal structures of the WhiB3:σA4 complex without and with DNA at 1.5Å and 2.45Å, respectively, to elucidate how WhiB3 interacts with DNA to regulate gene expression. These structures reveal that the WhiB3:σA4 complex shares a molecular interface similar to other structurally characterized Wbl proteins and also possesses a subclass-specific Arg-rich DNA-binding motif. We demonstrate that this newly defined Arg-rich motif is required for WhiB3 binding to DNA invitro and transcriptional regulation in Mycobacterium smegmatis. Together, our study provides empirical evidence of how WhiB3 regulates gene expression in Mtb by partnering with σA4 and engaging with DNA via the subclass-specific structural motif, distinct from the modes of DNA interaction by WhiB1 and WhiB7.

Cryptochrome-Timeless structure reveals circadian clock timing mechanisms.

Circadian rhythms influence many behaviours and diseases1,2. They arise from oscillations in gene expression caused by repressor proteins that directly inhibit transcription of their own genes. The fly circadian clock offers a valuable model for studying these processes, wherein Timeless (Tim) plays a critical role in mediating nuclear entry of the transcriptional repressor Period (Per) and the photoreceptor Cryptochrome (Cry) entrains the clock by triggering Tim degradation in light2,3. Here, through cryogenic electron microscopy of the Cry-Tim complex, we show how a light-sensing cryptochrome recognizes its target. Cry engages a continuous core of amino-terminal Tim armadillo repeats, resembling how photolyases recognize damaged DNA, and binds a C-terminal Tim helix, reminiscent of the interactions between light-insensitive cryptochromes and their partners in mammals. The structure highlights how the Cry flavin cofactor undergoes conformational changes that couple to large-scale rearrangements at the molecular interface, and how a phosphorylated segment in Tim may impact clock period by regulating the binding of Importin-α and the nuclear import of Tim-Per4,5. Moreover, the structure reveals that the N terminus of Tim inserts into the restructured Cry pocket to replace the autoinhibitory C-terminal tail released by light, thereby providing a possible explanation for how the long-short Tim polymorphism adapts flies to different climates6,7.

Structure Property and Reaction Mechanism of Boron-Based High-Voltage Electrolyte Additives via First-Principles Calculations

Boron-based additives are currently the mainstream film-forming additives. They generate B–F-containing species and then participate in the formation of the cathode–electrolyte interphase (CEI) film. However, little is known about their oxidative decomposition mechanisms, reaction processes, and the relationship between their molecular structure and interface stability in electrolyte. Here, the reaction mechanisms and processes of trimethyl borate (TMB) with fluorides (F–, PF6–, HF, and PF5) in electrolyte were calculated and studied by combining theoretical and experimental methods. TMB was found to be capable of reacting with fluorides and self-dimerize in a nucleophilic manner. In addition, a comparative study was performed with tris(2-cyanoethyl) borate (TCEB), structurally similar to TMB. TMB and TCEB had the same reaction sites and almost the same energy barriers, and they participated in similar reaction processes. The decomposition of boron-based additives was analyzed through simulations and experiments to fill the gap in the information on the reaction mechanisms and processes of boron-based additives. This work also explored the influence of molecular structure on the mechanism of film formation, thus providing theoretical guidance for the molecular structure design of high-pressure additives and offering ideas for developing electrolyte additives.

Designing Solvated Double-Layer Polymer Electrolytes with Molecular Interactions Mediated Stable Interfaces for Sodium Ion Batteries.

Unstable cathode-electrolyte and/or anode-electrolyte interface in polymer-based sodium-ion batteries (SIBs) will deteriorate their cycle performance. Herein, a unique solvated double-layer quasi-solid polymer electrolyte (SDL-QSPE) with high Na+ ion conductivity is designed to simultaneously improve stability on both cathode and anode sides. Different functional fillers are solvated with plasticizers to improve Na+ conductivity and thermal stability. The SDL-QSPE is laminated by cathode- and anode-facing polymer electrolyte to meet the independent interfacial requirements of the two electrodes. The interfacial evolution is elucidated by theoretical calculations and 3D X-ray microtomography analysis. The Na0.67 Mn2/3 Ni1/3 O2 |SDL-QSPE|Na batteries exhibit 80.4 mAh g-1 after 400 cycles at 1 C with the Coulombic efficiency close to 100 %, which significantly outperforms those batteries using the monolayer-structured QSPE.

Designing Solvated Double‐Layer Polymer Electrolytes with Molecular Interactions Mediated Stable Interfaces for Sodium Ion Batteries

AbstractUnstable cathode‐electrolyte and/or anode‐electrolyte interface in polymer‐based sodium‐ion batteries (SIBs) will deteriorate their cycle performance. Herein, a unique solvated double‐layer quasi‐solid polymer electrolyte (SDL‐QSPE) with high Na+ ion conductivity is designed to simultaneously improve stability on both cathode and anode sides. Different functional fillers are solvated with plasticizers to improve Na+ conductivity and thermal stability. The SDL‐QSPE is laminated by cathode‐ and anode‐facing polymer electrolyte to meet the independent interfacial requirements of the two electrodes. The interfacial evolution is elucidated by theoretical calculations and 3D X‐ray microtomography analysis. The Na0.67Mn2/3Ni1/3O2|SDL‐QSPE|Na batteries exhibit 80.4 mAh g−1 after 400 cycles at 1 C with the Coulombic efficiency close to 100 %, which significantly outperforms those batteries using the monolayer‐structured QSPE.

Allosteric Modulation of Membrane Proteins by Small Low-Affinity Ligands.

Membrane proteins may respond to a variety of ligands under an applied external stimulus. These ligands include small low-affinity molecules that account for functional effects in the mM range. Understanding the modulation of protein function by low-affinity ligands requires characterizing their atomic-level interactions under dilution, challenging the current resolution of theoretical and experimental routines. Part of the problem derives from the fact that small low-affinity ligands may interact with multiple sites of a membrane protein in a highly degenerate manner to a degree that it is better conceived as a partition phenomenon, hard to track at the molecular interface of the protein. Looking for new developments in the field, we rely on the classic two-state Boltzmann model to devise a novel theoretical description of the allosteric modulation mechanism of membrane proteins in the presence of small low-affinity ligands and external stimuli. Free energy stability of the partition process and its energetic influence on the protein coupling with the external stimulus are quantified. The outcome is a simple formulation that allows the description of the equilibrium shifts of the protein in terms of the grand-canonical partition function of the ligand at dilute concentrations. The model's predictions of the spatial distribution and response probability shift across a variety of ligand concentrations, and thermodynamic conjugates can be directly compared to macroscopic measurements, making it especially useful to interpret experimental data at the atomic level. Illustration and discussion of the theory is shown in the context of general anesthetics and voltage-gated channels for which structural data are available.

MED13L and its disease-associated variants influence the dendritic development of cerebral cortical neurons in the mammalian brain.

The mediator complex comprises multiple subcellular subunits that collectively function as a molecular interface between RNA polymerase II and gene-specific transcription factors. Recently, genetic variants to one subunit of the complex, known as MED13L (mediator complex subunit 13 like), have been implicated in syndromic intellectual disability and distinct facial features, frequently accompanied by congenital heart defects. We investigated the impact of five disease-associated MED13L variants on the subcellular localization and biochemical stability of MED13L protein in vitro and in vivo. In overexpression assays using cortical neurons from embryonic mouse cerebral cortices transduced by in utero electroporation-mediated gene transfer, we found that mouse orthologues of human MED13L-p.P866L and -p.T2162M missense variants accumulated in the nucleus, while the p.S2163L and p.S2177Y variants were diffusely distributed in the cytoplasm. In contrast, we found that the p.Q1922* truncation variant was barely detectable in transduced cells, a phenotype reminiscent of this variant that results in MED13L haploinsufficiency in humans. Next, we analyzed these variants for their effects on neuronal migration, dendritic growth, spine morphology, and axon elongation of cortical neurons in vivo. There, we found that overexpression of the p.P866L variant resulted in reduced number and length of dendrites of cortical layer II/III pyramidal neurons. Furthermore, we show that mMED13L-knockdown abrogated dendritic growth in vivo, and this effect was significantly rescued by co-electroporation of an RNAi-resistant mMED13L, but weakly by the p.T2162M variant, and not at all by the p.S2163L variant. However, overexpression of the p.S2163L variant inhibited mature dendritic spine formation in vivo. Expression of each of the 5 variants did not affect neuronal cell migration and callosal axon elongation in vivo. Taken together, our results demonstrate that MED13L expression is relevant to corticogenesis and influences the dendritic branching characteristics of cortical excitatory neurons. Our study also suggests that disease-associated MED13L variants may directly cause morphological and functional defects in cortical neurons in different ways.

Universal Molecular Control Strategy for Scalable Fabrication of Perovskite Light-Emitting Diodes

Despite the rapid progress in perovskite light-emitting diodes (PeLEDs), the electroluminescence performance of large-area perovskite devices lags far behind that of laboratory-size ones. Here, we report a 3.5 cm × 3.5 cm large-area PeLED with a record-high external quantum efficiency of 12.1% by creating an amphipathic molecular interface modifier of betaine citrate (BC) between the perovskite layer and the underlying hole transport layer (HTL). It is found that the surface wettability for various HTLs can be efficiently improved as a result of the coexistence of methyl and carboxyl groups in the BC molecules that makes favorable groups to selectively contact with the HTL surface and increases the surface free energy, which greatly facilitates the scalable process of solution-processed perovskite films. Moreover, the luminous performance of perovskite emitters is simultaneously enhanced through the coordination between C═O in the carboxyl groups and Pb dangling bonds.

Reinforced Hydrophobic Molecular Layer Promoting Waterproof Lithium for High-Performance Lithium-Metal Batteries

The employment of lithium (Li) metal is crucial to sustainable Li metal batteries (LMBs) with realistically high energy density. The management and usage of Li in reality, however, remain high challenge due to the desirable of obtaining an undamaged Li structure arising from the indispensable in extenuating strongly environmental dependence of Li during stored procedure and minimizing the Li depletion and pulverization on long-term cycles. Herein, we impair the molecular hydrogen bonding cooperation between lithium and water molecules on the surface of Li to demonstrate an achievement of environmental independent and durable Li via integrating a reinforced molecular hydrophobic interface on the surface of Li. As a result, the molecular hydrophobic interface modified Li metal can exhibit dendrite-free Li deposition and achieve stable operation for 200 cycles in Li-S full cell at a current of 1 C.

A conformally bonded molecular interface retarded iodine migration for durable perovskite solar cells

A molecular hole transport material retards the iodine migration and delivers high stability in a harsh 85 °C MPP test.

Low-temperature resistance of fluorine rubber with modified Si-based nanoparticles

Fluorine rubber contains fluorine atoms with strong electronegativity, which endow it with novel properties, such as oil resistance, heat resistance, chemical resistance, but also lead to poor low temperature resistance. Si-based nanoparticles are used as the new active crosslinking point of fluorine rubber, which can break the original regular structure to improve the low-temperature resistance and ensuring the mechanical properties of fluorine rubber. The relative optimal silane coupling agent is selected according to the relative concentration and the interaction energy of the molecular interface in different models. The optimal silane coupling agent can avoid the agglomeration of Si-based nanoparticles in fluorine rubber and form flexible bridge between inorganic Si-based nanoparticles and fluorine rubber long chains. It is discovered that the mechanical and low-temperature properties of the modified Si-based nanoparticles/fluorine rubber (FKM-M Si) was optimal compared with pure fluorine rubber (P-FKM) and unmodified Si-based nanoparticles/fluorine rubber (FKM-UM Si). The brittleness temperature (T b ) is reduced from -18.0 °C to -29.0 °C, allowing for a wider range of applications for FKM-M Si. This study provided a potential for the application of fluorine rubber composites in harsh low-temperature environment. • The silicon nanoparticles have larger Si–O–Si bond angles, high orientation freedom and good flexibility. • Improving the dispersion of silicon nanoparticles in fluorine rubber by chemical modification. • Unique nanocomposite structure is the key point of the low temperature resistance.

One-step synthesis of low-cost perylenediimide-based cathode interfacial materials for efficient inverted perovskite solar cells

Interface engineering plays an important role in improving the performance of perovskite devices. Herein, we reported two perylenediimide small molecular cathode interface materials (CIMs), PDI-2N and PDI-4N, synthesized by a simple method and with good alcohol soluble, which could be used as cathode interfacial layer (CIL) for high-performance inverted perovskite solar cells (PVSCs). The PDI-4N exhibits larger electrical conductivity, electron mobility and self-doping properties than PDI-2N because of more dimethylamino functional groups in the amide positions. Based on these superiorities, a peak PCE of 21.33% with PDI-4N as CIL was achieved, which is the highest PCE for PDI-based interlayer materials as the cathode interlayer in inverted PVSCs. While the PCE with PDI-2N as CIL is only 17.41%. The significant improvement in device efficiency for PDI-4N based device is due to reduced defect density, lower dark current, larger recombination resistance and better surface morphology, which improved charge transport and collection at the PC61BM/Ag interface. Moreover, the ambient stabilities of PVSCs with PDI-2N and PDI-4N as CIL show that the CILs can effectively improve the device stability, and good stability with a PCE loss of only ∼3.0% after 600 h is also obtained. In a word, this work will provide us with molecular design approach by one-step to develop novel cathode interface materials with functional side chains for high-efficiency PVSCs.

Structure and functional mapping of the KRAB‐KAP1 repressor complex

Transposable elements are a genetic reservoir from which new genes and regulatory elements can emerge. However, expression of transposable elements can be pathogenic and is therefore tightly controlled. KRAB domain‐containing zinc finger proteins (KRAB‐ZFPs) recruit the co‐repressor KRAB‐associated protein 1 (KAP1/TRIM28) to regulate many transposable elements, but how KRAB‐ZFPs and KAP1 interact remains unclear. Here, we report the crystal structure of the KAP1 tripartite motif (TRIM) in complex with the KRAB domain from a human KRAB‐ZFP, ZNF93. Structure‐guided mutations in the KAP1‐KRAB binding interface abolished repressive activity in an epigenetic transcriptional silencing assay. Deposition of H3K9me3 over thousands of loci is lost genome‐wide in cells expressing a KAP1 variant with mutations that abolish KRAB binding. Our work identifies and functionally validates the KRAB‐KAP1 molecular interface, which is critical for a central transcriptional control axis in vertebrates. In addition, the structure‐based prediction of KAP1 recruitment efficiency will enable optimization of KRABs used in CRISPRi.