RESUMO
The introduction of molecularly woven three-dimensional (3D) covalent organic framework (COF) crystals into polymers of varying types invokes different forms of contact between filler and polymer. Whereas the combination of woven COFs with amorphous and brittle polymethyl methacrylate results in surface interactions, the use of the liquid-crystalline polymer polyimide induces the formation of polymer-COF junctions. These junctions are generated by the threading of polymer chains through the pores of the nanocrystals, thus allowing for spatial arrangement of polymer strands. This offers a programmable pathway for unthreading polymer strands under stress and leads to the in situ formation of high-aspect-ratio nanofibrils, which dissipate energy during the fracture. Polymer-COF junctions also strengthen the filler-matrix interfaces and lower the percolation thresholds of the composites, enhancing strength, ductility, and toughness of the composites by adding small amounts (~1 weight %) of woven COF nanocrystals. The ability of the polymer strands to closely interact with the woven framework is highlighted as the main parameter to forming these junctions, thus affecting polymer chain penetration and conformation.
RESUMO
We synthesized two isoreticular furan-based metal-organic frameworks (MOFs), MOF-LA2-1(furan) and MOF-LA2-2(furan) with rod-like secondary building units (SBUs) featuring 1D channels, as sorbents for atmospheric water harvesting (LA = long arm). These aluminum-based MOFs demonstrated a combination of high water uptake and stability, exhibiting working capacities of 0.41 and 0.48 gwater/gMOF (under isobaric conditions of 1.70 kPa), respectively. Remarkably, both MOFs showed a negligible loss in water uptake after 165 adsorption-desorption cycles. These working capacities rival that of MOF-LA2-1(pyrazole), which has a working capacity of 0.55 gwater/gMOF. The current MOFs stand out for their high water stability, as evidenced by 165 cycles of water uptake and release. MOF-LA2-2(furan) is the first aluminum MOF to employ a double 'long arm' extension strategy, which is confirmed through single-crystal X-ray diffraction (SCXRD). The MOFs were synthesized by using a straightforward synthesis route. This study offers valuable insights into the design of durable, water-stable MOFs and underscores their potential for efficient water harvesting.
RESUMO
We have developed two series of amine-functionalized zirconium (Zr) metal-organic framework-808 (MOF-808), which were produced by postsynthetic modifications to have either amino acids coordinated to Zr ions (MOF-808-AAs) or polyamines covalently bound to the chloro-functionalized structure (MOF-808-PAs). These MOF variants were comprehensively characterized by liquid-state 1H nuclear magnetic resonance (NMR) measurements and potentiometric acid-base titration to determine the amounts of amines, energy-dispersive X-ray spectroscopy to assess the extent of covalent substitution by polyamines, powder X-ray diffraction analysis to verify the maintenance of the MOF crystallinity and structure after postsynthetic modifications, nitrogen sorption isotherm measurements to confirm retention of the porosity, and water sorption isotherm measurements to find the water uptake in the pores of each member of the series. Evaluation and testing of these compounds in direct air capture (DAC) of CO2 showed improved CO2 capture performance for the functionalized forms, especially under humid conditions: In dry conditions, the l-lysine- and tris(3-aminopropyl)amine-functionalized variants, termed as MOF-808-Lys and MOF-808-TAPA, exhibited the highest CO2 uptakes at 400 ppm, measuring 0.612 and 0.498 mmol g-1, and further capacity enhancement was achieved by introducing 50% relative humidity, resulting in remarkable uptakes of 1.205 and 0.872 mmol g-1 corresponding to 97 and 75% increase compared to the dry uptakes, respectively. The mechanism underlying the enhanced uptake efficiency was revealed by 13C solid-state NMR and temperature-programmed desorption measurements, indicating the formation of bicarbonate species, and therefore a stoichiometry of 1:1 CO2 to each amine site.
RESUMO
The synthesis of crystalline polyphenylene covalent organic frameworks (COFs) was accomplished by linking fluorinated tris(4-acetylphenyl)benzene building units using aldol cyclotrimerization. The structures of the two COFs, reported here, were confirmed by powder X-ray diffraction techniques, Fourier transform infrared, and solid-state 13C CP/MAS NMR spectroscopy. The results showed that the COFs were porous and chemically stable in corrosive, harsh environments for at least 1 week. Accordingly, postsynthetically modified derivatives of these COFs using primary amines showed CO2 uptake from air and flue gas.
RESUMO
Zeolitic imidazolate frameworks (ZIFs) are a subclass of reticular structures based on tetrahedral four-connected networks of zeolites and minerals. They are composed of transition-metal ions and imidazolate-type linkers, and their pore size and shape, surface area, and functionality can be precisely controlled. Despite their potential, two questions remain unanswered: how to synthesize more diverse ZIF structures and how ZIFs differentiate from other crystalline solids. In other words, how can we use our understanding of their unique structures to better design and synthesize ZIFs? In this Review, we first summarize the methods for synthesizing a wide range of ZIFs. We then review the crystal structure of ZIFs and describe the relationship between their structure and properties using an in-depth analysis. We also discuss several important and intrinsic features that make ZIFs stand out from MOFs and discrete molecular cages. Finally, we outline the future direction for this class of porous crystals.
RESUMO
We construct a data set of metal-organic framework (MOF) linkers and employ a fine-tuned GPT assistant to propose MOF linker designs by mutating and modifying the existing linker structures. This strategy allows the GPT model to learn the intricate language of chemistry in molecular representations, thereby achieving an enhanced accuracy in generating linker structures compared with its base models. Aiming to highlight the significance of linker design strategies in advancing the discovery of water-harvesting MOFs, we conducted a systematic MOF variant expansion upon state-of-the-art MOF-303 utilizing a multidimensional approach that integrates linker extension with multivariate tuning strategies. We synthesized a series of isoreticular aluminum MOFs, termed Long-Arm MOFs (LAMOF-1 to LAMOF-10), featuring linkers that bear various combinations of heteroatoms in their five-membered ring moiety, replacing pyrazole with either thiophene, furan, or thiazole rings or a combination of two. Beyond their consistent and robust architecture, as demonstrated by permanent porosity and thermal stability, the LAMOF series offers a generalizable synthesis strategy. Importantly, these 10 LAMOFs establish new benchmarks for water uptake (up to 0.64 g g-1) and operational humidity ranges (between 13 and 53%), thereby expanding the diversity of water-harvesting MOFs.
RESUMO
Following acute injury, stromal cells promote tissue regeneration by a diversity of mechanisms. Time-resolved single-cell RNA sequencing of muscle mesenchymal stromal cells (MmSCs) responding to acute injury identified an 'early-responder' subtype that spiked on day 1 and expressed a notable array of transcripts encoding immunomodulators. IL-1ß, TNF-α and oncostatin M each strongly and rapidly induced MmSCs transcribing this immunomodulatory program. Macrophages amplified the program but were not strictly required for its induction. Transfer of the inflammatory MmSC subtype, tagged with a unique surface marker, into healthy hindlimb muscle induced inflammation primarily driven by neutrophils and macrophages. Among the abundant inflammatory transcripts produced by this subtype, Cxcl5 was stroma-specific and highly upregulated with injury. Depletion of this chemokine early after injury revealed a substantial impact on recruitment of neutrophils, a prolongation of inflammation to later times and an effect on tissue regeneration. Mesenchymal stromal cell subtypes expressing a comparable inflammatory program were found in a mouse model of muscular dystrophy and in several other tissues and pathologies in both mice and humans. These 'early-responder' mesenchymal stromal cells, already in place, permit rapid and coordinated mobilization and amplification of critical cell collaborators in response to injury.
Assuntos
Inflamação , Células-Tronco Mesenquimais , Humanos , Camundongos , Animais , Inflamação/metabolismo , Macrófagos/metabolismo , Células-Tronco Mesenquimais/metabolismo , Neutrófilos/metabolismo , CicatrizaçãoRESUMO
We leveraged the power of ChatGPT and Bayesian optimization in the development of a multi-AI-driven system, backed by seven large language model-based assistants and equipped with machine learning algorithms, that seamlessly orchestrates a multitude of research aspects in a chemistry laboratory (termed the ChatGPT Research Group). Our approach accelerated the discovery of optimal microwave synthesis conditions, enhancing the crystallinity of MOF-321, MOF-322, and COF-323 and achieving the desired porosity and water capacity. In this system, human researchers gained assistance from these diverse AI collaborators, each with a unique role within the laboratory environment, spanning strategy planning, literature search, coding, robotic operation, labware design, safety inspection, and data analysis. Such a comprehensive approach enables a single researcher working in concert with AI to achieve productivity levels analogous to those of an entire traditional scientific team. Furthermore, by reducing human biases in screening experimental conditions and deftly balancing the exploration and exploitation of synthesis parameters, our Bayesian search approach precisely zeroed in on optimal synthesis conditions from a pool of 6 million within a significantly shortened time scale. This work serves as a compelling proof of concept for an AI-driven revolution in the chemistry laboratory, painting a future where AI becomes an efficient collaborator, liberating us from routine tasks to focus on pushing the boundaries of innovation.
RESUMO
We present a new framework integrating the AI model GPT-4 into the iterative process of reticular chemistry experimentation, leveraging a cooperative workflow of interaction between AI and a human researcher. This GPT-4 Reticular Chemist is an integrated system composed of three phases. Each of these utilizes GPT-4 in various capacities, wherein GPT-4 provides detailed instructions for chemical experimentation and the human provides feedback on the experimental outcomes, including both success and failures, for the in-context learning of AI in the next iteration. This iterative human-AI interaction enabled GPT-4 to learn from the outcomes, much like an experienced chemist, by a prompt-learning strategy. Importantly, the system is based on natural language for both development and operation, eliminating the need for coding skills, and thus, make it accessible to all chemists. Our collaboration with GPT-4 Reticular Chemist guided the discovery of an isoreticular series of MOFs, with each synthesis fine-tuned through iterative feedback and expert suggestions. This workflow presents a potential for broader applications in scientific research by harnessing the capability of large language models like GPT-4 to enhance the feasibility and efficiency of research activities.
RESUMO
Although reticular chemistry has commonly utilized mutually embracing tetrahedral metal complexes as crossing points to generate three-dimensional molecularly woven structures, weaving in two dimensions remains largely unexplored. We report a new strategy to access 2D woven COFs by controlling the angle of the usually linear linker, resulting in the successful synthesis of a 2D woven pattern based on chain-link fence. The synthesis was accomplished by linking aldehyde-functionalized copper(I) bisphenanthroline complexes with bent 4,4'-oxydianiline building units. This results in the formation of a crystalline solid, termed COF-523-Cu, whose structure was characterized by spectroscopic techniques and electron and X-ray diffraction techniques to reveal a molecularly woven, twofold-interpenetrated chain-link fence. The present work significantly advances the concept of molecular weaving and its practice in the design of complex chemical structures.
RESUMO
We use prompt engineering to guide ChatGPT in the automation of text mining of metal-organic framework (MOF) synthesis conditions from diverse formats and styles of the scientific literature. This effectively mitigates ChatGPT's tendency to hallucinate information, an issue that previously made the use of large language models (LLMs) in scientific fields challenging. Our approach involves the development of a workflow implementing three different processes for text mining, programmed by ChatGPT itself. All of them enable parsing, searching, filtering, classification, summarization, and data unification with different trade-offs among labor, speed, and accuracy. We deploy this system to extract 26â¯257 distinct synthesis parameters pertaining to approximately 800 MOFs sourced from peer-reviewed research articles. This process incorporates our ChemPrompt Engineering strategy to instruct ChatGPT in text mining, resulting in impressive precision, recall, and F1 scores of 90-99%. Furthermore, with the data set built by text mining, we constructed a machine-learning model with over 87% accuracy in predicting MOF experimental crystallization outcomes and preliminarily identifying important factors in MOF crystallization. We also developed a reliable data-grounded MOF chatbot to answer questions about chemical reactions and synthesis procedures. Given that the process of using ChatGPT reliably mines and tabulates diverse MOF synthesis information in a unified format while using only narrative language requiring no coding expertise, we anticipate that our ChatGPT Chemistry Assistant will be very useful across various other chemistry subdisciplines.
RESUMO
Herein, we report the synthesis of a nitrone-linked covalent organic framework, COF-115, by combining N, N', N', N'''-(ethene-1, 1, 2, 2-tetrayltetrakis(benzene-4, 1-diyl))tetrakis(hydroxylamine) and terephthaladehyde via a polycondensation reaction. The formation of the nitrone functionality was confirmed by solid-state 13 C multi cross-polarization magic angle spinning NMR spectroscopy of the 13 C-isotope-labeled COF-115 and Fourier-transform infrared spectroscopy. The permanent porosity of COF-115 was evaluated through low-pressure N2 , CO2 , and H2 sorption experiments. Water vapor and carbon dioxide sorption analysis of COF-115 and the isoreticular imine-linked COF indicated a superior potential of N-oxide-based porous materials for atmospheric water harvesting and CO2 capture applications. Density functional theory calculations provided valuable insights into the difference between the adsorption properties of these COFs. Lastly, photoinduced rearrangement of COF-115 to the associated amide-linked material was successfully demonstrated.
RESUMO
Metal-organic frameworks (MOFs) have emerged as a class of porous materials with facile uptake and release of water, turning them into excellent substrates for real-world atmospheric water harvesting applications. The performance of different MOF systems was experimentally characterized at the bulk level by assessing the total amount of water taken up and the release kinetics, leaving the question behind of what the upper limit of the pristine materials actually is. Moreover, recent devices rely on fluidized bed reactors that exploit the harvesting capacities of MOFs at the single-crystal (SC) level. In this publication, we present a novel methodology based on Raman spectroscopy, for acquiring water adsorption isotherms and kinetic curves with a sub-micrometer resolution that provides valuable insights into the material behavior probing the pristine MOF at the SC level. We investigated isolated MOF-801 particles in situ and could dissect contributions of intra- and inter-particle effects on the water harvesting performance of MOF-801 via adsorption-desorption isotherms and kinetic curves. Using spontaneous Raman spectroscopy, we found an almost 20-fold faster uptake for the undisturbed crystalline material. Correlative imaging based on four-wave mixing and coherent anti-Stokes Raman scattering further localized the uptaken water inside MOF-801 and identified inter-particle condensation as the main source for the discrepancies between the performance at the bulk and SC level. Our studies determined an upper limit of around 91.9 L/kgMOF/day for MOF-801.
RESUMO
A linker extension strategy for generating metal-organic frameworks (MOFs) with superior moisture-capturing properties is presented. Applying this design approach involving experiment and computation results in MOF-LA2-1 {[Al(OH)(PZVDC)], where PZVDC2- is (E)-5-(2-carboxylatovinyl)-1H-pyrazole-3-carboxylate}, which exhibits an approximately 50% water capacity increase compared to the state-of-the-art water-harvesting material MOF-303. The power of this approach is the increase in pore volume while retaining the ability of the MOF to harvest water in arid environments under long-term uptake and release cycling, as well as affording a reduction in regeneration heat and temperature. Density functional theory calculations and Monte Carlo simulations give detailed insight pertaining to framework structure, water interactions within its pores, and the resulting water sorption isotherm.
RESUMO
We report a synthetic strategy to link titanium-oxo (Ti-oxo) clusters into metal-organic framework (MOF) glasses with high porosity though the carboxylate linkage. A new series of MOF glasses was synthesized by evaporation of solution containing Ti-oxo clusters Ti16 O16 (OEt)32 , linkers, and m-cresol. The formation of carboxylate linkages between the Ti-oxo clusters and the carboxylate linkers was confirmed by Fourier-transform infrared (FT-IR) spectroscopy. The structural integrity of the Ti-oxo clusters within the glasses was evidenced by both X-ray absorption near edge structure (XANES) and 17 O magic-angle spinning (MAS) NMR. After ligand exchange and activation, the fumarate-linked MOF glass, termed Ti-Fum, showed a N2 Brunauer-Emmett-Teller (BET) surface areas of 923â m2 g-1 , nearly three times as high as the phenolate-linked MOF glass with the highest BET surface area prior to this report.
RESUMO
Periodicity and aperiodicity coexist in a nonchaotic, information-rich crystal structure.
RESUMO
Metal-organic frameworks (MOFs) are excellent candidates for water harvesting from desert air. MOF-303 (Al(OH)(PZDC), where PZDC is 1-H-pyrazole-3,5-dicarboxylate), a robust and water-stable MOF, is a particularly promising water-harvesting sorbent that can take up water at low relative humidity and release it under mild heating. Accordingly, development of a facile, high-yield synthesis method for its production at scale is highly desirable. Here we report detailed protocols for the green, water-based preparation of MOF-303 on both gram and kilogram scales. Specifically, four synthetic methods (solvothermal, reflux, vessel and microwave), involving different equipment requirements, are presented to guarantee general accessibility. Typically, the solvothermal method takes ~24 h to synthesize MOF-303, while the reflux and vessel methods can reduce the time to 4-8 h. With the microwave-assisted method, the reaction time can be further reduced to just 5 min. In addition, we provide guidance on the characterization of MOF-303, as well as water-harvesting MOFs in general, to ensure high quality of the product in terms of its purity, crystallinity, porosity and water uptake. Furthermore, to address the need for future commercialization of this material, we demonstrate that our protocol can be employed to produce 3.5 kg per batch with a yield of 91%. MOF-303 synthesized at this large scale shows similar crystallinity and water uptake capacity compared to the respective material produced at a small scale. Our synthetic procedure is green and water-based, and can produce the MOF within hours.
Assuntos
Ácidos Carboxílicos , Estruturas Metalorgânicas , Transporte Biológico , Micro-Ondas , ÁguaRESUMO
Foxp3+CD4+ regulatory T cells (Tregs) are famous for their role in maintaining immunological tolerance. With their distinct transcriptomes, growth-factor dependencies and T-cell receptor (TCR) repertoires, Tregs in nonlymphoid tissues, termed "tissue-Tregs," also perform a variety of functions to help assure tissue homeostasis. For example, they are important for tissue repair and regeneration after various types of injury, both acute and chronic. They exert this influence by controlling both the inflammatory tenor and the dynamics of the parenchymal progenitor-cell pool in injured tissues, thereby promoting efficient repair and limiting fibrosis. Thus, tissue-Tregs are seemingly attractive targets for immunotherapy in the context of tissue regeneration, offering several advantages over existing therapies. Using skeletal muscle as a model system, we discuss the existing literature on Tregs' role in tissue regeneration in acute and chronic injuries, and various approaches for their therapeutic modulation in such contexts, including exercise as a natural Treg modulator.
Assuntos
Músculo Esquelético , Linfócitos T Reguladores , Tolerância ImunológicaRESUMO
Development of multivariate metal-organic frameworks (MOFs) as derivatives of the state-of-art water-harvesting material MOF-303 {[Al(OH)(PZDC)], where PZDC2- is 1H-pyrazole-3,5-dicarboxylate} was shown to be a powerful tool to generate efficient water sorbents tailored to a given environmental condition. Herein, a new multivariate MOF-303-based water-harvesting framework series from readily available reactants is developed. The resulting MOFs exhibit a larger degree of tunability in the operational relative humidity range (16%), regeneration temperature (14 °C), and desorption enthalpy (5 kJ mol-1) than reported previously. Additionally, a high-yielding (≥90%) and scalable (â¼3.5 kg) synthesis is demonstrated in water and with excellent space-time yields, without compromising framework crystallinity, porosity, and water-harvesting performance.
Assuntos
Estruturas Metalorgânicas , Água , Porosidade , TemperaturaRESUMO
We report a postsynthetic strategy and its implementation to make covalent organic frameworks (COFs) with irreversible hydrazide linkages. This involved the synthesis of three 2D and 3D hydrazine-linked frameworks and their partial oxidation. The linkage synthesis and functional group transformation-hydrazine and hydrazide-were evidenced by 15N multi-CP-MAS NMR. In addition, the isothermal water uptake profiles of these frameworks were studied, leading to the discovery of one hydrazine-hydrazide-linked COF suitable for water harvesting from air in arid conditions. This COF displayed characteristic S-shaped water sorption profiles, a steep pore-filling step below 18% relative humidity at 25 °C, and a total uptake capacity of 0.45 g g-1. We found that even small changes made on the molecular level can lead to major differences in the water isotherm profiles, therefore pointing to the utility of water sorption analysis as a complementary analytical tool to study linkage transformations.