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Many DNA-processing enzymes have been shown to contain a [4Fe4S] cluster, a common redox cofactor in biology. Using DNA electrochemistry, we find that binding of the DNA polyanion promotes a negative shift in [4Fe4S] cluster potential, which corresponds thermodynamically to a â¼500-fold increase in DNA-binding affinity for the oxidized [4Fe4S]3+ cluster versus the reduced [4Fe4S]2+ cluster. This redox switch can be activated from a distance using DNA charge transport (DNA CT) chemistry. DNA-processing proteins containing the [4Fe4S] cluster are enumerated, with possible roles for the redox switch highlighted. A model is described where repair proteins may signal one another using DNA-mediated charge transport as a first step in their search for lesions. The redox switch in eukaryotic DNA primases appears to regulate polymerase handoff, and in DNA polymerase δ, the redox switch provides a means to modulate replication in response to oxidative stress. We thus describe redox signaling interactions of DNA-processing [4Fe4S] enzymes, as well as the most interesting potential players to consider in delineating new DNA-mediated redox signaling networks.
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DNA Glicosilases/química , DNA Helicases/química , DNA Polimerase Dirigida por DNA/química , DNA/química , Endonucleases/química , Genoma , Proteínas Ferro-Enxofre/química , Animais , Bactérias/genética , Bactérias/metabolismo , DNA/metabolismo , DNA/ultraestrutura , Dano ao DNA , DNA Glicosilases/metabolismo , DNA Glicosilases/ultraestrutura , DNA Helicases/metabolismo , DNA Helicases/ultraestrutura , Reparo do DNA , Replicação do DNA , DNA Polimerase Dirigida por DNA/metabolismo , DNA Polimerase Dirigida por DNA/ultraestrutura , Espectroscopia de Ressonância de Spin Eletrônica , Endonucleases/metabolismo , Endonucleases/ultraestrutura , Proteínas Ferro-Enxofre/metabolismo , Proteínas Ferro-Enxofre/ultraestrutura , Oxirredução , Ligação Proteica , Transdução de Sinais , TermodinâmicaRESUMO
We report a 100-million atom-scale model of an entire cell organelle, a photosynthetic chromatophore vesicle from a purple bacterium, that reveals the cascade of energy conversion steps culminating in the generation of ATP from sunlight. Molecular dynamics simulations of this vesicle elucidate how the integral membrane complexes influence local curvature to tune photoexcitation of pigments. Brownian dynamics of small molecules within the chromatophore probe the mechanisms of directional charge transport under various pH and salinity conditions. Reproducing phenotypic properties from atomistic details, a kinetic model evinces that low-light adaptations of the bacterium emerge as a spontaneous outcome of optimizing the balance between the chromatophore's structural integrity and robust energy conversion. Parallels are drawn with the more universal mitochondrial bioenergetic machinery, from whence molecular-scale insights into the mechanism of cellular aging are inferred. Together, our integrative method and spectroscopic experiments pave the way to first-principles modeling of whole living cells.
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Células/metabolismo , Metabolismo Energético , Adaptação Fisiológica/efeitos da radiação , Trifosfato de Adenosina/metabolismo , Benzoquinonas/metabolismo , Membrana Celular/metabolismo , Membrana Celular/efeitos da radiação , Células/efeitos da radiação , Cromatóforos/metabolismo , Citocromos c2/metabolismo , Difusão , Transporte de Elétrons/efeitos da radiação , Metabolismo Energético/efeitos da radiação , Meio Ambiente , Ligação de Hidrogênio , Cinética , Luz , Simulação de Dinâmica Molecular , Fenótipo , Proteínas/metabolismo , Rhodobacter sphaeroides/fisiologia , Rhodobacter sphaeroides/efeitos da radiação , Eletricidade Estática , Estresse Fisiológico/efeitos da radiação , TemperaturaRESUMO
Proteins play a key role in biological electron transport, but the structure-function relationships governing the electronic properties of peptides are not fully understood. Despite recent progress, understanding the link between peptide conformational flexibility, hierarchical structures, and electron transport pathways has been challenging. Here, we use single-molecule experiments, molecular dynamics (MD) simulations, nonequilibrium Green's function-density functional theory (NEGF-DFT), and unsupervised machine learning to understand the role of secondary structure on electron transport in peptides. Our results reveal a two-state molecular conductance behavior for peptides across several different amino acid sequences. MD simulations and Gaussian mixture modeling are used to show that this two-state molecular conductance behavior arises due to the conformational flexibility of peptide backbones, with a high-conductance state arising due to a more defined secondary structure (beta turn or 310 helices) and a low-conductance state occurring for extended peptide structures. These results highlight the importance of helical conformations on electron transport in peptides. Conformer selection for the peptide structures is rationalized using principal component analysis of intramolecular hydrogen bonding distances along peptide backbones. Molecular conformations from MD simulations are used to model charge transport in NEGF-DFT calculations, and the results are in reasonable qualitative agreement with experiments. Projected density of states calculations and molecular orbital visualizations are further used to understand the role of amino acid side chains on transport. Overall, our results show that secondary structure plays a key role in electron transport in peptides, which provides broad avenues for understanding the electronic properties of proteins.
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Simulação de Dinâmica Molecular , Peptídeos , Estrutura Secundária de Proteína , Transporte de Elétrons , Peptídeos/química , Peptídeos/metabolismo , Ligação de HidrogênioRESUMO
Macromolecules bearing open-shell entities offer unique transport properties for both electronic and spintronic devices. This work demonstrates that, unlike their conjugated polymer counterparts, the charge carriers in radical polymers (i.e., macromolecules with nonconjugated backbones and with stable open-shell sites present at their pendant groups) are singlet cations, which opens significant avenues for manipulating macromolecular design for advanced solid-state transport in these highly transparent conductors. Despite this key point, magnetoresistive effects are present in radical polymer thin films under applied magnetic fields due to the presence of impurity sites in low (i.e., <1%) concentrations. Additionally, thermal annealing of poly(4-glycidyloxy-2,2,6,6- tetramethylpiperidine-1-oxyl) (PTEO), a nonconjugated polymer with stable open-shell pendant groups, facilitated better electron exchange and pairwise spin interactions resulting in an unexpected magnetoresistance signal at relatively low field strengths (i.e., <2 T). The addition of 4-hydroxy-2,2,6,6-tetramethylpiperidin-N-oxy (TEMPO-OH), a paramagnetic species, increased the magnitude of the MR effect when the small molecule was added to the radical polymer matrix. These macroscopic experimental observables are explained using computational approaches that detail the fundamental molecular principles. This intrinsic localized charge transport behavior differs from the current state of the art regarding closed-shell conjugated macromolecules, and it opens an avenue towards next-generation transport in organic electronic materials.
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Solid-state defects are attractive platforms for quantum sensing and simulation, e.g., in exploring many-body physics and quantum hydrodynamics. However, many interesting properties can be revealed only upon changes in the density of defects, which instead is usually fixed in material systems. Increasing the interaction strength by creating denser defect ensembles also brings more decoherence. Ideally one would like to control the spin concentration at will while keeping fixed decoherence effects. Here, we show that by exploiting charge transport, we can take some steps in this direction, while at the same time characterizing charge transport and its capture by defects. By exploiting the cycling process of ionization and recombination of NV centers in diamond, we pump electrons from the valence band to the conduction band. These charges are then transported to modulate the spin concentration by changing the charge state of material defects. By developing a wide-field imaging setup integrated with a fast single photon detector array, we achieve a direct and efficient characterization of the charge redistribution process by measuring the complete spectrum of the spin bath with micrometer-scale spatial resolution. We demonstrate a two-fold concentration increase of the dominant spin defects while keeping the T2 of the NV center relatively unchanged, which also provides a potential experimental demonstration of the suppression of spin flip-flops via hyperfine interactions. Our work paves the way to studying many-body dynamics with temporally and spatially tunable interaction strengths in hybrid charge-spin systems.
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Dynamic molecular devices operating with time- and history-dependent performance raised new challenges for the fundamental study of microscopic non-steady-state charge transport as well as functionalities that are not achievable by steady-state devices. In this study, we reported a generic dynamic mode of molecular devices by addressing the transient redox state of ubiquitous quinone molecules in the junction by proton/water transfer. The diffusion limited slow proton/water transfer-modulated fast electron transport, leading to a non-steady-state transport process, as manifested by the negative differential resistance, dynamic hysteresis, and memory-like behavior. A quantitative paradigm for the study of the non-steady-state charge transport kinetics was further developed by combining the theoretical model and transient state characterization, and the principle of the dynamic device can be revealed by the numerical simulator. On applying pulse stimulation, the dynamic device emulated the neuron synaptic response with frequency-dependent depression and facilitation, implying a great potential for future nonlinear and brain-inspired devices.
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The discovery of quantum interference (QI) is widely considered as an important advance in molecular electronics since it provides unique opportunities for achieving single-molecule devices with unprecedented performance. Although some pioneering studies suggested the presence of spin qubit coherence and QI in collective systems such as thin films, it remains unclear whether the QI can be transferred step-by-step from single molecules to different length scales, which hinders the application of QI in fabricating active molecular devices. Here, we found that QI can be transferred from a single molecule to their assemblies. We synthesized and investigated the charge transport through the molecular cages using 1,3-dipyridylbenzene (DPB) as a ligand block with a destructive quantum interference (DQI) effect and 2,5-dipyridylfuran (DPF) as a control building block with a constructive quantum interference (CQI) effect using both single-molecule break junction and large area junction techniques. Combined experiments and calculations revealed that both DQI and CQI had been transferred from the ligand blocks to the molecular cages and the monolayer thin film of the cages. Our work introduced QI effects from a ligand to the molecular cage comprising 732 atoms and even their monolayers, suggesting that the quantum interference could be scaled up within the phase-coherent distance.
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Elucidating charge transport (CT) through proteins is critical for gaining insights into ubiquitous CT chain reactions in biological systems and developing high-performance bioelectronic devices. While intra-protein CT has been extensively studied, crucial knowledge about inter-protein CT via interfacial amino acids is still absent due to the structural complexity. Herein, by loading cytochrome c (Cyt c) on well-defined peptide self-assembled monolayers to mimic the protein-protein interface, we provide a precisely controlled platform for identifying the roles of interfacial amino acids in solid-state CT via peptide-Cyt c junctions. The terminal amino acid of peptides serves as a fine-tuning factor for both the interfacial interaction between peptides and Cyt c and the immobilized Cyt c orientation, resulting in a nearly 10-fold difference in current through peptide-Cyt c junctions with varied asymmetry. This work provides a valuable platform for studying CT across proteins and contributes to the understanding of fundamental principles governing inter-protein CT.
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Aminoácidos , Citocromos c , Citocromos c/química , Citocromos c/metabolismo , Peptídeos/metabolismo , Proteínas , Transporte de ElétronsRESUMO
2D Dion-Jacobson (DJ) perovskites have emerged as promising photovoltaic materials, but the insulating organic spacer has hindered the efficient charge transport. Herein, we successfully synthesized a terthiophene-based semiconductor spacer, namely, 3ThDMA, for 2D DJ perovskite. An interesting finding is that the energy levels of 3ThDMA extensively overlap with the inorganic components and directly contribute to the band formation of (3ThDMA)PbI4, leading to enhanced charge transport across the organic spacer layers, whereas no such orbital interactions were found in (UDA)PbI4, a DJ perovskite based on 1,11-undecanediaminum (UDA). The devices based on (3ThDMA)MAn-1PbnI3n+1 (nominal n = 5) obtained a champion efficiency of 15.25%, which is a record efficiency for 2D DJ perovskite solar cells using long-conjugated spacers (conjugated rings ≥ 3) and a 22.60% efficiency for 3ThDMA-treated 3D PSCs. Our findings provide an important insight into understanding the orbital interactions in 2D DJ perovskite using an organic semiconductor spacer for efficient solar cells.
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Heterogeneous interfaces in most devices play a key role in the material performance. Exploring the atomic structure and electronic properties of metal-molecule interfaces is critical for various potential applications, such as surface sensing, molecular recognition, and molecular electronic devices. This study unveils a ubiquitous interfacial stereoelectronic effect in conjugated molecular junctions by combining first-principles simulation and scanning tunneling microscopy break junction technology. Single-molecule junctions with same-side interfacial anchoring (cis configuration) exhibit higher conductance than those with opposite-side interfacial anchoring (trans configuration). The cis and trans configurations can undergo reversible conversions, resulting in a conductance switching. The stability of these configurations can be adjusted by an electric field, achieving precise regulation of conductance states. Our findings provide important insights for designing high-quality materials and enhancing the device performance.
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Inversion symmetry breaking has played an important role in recent discoveries of nonreciprocal charge transport. Niobium diselenide, for example, lacks an inversion center in the monolayer form and can host prominent nonreciprocal transport property. Here, however, we observe a nonreciprocal transport signal in the second-harmonic channel of bulk-like NbSe2, in which inversion symmetry of the lattice seems preserved. The second-harmonic signal occurs along different in-plane current orientations and appears not only in the vortex-liquid regime but also even in the superconducting fluctuation regime without an applied magnetic field. By adding a direct current (DC) bias, we quantify the symmetry breaking effect in the vortex-liquid regime. The DC bias also suggests that the rectification effect at the contacts may account for the seemingly nonreciprocal transport at zero magnetic field. Our results demonstrate that DC biasing is a useful knob for addressing nonreciprocal charge transport in a wide range of materials.
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In this study, we examined the nanostructured molecular packing and orientations of poly[[N,N'-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5'-(2,2'-bithiophene)] (P(NDI2OD-T2)) films formed on water for the application of nanotechnology-based organic electronic devices. First, the nanoscale molecule-substrate interaction between the polymer and water was modulated by controlling the alkyl side chain length in NDI-based copolymers. Increasing alkyl side chain lengths induced a nanomorphological transition from face-on to edge-on orientation, confirmed by molecular dynamics simulations revealing nanostructural behavior. Second, the nanoscale intermolecular interactions of P(NDI2OD-T2) were controlled by varying the volume ratio of the high-boiling-point additive solvent in the binary solvent blends. As the additive solvent ratio increased, the nanostructured molecular orientation of the P(NDI2OD-T2) films on water changed remarkably from edge-on to bimodal with more face-on crystallites, thereby affecting charge transport. Our finding provides essential insights for precise nanoscale morphological control on water substrates, enabling the formation of high-performance polymer films for organic electronic devices.
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Development of organic nonlinear optical materials has become progressively more important due to their emerging applications in new-generation photonic devices. A novel series of chromophores based on innovative thiophene and furan-fused cyclopentadienyl bridge with various powerful donor and acceptor moieties were designed and theoretically investigated for applications in nonlinear optics. To unravel the structure-property relationship between this new push-pull conjugated systems and their nonlinear optical property, multiple methods, including density of states analysis, coupled perturbed Kohn-Sham (CPKS) method, sum-over-states (SOS) model, the two-level model (TSM), hyperpolarizability density analysis, and the (hyper)polarizability contribution decomposition, were performed to comprehensively investigated the nonlinear optical and electronic properties of this new π-system. Due to excellent charge transfer ability of new bridge and distinctive structure of donor and acceptor, the designed chromophores exhibit deep HOMO levels, low excitation energy, high dipole moment difference and large hyperpolarizability, indicating the appealing air-stable property and remarkable electrooptic performance of them. Importantly, THQ-CS-A3 and PA-CS-A3 shows outstanding NLO response properties with ßtot value of 6953.9 × 10-30 and 5066.0 × 10-30 esu in AN, respectively. The influence of the push-pull strength, the heterocycle and the π-conjugation of new bridge on the nonlinear optical properties of this novel powerful systems are clarified. This new series of chromophores exhibit remarkable electro-optical Pockels and optical rectification effect. More interestingly, PA-CS-A3 and THQ-CS-A2 also show appealing SHG effect. This study will help people understand the nature of nonlinear optical properties of innovative heteroarene-fused based cyclopentadienyl chromophores and offer guidance for the rational design of chromophores with outstanding electrooptic (EO) performance in the future.
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Chemically inert organic networks exhibiting electrical conductivity comparable to metals can advance organic electronics, catalysis, and energy storage systems. Covalent-organic frameworks (COFs) have emerged as promising materials for those applications due to their high crystallinity, porosity, and tunable functionality. However, their low conductivity has limited their practical utilization. In this study, copper-coordinated-fluorinated-phthalocyanine and 2,3,6,7-tetrahydroxy-9,10-anthraquinone-based COF (CuPc-AQ-COF) films with ultrahigh conductivity are developed. The COF films exhibit an electrical conductivity of 1.53 × 103 S m-1 and a Hall mobility of 6.02 × 102 cm2 V-1 s-1 at 298 K, reaching the level of metals. The films are constructed by linking phthalocyanines and anthraquinones through vapor-assisted synthesis. The high conductivity properties of the films are attributed to the molecular design of the CuPc-AQ-COFs and the generation of high-quality crystals via the vapor-assisted method. Density functional theory analysis reveals that an efficient donor-acceptor system between the copper-coordinated phthalocyanines and anthraquinones significantly promotes charge transfer. Overall, the CuPc-AQ-COF films set new records of COF conductivity and mobility and represent a significant step forward in the development of COFs for electronic, catalytic, and electrochemical applications.
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Antimony-based chalcogenides have emerged as promising candidates for next-generation thin film photovoltaics. Particularly, binary Sb2 S3 thin films have exhibited great potential for optoelectronic applications, due to the facile and low-cost fabrication, simple composition, decent charge transport and superior stability. However, most of the reported efficient Sb2 S3 solar cells are realized based on chemical bath deposition and hydrothermal methods, which require large amount of solution and are normally very time-consuming. In this work, Ag ions are introduced within the Sb2 S3 sol-gel precursors, and effectively modulated the crystallization and charge transport properties of Sb2 S3 . The crystallinity of the Sb2 S3 crystal grains are enhanced and the charge carrier mobility is increased, which resulted improved charge collection efficiency and reduced charge recombination losses, reflected by the greatly improved fill factor and open-circuit voltage of the Ag incorporated Sb2 S3 solar cells. The champion devices reached a record high power conversion efficiency of 7.73% (with antireflection coating), which is comparable with the best photovoltaic performance of Sb2 S3 solar cells achieved based on chemical bath deposition and hydrothermal techniques, and pave the great avenue for next-generation solution-processed photovoltaics.
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Halide composition engineering has been demonstrated as an effective strategy for optical and electronic properties modulation in 3D perovskites. While the impact of halide mixing on the structural and charge transport properties of 3D perovskitoids remains largely unexplored. Herein, it is demonstrated that bromine (Br) mixing in 3D (NMPDA)Pb2 I6 (NMPDA = N-methyl-1,3-propane diammonium) perovskitoid yields stabilized (NMPDA)Pb2 I4 Br2 with specific ordered halide sites, where Br ions locate at the edge-sharing sites. The halide ordered structure enables stronger H-bonds, shorter interlayer distance, and lower octahedra distortion in (NMPDA)Pb2 I4 Br2 with respect to the pristine (NMPDA)Pb2 I6 . These attributes further result in high ion migration activation energy, low defect states density, and enhanced carrier mobility-lifetime product (µτ), as underpinned by the electrical properties investigation and DFT calculations. Remarkably, the parallel configured photodetector based on (NMPDA)Pb2 I4 Br2 single crystal delivers a high on/off current ratio of 3.92 × 103 , a satisfying photoresponsivity and detectivity of 0.28 A W-1 and 3.05 × 1012 Jones under 10.94 µW cm-2 irradiation, superior to that of (NMPDA)Pb2 I6 and the reported 3D perovskitoids. This work sheds novel insight on exploring 3D mixed halide perovskitoids toward advanced and stable optoelectronic devices.
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CdSe nanoplatelets (NPLs) are promising 2D semiconductors for optoelectronic applications, in which efficient charge transport properties are desirable. It is reported that thermal annealing constitutes an effective strategy to control the optical absorption and electrical properties of CdSe NPLs by tuning the inter-NPL distance. Combining optical absorption, transmission electron microscopy, and thermogravimetric analysis, it is revealed that the thermal decomposition of ligands (e.g., cadmium myristate) governs the inter-NPL distance and thus the inter-NPL electronic coupling strength. Employing ultrafast terahertz spectroscopy, it is shown that this enhanced electronic coupling increases both the free carrier generation efficiency and the short-range mobility in NPL solids. The results show a straightforward method of controlling the interfacial electronic coupling strength for developing functional optoelectronic devices through thermal treatments.
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Quasi-2D perovskites have attracted much attention in perovskite photovoltaics due to their excellent stability. However, their photoelectric conversion efficiency (PCE) still lags 3D counterparts, particularly with high short-circuit current (JSC) loss. The quantum confinement effect is pointed out to be the sole reason, which introduces widened bandgap and poor exciton dissociation, and undermines the light capture and charge transport. Here, the gradient incorporation of formamidinium (FA) cations into quasi-2D perovskite is proposed to address this issue. It is observed that FA prefers to incorporate into the larger n value phases near the film surface compared to the smaller n value phases in the bulk, resulting in a narrow bandgap and gradient structure within the film. Through charge dynamic analysis using in situ light-dark Kelvin probe force microscopy and transient absorption spectroscopy, it is demonstrated that incorporating 10% FA significantly facilitates efficient charge transfer between low n-value phases in the bulk and high n-value nearby film surface, leading to reduced charge accumulation. Ultimately, the device based on (AA)2(MA0.9FA0.1)4Pb5I16, where AA represents n-amylamine renowned for its exceptional environmental stability as a bulky organic ligand, achieves an impressive power conversion efficiency (PCE) of 18.58% and demonstrates enhanced illumination and thermal stability.
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Solid-state symmetrical battery represents a promising paradigm for future battery technology. However, its development is hindered by the deficiency of high-performance bipolar electrodes and compatible solid electrolytes. Herein, a quasi-solid-state all-V2O5 battery constructed by a binder-free carbon fabric-V2O5 nanowires@graphene (CVOG) bipolar electrode and a softly cross-linked polyethylene oxide-based solid polymer electrolyte (SPE) is reported. The synergetic effect of nano-structuring of V2O5, hierarchical conductive network, and graphene wrapping endows the CVOG electrode with boosted reaction kinetics and suppressed vanadium dissolution. The cathodic and anodic reactions of CVOG are decoupled by electrochemical analysis, conceiving the feasibility of constructing all-V2O5 full battery. In manifesting the solid-state all-V2O5 battery, the robust and elastic SPE exhibits high ionic conductivity, tight/self-adaptable electrolyte-electrode contact, and a low charge-transfer barrier. The resultant solid-state full battery exhibits a high reversible capacity of 158 mAh g-1 at 0.1 C, good capacity retention of over 61% from 0.1 C to 2 C, and remarkable cycling stability of 77% capacity retention after 1000 cycles at 1 C, which surpass other solid-state symmetrical batteries. Hence, this work provides a practice of high-performance solid-state batteries with symmetrical configuration and is constructive for next-generation battery technology.
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Bismuth halide hybrid perovskites have emerged as promising alternatives to their lead halide homologs because of high chemical stability, low toxicity, and structural diversity. However, their advancements in optoelectronic field are plagued with poor charge transport, due to considerable microstrain triggered by bulky spacer. Herein, the di-tertiary ammonium spacer (N,N,N',N'-tetramethyl-1,4-butanediammonium, TMBD) is explored to direct stable 1D bismuth bromide lattice structure with relaxed microstrain. Compared to the primary pentamethylenediamine (PD)2+, the (TMBD)2+ adopting alternating alignment enables a unique H-bonds mode to distort the configuration of inorganic layers to form corner-sharing [BiBr5] near-regular chains with narrower bandgap, lower exciton binding energy, and reduced carrier-lattice interactions, thereby facilitating charge-carrier transport. Moreover, the (TMBD)2+ spacers largely suppress ion migration in perovskite lattice, as substantiated by the experimental and theoretical investigations. Consequently, (TMBD)BiBr5 single crystal photodetector delivers a 185-fold increase in current on/off ratio with respect to (PD)BiBr5 under white light irradiation, considerable responsivity (≈82.97 mA W-1), detectivity (≈8.06 ×1011 Jones) under weak light (0.02 mW cm-2) irradiation, in the top rank of the reported hybrid bismuth halide perovskites. This finding offers novel design criterion for high-performance lead-free perovskites.