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The COVID-19 pandemic urgently needs therapeutic and prophylactic interventions. Here, we report the rapid identification of SARS-CoV-2-neutralizing antibodies by high-throughput single-cell RNA and VDJ sequencing of antigen-enriched B cells from 60 convalescent patients. From 8,558 antigen-binding IgG1+ clonotypes, 14 potent neutralizing antibodies were identified, with the most potent one, BD-368-2, exhibiting an IC50 of 1.2 and 15 ng/mL against pseudotyped and authentic SARS-CoV-2, respectively. BD-368-2 also displayed strong therapeutic and prophylactic efficacy in SARS-CoV-2-infected hACE2-transgenic mice. Additionally, the 3.8 Å cryo-EM structure of a neutralizing antibody in complex with the spike-ectodomain trimer revealed the antibody's epitope overlaps with the ACE2 binding site. Moreover, we demonstrated that SARS-CoV-2-neutralizing antibodies could be directly selected based on similarities of their predicted CDR3H structures to those of SARS-CoV-neutralizing antibodies. Altogether, we showed that human neutralizing antibodies could be efficiently discovered by high-throughput single B cell sequencing in response to pandemic infectious diseases.
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Anticuerpos Monoclonales/aislamiento & purificación , Anticuerpos Neutralizantes/aislamiento & purificación , Linfocitos B/inmunología , Infecciones por Coronavirus/inmunología , Neumonía Viral/inmunología , Análisis de la Célula Individual , Animales , Anticuerpos Monoclonales/administración & dosificación , Anticuerpos Monoclonales/química , Anticuerpos Monoclonales/metabolismo , Anticuerpos Neutralizantes/administración & dosificación , Anticuerpos Neutralizantes/química , Anticuerpos Neutralizantes/metabolismo , COVID-19 , Convalecencia , Secuenciación de Nucleótidos de Alto Rendimiento , Humanos , Ratones , Pandemias , Análisis de Secuencia de ARN , Glicoproteína de la Espiga del Coronavirus/química , Glicoproteína de la Espiga del Coronavirus/metabolismo , Exones VDJRESUMEN
Understanding how potent neutralizing antibodies (NAbs) inhibit SARS-CoV-2 is critical for effective therapeutic development. We previously described BD-368-2, a SARS-CoV-2 NAb with high potency; however, its neutralization mechanism is largely unknown. Here, we report the 3.5-Å cryo-EM structure of BD-368-2/trimeric-spike complex, revealing that BD-368-2 fully blocks ACE2 recognition by occupying all three receptor-binding domains (RBDs) simultaneously, regardless of their "up" or "down" conformations. Also, BD-368-2 treats infected adult hamsters at low dosages and at various administering windows, in contrast to placebo hamsters that manifested severe interstitial pneumonia. Moreover, BD-368-2's epitope completely avoids the common binding site of VH3-53/VH3-66 recurrent NAbs, evidenced by tripartite co-crystal structures with RBDs. Pairing BD-368-2 with a potent recurrent NAb neutralizes SARS-CoV-2 pseudovirus at pM level and rescues mutation-induced neutralization escapes. Together, our results rationalized a new RBD epitope that leads to high neutralization potency and demonstrated BD-368-2's therapeutic potential in treating COVID-19.
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Anticuerpos Neutralizantes/inmunología , Anticuerpos Antivirales/inmunología , Betacoronavirus/inmunología , Infecciones por Coronavirus/patología , Neumonía Viral/patología , Animales , Anticuerpos Neutralizantes/química , Anticuerpos Neutralizantes/uso terapéutico , Anticuerpos Antivirales/química , Anticuerpos Antivirales/uso terapéutico , Reacciones Antígeno-Anticuerpo , Sitios de Unión , COVID-19 , Infecciones por Coronavirus/tratamiento farmacológico , Infecciones por Coronavirus/virología , Cricetinae , Microscopía por Crioelectrón , Modelos Animales de Enfermedad , Epítopos/química , Epítopos/inmunología , Femenino , Pulmón/patología , Masculino , Simulación de Dinámica Molecular , Pandemias , Neumonía Viral/tratamiento farmacológico , Neumonía Viral/virología , Estructura Cuaternaria de Proteína , SARS-CoV-2 , Glicoproteína de la Espiga del Coronavirus/química , Glicoproteína de la Espiga del Coronavirus/inmunologíaRESUMEN
Controlling physicochemical processes that drive changes in supramolecular aggregates is an important objective toward creating artificial soft micro- and nanomachines. Previous research explored the morphology control of membrane-based materials subjected to externally imposed chemical stimuli. Here, we modulate the microscale morphology of pH-responsive assemblies by using biocatalysis to internally generate changes in global pH. Catalytic reactions offer flexibility in the mechanism and rate at which stimuli are introduced to responsive assemblies, ultimately enabling precision and control over size and morphology. We observed, by dynamic light scattering and fluorescence microscopy, substantial microscale differences between assemblies subjected to manually titrated pH changes compared to biocatalytically activated pH changes, including the growth of giant vesicles from micelles. Coarse-grained molecular dynamics simulations of these metastable self-assembled structures provided insight into the thermodynamics and kinetics of the preferred structures. These results demonstrate the feasibility of using biocatalytic reactions to modulate the size and morphology of supramolecular assemblies, from micelles to giant vesicles.
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Biocatálisis , Micelas , Concentración de Iones de Hidrógeno , Simulación de Dinámica Molecular , Lipasa/química , Lipasa/metabolismo , Cinética , TermodinámicaRESUMEN
Titanium-oxo cluster (TOC)-based metal-organic frameworks (MOFs) have received considerable attention in recent years due to their ability to expand the application of TOCs to fields that require highly stable frameworks. Herein, a new cyclic TOC formulated as [Ti6O6(OiPr)8(TTFTC)(phen)2]2 (1, where TTFTC = tetrathiafulvalene tetracarboxylate and phen = phenanthroline) was crystallographically characterized. TOC 1 takes a rectangular ring structure with two phen-modified Ti6 clusters as the width and two TTFTC ligands as the length. An intracluster ligand-to-ligand (TTF-to-phen) charge transfer in 1 was found for TOCs for the first time. Compound 1 undergoes topotactic conversion to generate stable TOC-MOF P1, in which the rectangular framework in 1 formed by a TOC core and ligands is retained, as verified by comprehensive characterization. P1 shows an efficient and rapid selective adsorption capacity for cationic dyes. The experimental adsorption capacity (qex) of P1 reaches a value of up to 789.2 mg/g at 298 K for the crystal violet dye, which is the highest among those of various adsorbents. The calculated models are first used to reveal the structure-property relationship of the cyclic host to different guest dyes. The results further confirmed the host MOF structure of P1.
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Strategy selection is critical for constellation deployment missions, both in terms of energy consumption and time cost. The different effects of impulse thrust and continuous thrust on orbit elements lead to a different choice of strategy. With impulse thrust, constellation types are differentiated according to high and medium-low inclinations. Constellations with high inclination are deployed using a strategy that controls the inclination. Constellations with medium-low inclination are deployed using a strategy that controls the semi-long axis. With continuous thrust, constellations are classified according to high, medium, and low inclination. High inclination constellations are deployed with a strategy of controlling inclination. Medium inclination constellations are deployed with a strategy that controls the semi-long axis. Low inclination constellations are deployed with a strategy of directly applying continuous thrust.
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The development of top-down active control over bottom-up colloidal assembly processes has the potential to produce materials, surfaces, and objects with applications in a wide range of fields spanning from computing to materials science to biomedical engineering. In this review, we summarize recent progress in the field using a taxonomy based on how active control is used to guide assembly. We find there are three distinct scenarios: (1) navigating kinetic pathways to reach a desirable equilibrium state, (2) the creation of a desirable metastable, kinetically trapped, or kinetically arrested state, and (3) the creation of a desirable far-from-equilibrium state through continuous energy input. We review seminal works within this framework, provide a summary of important application areas, and present a brief introduction to the fundamental concepts of control theory that are necessary for the soft materials community to understand this literature. In addition, we outline current and potential future applications of actively-controlled colloidal systems, and we highlight important open questions and future directions.
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Metal-organic frameworks (MOFs) have attracted noticeable attention as promising candidates for electrochemical energy storage. However, the lack of electrical conductivity and the weak stability of most MOFs result in poor electrochemical performances. Here, a tetrathiafulvalene (TTF)-based complex, formulated as [(CuCN)2(TTF(py)4)] (1) (TTF-(py)4 = tetra(4-pyridyl)-TTF), is assembled by in situ generation of coordinated CN- from a nontoxic source. Single-crystal X-ray diffraction analysis reveals that compound 1 possesses a two-dimensional layered planar structure, which is further stacked in parallel to form a three-dimensional supramolecular framework. The planar coordination environment of 1 is the first example of a TTF-based MOF. Attributed to the unique structure and redox TTF ligand, the electrical conductivity of 1 is significantly increased by 5 orders of magnitude upon iodine treatment. The iodine-treated 1 (1-ox) electrode displays typical battery-type behavior through electrochemical characterizations. The supercapattery based on the 1-ox positrode and AC negatrode presents a high specific capacity of 266.5 C g-1 at a specific current of 1 A g-1 with a remarkable specific energy of 62.9 Wh kg-1 at a specific power of 1.1 kW kg-1. The excellent electrochemical performance of 1-ox is one of the best among those reported supercapatteries, demonstrating a new strategy for developing MOF-based electrode materials.
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Family with sequence similarity 20C (Fam20C), the physiological Golgi casein kinase, phosphorylates numerous secreted proteins that are involved in a wide variety of biological processes. However, the role of Fam20C in regulating proteins in the endoplasmic reticulum (ER) lumen is largely unknown. Here, we report that Fam20C interacts with various luminal proteins and that its depletion results in a more reduced ER lumen. We further show that ER oxidoreductin 1α (Ero1α), the pivotal sulfhydryl oxidase that catalyzes disulfide formation in the ER, is phosphorylated by Fam20C in the Golgi apparatus and retrograde-transported to the ER mediated by ERp44. The phosphorylation of Ser145 greatly enhances Ero1α oxidase activity and is critical for maintaining ER redox homeostasis and promoting oxidative protein folding. Notably, phosphorylation of Ero1α is induced under hypoxia, reductive stress, and secretion-demanding conditions such as mammalian lactation. Collectively, our findings open a door to uncover how oxidative protein folding is regulated by phosphorylation in the secretory pathway.
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Quinasa de la Caseína I/metabolismo , Retículo Endoplásmico/metabolismo , Proteínas de la Matriz Extracelular/metabolismo , Glicoproteínas de Membrana/metabolismo , Oxidorreductasas/metabolismo , Procesamiento Proteico-Postraduccional , Células HeLa , Células Hep G2 , Humanos , Proteínas de la Membrana/metabolismo , Chaperonas Moleculares/metabolismo , Oxidación-Reducción , Fosforilación , Transporte de ProteínasRESUMEN
Titanium-oxo clusters (TOCs) have been studied for applications in catalysis, energy storage and transfer, light emission, and so on; however, use of TOCs for the selective adsorption of dyes has not yet been reported. Herein, a TOC compound formulated as [Ti6O3(OiPr)14(TTFTC)]4 (1, TTFTC = tetrathiafulvalene-tetracarboxylate) was successfully prepared and crystallographically characterized. Compound 1 has a cyclic structure assembled by four Ti6 clusters and four rodlike TTFTC connectors. Red compound 1 self-condenses to form a black polymeric organic-inorganic hybrid material (denoted as B-1), which was characterized by various techniques. B-1 is an amorphous TiO material that is formed by the irregular condensation of 1 by the removal of alkoxyl groups. B-1 exhibits high dye adsorption efficiency toward cationic dyes with a qe value of 651.3 mg/g at 298 K for methylene blue (MB). Moreover, B-1 can be used to selectively remove MB not only from mixed cationic-anionic dye solutions but also from some mixed cationic dyes, which is related to their structures. Kinetic, isotherm, and thermodynamic studies demonstrated that the pseudo-second-order kinetic model and Freundlich model show a good fit to the experimental data. The adsorption process involves an exothermic and entropy decreasing process. In addition, dye-adsorbed B-1 can be further used as a photocurrent-responsive material. The work opens up a new field for the application of TOCs in the selective adsorption and removal of dyes.
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Photoelectrocatalysis (PEC) has shown great advantages in sustainable organic synthesis and wastewater treatment because the PEC process can minimize electron-hole recombination, thereby improving the photocatalytic performance. Here, we report a convenient procedure for preparing immobilized BiOX-TiO2 photoelectrocatalytic electrodes from a titanium-oxo compound (TOC)-modified carbon fiber cloth (CFC). Crystalline TOCs composed of Ti12 cations and bismuth halide anions, [Ti12O14(OiPr)18][Bi3Br11(THF)2] (1) and [Ti12O14(OiPr)18][Bi4I14(THF)2] (2), were grown on CFC. Taking advantage of the easy hydrolysis of the titanium-oxo cation and bismuth halide anion, we could easily transform these CFC-immobilized crystals into BiOX-TiO2/CFC (X = Br or I) photocatalysts, which facilitates recycling of the catalysts. The photocatalytic dye degradation test showed that the efficiency did not decrease obviously after 10 photocatalytic cycles. Using BiOX-TiO2-modified CFC as electrodes, electrocatalysis (EC), photocatalysis (PC), and PEC were examined. PEC showed an attractive synergistic effect of EC and PC. These TOC-modified CFCs would be potential candidates for catalytic electrodes for sustainable wastewater purification.
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Organic-inorganic hybrid metal-polyphenols as stable structural modules have gained extensive interest due to their diverse applications. However, titanium-oxo compounds (TOCs) with large molecular polyphenols have been less explored, and they were expected to be different from small polyphenols with isolated metal ions. Herein, 4-methyl-esculetin (Mesc), a catechol derivative, was selected to construct three TOCs, namely, [Ti17O24(Mesc)4(OiPr)16] (1), [Ti12O14(OiPr)18][Ti16O14(Mesc)12(OiPr)14] (2), and [Ti3O(Mesc)2(OAc)2(OiPr)4] (3). These compounds were structurally characterized. Photocurrent responses were evaluated using the compound-sensitized TiO2 electrodes. It was found that the current densities of 1-3 electrodes are in the order of 1 â« 3 > 2, which relates to the ligand-to-TiO core and ligand-to-ligand charge transfers (LMCT and LLCT, respectively). Density functional theory calculations showed that the lowest band gap of 1 originates from its LLCT. Compound 1 reacted with polyphenol tannin (TA) to form a fully transparent and robust gel (1-TA), and the gelation properties were investigated. Using the gel as a nano-TiO2 fixing agent, solar cell electrodes were prepared by a low-temperature wet method. The photocurrent responsive behavior of the 1-TA/TiO2 electrode was compared with that of the 1-sensitized traditional high-temperature-treated TiO2 electrode. Although the current density of the former is somewhat lower than that of the traditional electrode, the low-temperature wet preparation of the 1-TA/TiO2 electrode is more energy-efficient and sustainable.
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The guanylate-binding proteins (GBPs) belong to the dynamin superfamily of GTPases and function in cell-autonomous defense against intracellular pathogens. IpaH9.8, an E3 ligase from the pathogenic bacterium Shigella flexneri, ubiquitinates a subset of GBPs and leads to their proteasomal degradation. Here we report the structure of a C-terminally truncated GBP1 in complex with the IpaH9.8 Leucine-rich repeat (LRR) domain. IpaH9.8LRR engages the GTPase domain of GBP1, and differences in the Switch II and α3 helix regions render some GBPs such as GBP3 and GBP7 resistant to IpaH9.8. Comparisons with other IpaH structures uncover interaction hot spots in their LRR domains. The C-terminal region of GBP1 undergoes a large rotation compared to previously determined structures. We further show that the C-terminal farnesylation modification also plays a role in regulating GBP1 conformation. Our results suggest a general mechanism by which the IpaH proteins target their cellular substrates and shed light on the structural dynamics of the GBPs.
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Proteínas Bacterianas/química , Simulación de Dinámica Molecular , Shigella flexneri/enzimología , Ubiquitina-Proteína Ligasas/química , Proteínas Bacterianas/genética , Dominios Proteicos , Shigella flexneri/genética , Ubiquitina-Proteína Ligasas/genéticaRESUMEN
Biological cells have long been of interest to researchers due to their capacity to actively control their shape. Accordingly, there is significant interest in generating simplified synthetic protocells that can alter their shape based on an externally or internally generated stimulus. To date, most progress has been made towards controlling the global shape of a protocell, whereas less is known about generating a local shape change. Here, we seek to better understand the possible mechanisms for producing local morphological changes in a popular protocell system, the block copolymer vesicle. Accordingly, we have combined Dissipative Particle Dynamics (DPD) and the Split Reactive Brownian Dynamics algorithm (SRBD) to produce a simulation tool that is capable of modeling the dynamics of self-assembled polymer structures as they undergo chemical reactions. Using this Reactive DPD or RDPD method, we investigate local morphological change driven by either the microinjection of a stimulus or an enzymatically-produced stimulus. We find that sub-vesicle-scale morphological change can be induced by either a solvent stimulus that swells the vesicle membrane, or by a reactant stimulus that alters the chemistry of the block polymer in the membrane corona. Notably, the latter method results in a more persistent local deformation than the former, which we attribute to the slower diffusion of polymer chains relative to the solvent. We quantify this deformation and show that it can be modulated by altering the interaction parameter of the parts of the polymer chain that are affected by the stimulus.
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Simulación de Dinámica Molecular , Polímeros , Difusión , SolventesRESUMEN
Despite the numerous titanium-oxo clusters (TOCs) which have been reported, the nature of small clusters (nuclearity < 10) as model compounds showed large deviation from that of nanoscale TiO materials. Therefore, theoretical and experimental studies for large TOCs merit more attention. We recently prepared and crystallographically characterized a series of large TOCs: Ti11O15(OiPr)16(Cophen) (1), Ti11O15(OiPr)16(Mnphen) (2), Ti10O14(OEt)16(Mnphen)2 (3), and Ti10O14(OEt)16(Mnphphen)2 (4) (phen = 1,10-phenanthroline, phphen = 4,7-biphenyl-phen). These compounds are derivatives of a Ti12 parent cluster by replacing one or two of the five-coordinated titanium atoms of the Ti12 cluster with a transition metal M, Co(II) and Mn(II), that is chelated by a phen group. The effects of mono- and bis-substituted Mphen on the charge and structure of the clusters are discussed. Theoretical evaluation of the frontier orbitals of the clusters is carried out on the basis of the precisely defined crystal structures. Different from the dye molecule to TiO core charge transfer for the dye-modified TOCs, charge transfer in these clusters is from TiO/TiOM to phen/Mphen. The effects of different metal ions and the number of substituted Mphen moieties on the photocurrent properties are evaluated. The results will be of interest to research on cluster chemistry, especially on the TOC chemistry.
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Titanium oxides and bismuth halides or oxyhalides have been known to be excellent semiconductors with both excellent photocatalytic and photoelectric properties. The design of supersalts assembled by titanium-oxo clusters (TOCs) and bismuth iodide clusters is a hopeful strategy for exploring the chemistry and application of new titanium-oxo clusters. We report herein a series of unusual ionic TOCs with Ti12 oxo cluster cations and bismuth iodide anions, [Ti12O15(OiPr)17]3[Bi3I12] (Bi3), [Ti12O14(OiPr)18][Bi4I14(THF)2] (Bi4), and [Ti12O14(OiPr)18][Ti11BiO14(OiPr)17][Bi6I22] (Bi6). Single-crystal X-ray analysis revealed that the type and charge of the Ti12 clusters varied with the charges of different bismuth iodide clusters. Taking advantage of the easy hydrolysis of the TOCs and BiI clusters in water, we used these supersalt crystals as single-source precursors to prepare a p-n-type BiOI-TiO photocatalyst. The heterojunction materials were carefully characterized by powder X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, high-resolution transmission electron microscopy, etc. The synergistic effect of the two components of BiOI and TiO on the photocatalytic degradation of RhB in water is demonstrated. This is a very convenient method for obtaining a p-n-type BiOI-TiO heterojuction photocatalyst by just placing the ground TOC crystals into water.
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Although pristine metal-organic framework (MOF) anodes for lithium-ion batteries (LIBs) show moderate activities and relatively stable cycling, the poor rate capability of the MOF anodes limited their applications in the development of a new generation of energy storage. Herein, the electric active CoII ion is selected to coordinate with redox-active S-rich tetrathiafulvalene (TTF) derivatives to create two TTF-Co-MOFs, formulated as [Co2(py-TTF-py)2(BDC)2]·2DMF·H2O (TTF-Co-MOF 1) and [Co2(py-TTF-py)2(BPDC)2]·3DMF·3H2O (TTF-Co-MOF 2), where py-TTF-py = 2,6-bis(4'-pyridyl)tetrathiafulvalene, H2BDC = terephthalic acid, H2BPDC = biphenyl-4,4'-dicarboxylic acid, and DMF = N,N-dimethylformamide. Crystallographic characterization indicated that the two MOFs possess similar 2-fold-interpenetrating 3D frameworks but with two different pore sizes. The pore-size-dependent performances of the TTF-Co-MOFs were explored to optimize the MOFs as the anode materials for LIBs. TTF-Co-MOF 1 presents a high reversible specific capacity of 1186.6 mAh g-1 at 200 mA g-1 after 287 cycles. The rate capability is greatly enhanced by the introduction of CoII into TTF-based MOFs with specific capacities of 1028.6 mAh g-1 at 5 A g-1 and 966.5 mAh g-1 at 10 A g-1. On the basis of the series analysis of theoretical calculations, electrochemical impedance spectroscopy, and crystal structures, it is found that the CoII metal centers play a bridging role in charge transport within the MOF framework, which is beneficial for the transportation of Li ions. The competitive performances of TTF-Co-MOF 1 are attributed to the synergistic effect of the CoII metal centers and S-rich TTF ligand as well as suitable porosity. The study shed some light for the fabrication of advanced energy storage devices through the rational design of MOF-based anode materials.
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Two dimensional (2D) hybrid perovskites have attracted a great deal of interest because of their appropriate photovoltaic efficiency and environmental stability. Although some 2D hybrid perovskites with sulfur-containing amines have been reported, the cation having the mercaptan group has not been well explored yet. In this work, cysteamine (Cya, HS(CH2)2NH2), a mercaptan-containing amine, was introduced into 2D hybrid perovskite. Two 2D lead iodides with different structures, (HCya)2PbI4 (1) and (HCya)7Pb4I15 (2), were isolated as a red low-temperature phase and a yellow high-temperature phase, respectively. X-ray single-crystal structural analysis showed that the red phase 1 is a single layered corner-shared perovskite and that the yellow phase 2 is a corner/edge-shared quasi-2D perovskite. A thermo-induced reversible 1 to 2 phase transition was found in this synthetic system. The configuration of HCya cation greatly influences the crystallization equilibrium, generating different structures of the lead halides. The single-crystal structure of 1 is discussed in comparison with that of (HAE)2PbI4 (AE = HO(CH2)2NH2), an analogue of 1. The different effects of OH and SH groups on the 2D frameworks are studied based on their hydrogen bonding properties. More remarkably, although the two perovskites have similar structures, the (HCya)2PbI4 (1) has an intrinsic water stability that is much more stable than (HAE)2PbI4, which should be attributed to the affinity of the SH group with lead on the surface of the lead halide.
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Hybrid halide perovskites featuring as new materials of high-performance solar cells have attracted great research interest. The temperature-dependent dimensional transition of halide perovskites is a crucial handle in the preparation of perovskite films. Only the small cations of methylammonium (MA) or formamidinium (FA) have been involved for most of the dimensional transition materials. In this work, thiourea (tu) is introduced into hybrid halide materials. A new series of 1D ribbonlike hybrid lead iodides with tu and MA cations are reported that were crystallographically characterized as MAn(Htu)n+1PbnI4n+1 (n = 1-4 denoted as 1-4, respectively; in 1, MA is replaced by tu). The width of the perovskite ribbon increases from one PbI6 octahedron to four corner-fused octahedra. Compounds 2 and 3 can be turned into a black 3D perovskite after annealing. This is an unusual mixed MA-tu hybrid halide perovskite system, in which the tu molecule plays an important role in manipulating the dimensions and their photoconductive properties. Scanning electron microscopy of the blackened sample shows that there are a lot of regular vent holes on the smooth crystal surface with sizes of hundreds of nanometers. The tunable structures and porous crystals might be advantageous in the sense of material modulation.
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Most large organic cations in the low-dimensional hybrid halide perovskites deteriorate the photoelectric conversion efficiency of the cells. Integrating electronically active organic components into hybrid metal halides is an effective method to improve their photoelectric properties. In this work, a series of compounds obtained by hybridizing redox-active tetrakis(methylthio)tetrathiafulvalene (TMT-TTF) with bismuth chloride, formulated as [TMT-TTF]4[Bi6Cl22] (1 and 1'), [TMT-TTF]3[Bi4Cl16] (2), [TMT-TTF]2[Bi3Cl13] (3), [TMT-TTF]2[Bi2Cl10] (4), and {[TMT-TTF][Bi2Cl8]}n (5), were crystallographically characterized. These hybrids exhibit changeable oxidation states of the TTF moiety. The radical cation TTFâ¢+ exists in 1 and 1', while a mixed-valence TTFâ¢+/TTF2+ appears in 2 that has never been documented in any compounds and the dication TTF2+ exists in 3-5 that has never been introduced into hybrid organic-inorganic materials. The different charged states of the TTF cations lead to various degrees of connectivity of metal chloride anions, which exert a significant effect on the cation-anion arrangement and result in different supramolecular interactions between TMT-TTF and between cations and anions. The changeable oxidation states of the TTF moiety and varying degrees of metal chloride connectivity provide a good comparison among these hybridized bismuth chlorides. The order of conductivity is 2 > 1 > 1' > 3 ≈ 4 â« 5, which results from the synergistic effect of different oxidation states, the packing of TMT-TTF cations, and back charge transfer from the Bi-Cl anion to the TMT-TTF cation. Notably, the electrical conductivity and carrier mobility can be modulated with the fact that compound 2 has the highest performances in the dark, while in light, these properties of 1 and 1' are in turn higher than that of 2. The order of the photocurrent densities is in accordance with the increase of carrier mobility under irradiation of light. This work is the first systematic study of hybrid metal halides with various oxidation states of TTFs and presents a clear structure-property relationship and offers a fresh view on the design of new perovskite materials at the molecular level.
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Incorporation of Eu complexes into various organic or inorganic matrixes is one of the acceptable strategies to obtain displaying materials having practical applications. In this work, we report a convenient approach to preparing high luminescent organic-inorganic hybrid materials and films from the europium-titanium oxo-clusters (EuTOCs) having photoactive antenna ligands. Three Eu2Ti4 oxo-clusters were synthesized and crystallographically characterized. They are the first reported lanthanide-TOCs coordinated with 1,10-phenanthroline (phen) and 2,2'-bipyridine (bpy) as photoactive ligands, Eu2Ti4O6(phen)2(pa)10 (1) (pa = propionate), Eu2Ti4O6(bpy)2(pa)10 (2), and Eu2Ti4O6(phen)2(MA)10 (3) (MA = methacrylate). Benefitting from the photoactive antenna ligands and the rigid cluster structures, these clusters showed bright red luminescence with quantum yield in the range of 60-80% and long lifetime up to 3.0 ms. Unlike those physically mixed polymeric materials, the MA coordinated compound 3 can be self-polymerized to form a brilliant luminescent film. The film coated slide was used to develop a fluorescence sensor for biomolecule ascorbic acid (AA). The low detection limit and reusable properties suggest great potential for such EuTOC films in real applications.