Bonding of Polyethylenimine in Covalent Organic Frameworks for CO Capture from Air.

We have developed a polyethylenimine-functionalized covalent organic framework (COF) for capturing CO from the air. It was synthesized by the crystallization of an imine-linked COF, termed imine-COF-709, followed by linkage oxidation and polyamine installation through aromatic nucleophilic substitution. The chemistry of linkage oxidation and amine installation was fully characterized through Fourier transform infrared spectroscopy, elemental analysis, and solid-state nuclear magnetic resonance (ssNMR) spectroscopy.

Gas Adsorption in Flexible COF-506 and COF-506-Cu.

Flexible covalent-organic frameworks (COFs) display a variety of guest-dependent dynamic behaviors, but because these are an emerging class of materials, very little experimental adsorption data exists. This work examines the adsorption properties of COF-506 and COF-506-Cu utilizing various adsorbates as probe molecules. These materials have small surface areas (<100 m/g) but still have significant capacity for methanol and isopropanol compared to activated carbon, even though the COF contains approximately 1/10th the surface area of many activated carbons.

Carbon dioxide capture from open air using covalent organic frameworks.

Capture of CO from the air offers a promising approach to addressing climate change and achieving carbon neutrality goals. However, the development of a durable material with high capacity, fast kinetics and low regeneration temperature for CO capture, especially from the intricate and dynamic atmosphere, is still lacking. Here a porous, crystalline covalent organic framework (COF) with olefin linkages has been synthesized, structurally characterized and post-synthetically modified by the covalent attachment of amine initiators for producing polyamines within the pores.

Single and Multi-Hop Question-Answering Datasets for Reticular Chemistry with GPT-4-Turbo.

The rapid advancement in artificial intelligence and natural language processing has led to the development of large-scale datasets aimed at benchmarking the performance of machine learning models. Herein, we introduce "RetChemQA", a comprehensive benchmark dataset designed to evaluate the capabilities of such models in the domain of reticular chemistry. This dataset includes both single-hop and multi-hop question-answer pairs, encompassing approximately 45,000 question and answers (Q&As) for each type.

The propensity for covalent organic frameworks to template polymer entanglement.

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.

Water-Enhanced Direct Air Capture of Carbon Dioxide in Metal-Organic Frameworks.

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 H 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 CO showed improved CO 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 CO uptakes at 400 ppm, measuring 0.

Harvesting Water from Air with High-Capacity, Stable Furan-Based Metal-Organic Frameworks.

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.

Crystalline Polyphenylene Covalent Organic Frameworks.

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 C CP/MAS NMR spectroscopy. The results showed that the COFs were porous and chemically stable in corrosive, harsh environments for at least 1 week.

Shaping the Water-Harvesting Behavior of Metal-Organic Frameworks Aided by Fine-Tuned GPT Models.

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.

Structural Chemistry of Zeolitic Imidazolate Frameworks.

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.

ChatGPT Research Group for Optimizing the Crystallinity of MOFs and COFs.

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.

A discrete 'early-responder' stromal-cell subtype orchestrates immunocyte recruitment to injured tissue.

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-1β, TNF-α and oncostatin M each strongly and rapidly induced MmSCs transcribing this immunomodulatory program.

Directing Molecular Weaving of Covalent Organic Frameworks and Their Dimensionality by Angular Control.

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.

A GPT-4 Reticular Chemist for Guiding MOF Discovery.

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.

ChatGPT Chemistry Assistant for Text Mining and the Prediction of MOF Synthesis.

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.

A Porous Crystalline Nitrone-Linked Covalent Organic Framework.

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 C multi cross-polarization magic angle spinning NMR spectroscopy of the C-isotope-labeled COF-115 and Fourier-transform infrared spectroscopy. The permanent porosity of COF-115 was evaluated through low-pressure N , CO , and H sorption experiments.

Water Harvesting at the Single-Crystal Level.

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.

MOF Linker Extension Strategy for Enhanced Atmospheric Water Harvesting.

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 PZVDC is ()-5-(2-carboxylatovinyl)-1-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.

High-Porosity Metal-Organic Framework Glasses.

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 Ti O (OEt) , 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.

Decoding complex order in reticular frameworks.

Periodicity and aperiodicity coexist in a nonchaotic, information-rich crystal structure.

Broadly Tunable Atmospheric Water Harvesting in Multivariate Metal-Organic Frameworks.

Development of multivariate metal-organic frameworks (MOFs) as derivatives of the state-of-art water-harvesting material MOF-303 {[Al(OH)(PZDC)], where PZDC is 1-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) than reported previously.

High-yield, green and scalable methods for producing MOF-303 for water harvesting from desert air.

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.

Molecular and spatial epidemiology of HCV among people who inject drugs in Boston, Massachusetts.

Integration of genetic, social network, and spatial data has the potential to improve understanding of transmission dynamics in established HCV epidemics. Sequence data were analyzed from 63 viremic people who inject drugs recruited in the Boston area through chain referral or time-location sampling. HCV subtype 1a was most prevalent (57.

The potential for Treg-enhancing therapies in tissue, in particular skeletal muscle, regeneration.

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.