14 research outputs found
Mixed Conductive, Injectable, and Fluorescent Supramolecular Eutectogel Composites
Funding Information: This work was supported by Marie Sklodowska‐Curie Research and Innovation Staff Exchanges (RISE) under the grant agreement No 823989 “IONBIKE”. The financial support received from CONICET and ANPCyT (Argentina) is also gratefully acknowledged. M. C.‐G. thanks Emakiker Grant Program of POLYMAT. L. C. T. is grateful to Fundação para a Ciência e a Tecnologia (FCT/MCTES) in Portugal for her research contract under Scientific Employment Stimulus (2020.01555.CEECIND), and Associate Laboratory for Green Chemistry—LAQV, which is also financed by FCT/MCTES (UIDB/50006/2020 and UIDP/50006/2020). D. M. thanks “Ayuda RYC2021‐031668‐I financiada por MCIN/AEI/10.13039/501100011033 y por la Unión Europea NextGenerationEU/PRTR”. The authors thank the technical and human support provided by SGIker (UPV/EHU/ERDF, EU). Funding Information: This work was supported by Marie Sklodowska-Curie Research and Innovation Staff Exchanges (RISE) under the grant agreement No 823989 “IONBIKE”. The financial support received from CONICET and ANPCyT (Argentina) is also gratefully acknowledged. M. C.-G. thanks Emakiker Grant Program of POLYMAT. L. C. T. is grateful to Fundação para a Ciência e a Tecnologia (FCT/MCTES) in Portugal for her research contract under Scientific Employment Stimulus (2020.01555.CEECIND), and Associate Laboratory for Green Chemistry—LAQV, which is also financed by FCT/MCTES (UIDB/50006/2020 and UIDP/50006/2020). D. M. thanks “Ayuda RYC2021-031668-I financiada por MCIN/AEI/10.13039/501100011033 y por la Unión Europea NextGenerationEU/PRTR”. The authors thank the technical and human support provided by SGIker (UPV/EHU/ERDF, EU). Publisher Copyright: © 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.Eutectogels are an emerging family of soft ionic materials alternative to ionic liquid gels and organogels, offering fresh perspectives for designing functional dynamic platforms in water-free environments. Herein, the first example of mixed ionic and electronic conducting supramolecular eutectogel composites is reported. A fluorescent glutamic acid-derived low-molecular-weight gelator (LMWG) was found to self-assemble into nanofibrillar networks in deep eutectic solvents (DES)/poly(3,4-ethylenedioxythiophene) (PEDOT): chondroitin sulfate dispersions. These dynamic materials displayed excellent injectability and self-healing properties, high ionic conductivity (up to 10−2 S cm−1), good biocompatibility, and fluorescence imaging ability. This set of features turns the mixed conducting supramolecular eutectogels into promising adaptive materials for bioimaging and electrostimulation applications.publishersversionpublishe
Seven Post-synthetic Covalent Reactions in Tandem Leading to Enzyme-like Complexity within Metal–Organic Framework Crystals
Isomers of Metal–Organic Complex Arrays
Three metal–organic complex arrays (MOCAs) with
a specific sequence of metal centers
as well as that of amino acid units were synthesized. These MOCAs
are also isomers exhibiting a gelation capability dependent on the
location of the metal complexes in the arrays
Convergent Synthesis of a Metal–Organic Framework Supported Olefin Metathesis Catalyst
Synthesis
of a metal–organic framework (MOF)-supported olefin
metathesis catalyst has been accomplished for the first time following
a new, convergent approach where an aldehyde-functionalized derivative
of Hoveyda’s recently reported ruthenium catecholate olefin
metathesis catalyst is condensed with an amine-functionalized IRMOF-74-III.
The resulting material, denoted MOF-Ru, has well-defined, catalytically active ruthenium centers
confined within channels having a ca. 20 Å diameter. MOF-Ru is
a recyclable, single-site catalyst for self-cross-metathesis and ring-closing
metathesis of terminal olefins. Comparison of this heterogeneous catalyst
with a homogeneous analogue shows different responses to substrate
size and shape suggestive of confinement effects. The MOF-Ru catalyst
also displays greater resistance to double-bond migration that can
be attributed to greater catalyst stability. For the preparation of
well-defined, single-site heterogeneous catalysts where catalyst purity
is essential, the convergent approach employed here, where the catalytic
center is prepared ex situ and covalently linked to an intact MOF,
offers an attractive alternative to in situ catalyst preparation as
currently practiced in MOF chemistry
Modular Synthesis of Metal–Organic Complex Arrays Containing Precisely Designed Metal Sequences
A modular
synthetic approach is reported for the synthesis of heterometallic
metal–organic complex arrays (MOCAs). Modules of four metal
centers containing three different metals copper(II), nickel(II),
platinum(II), or ruthenium(II) are prepared using a solid-phase polypeptide
synthesis technique and then linked in solution to make MOCAs of eight
metal centers as linear, T-branched, and H-branched compounds. The
MOCA molecular topologies thus have specific unique linear and branched
sequences of metals along the peptide backbone
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Metal-organic frameworks with precisely designed interior for carbon dioxide capture in the presence of water.
The selective capture of carbon dioxide in the presence of water is an outstanding challenge. Here, we show that the interior of IRMOF-74-III can be covalently functionalized with primary amine (IRMOF-74-III-CH2NH2) and used for the selective capture of CO2 in 65% relative humidity. This study encompasses the synthesis, structural characterization, gas adsorption, and CO2 capture properties of variously functionalized IRMOF-74-III compounds (IRMOF-74-III-CH3, -NH2, -CH2NHBoc, -CH2NMeBoc, -CH2NH2, and -CH2NHMe). Cross-polarization magic angle spinning (13)C NMR spectra showed that CO2 binds chemically to IRMOF-74-III-CH2NH2 and -CH2NHMe to make carbamic species. Carbon dioxide isotherms and breakthrough experiments show that IRMOF-74-III-CH2NH2 is especially efficient at taking up CO2 (3.2 mmol of CO2 per gram at 800 Torr) and, more significantly, removing CO2 from wet nitrogen gas streams with breakthrough time of 610 ± 10 s g(-1) and full preservation of the IRMOF structure
Metal-organic frameworks with precisely designed interior for carbon dioxide capture in the presence of water.
The selective capture of carbon dioxide in the presence of water is an outstanding challenge. Here, we show that the interior of IRMOF-74-III can be covalently functionalized with primary amine (IRMOF-74-III-CH2NH2) and used for the selective capture of CO2 in 65% relative humidity. This study encompasses the synthesis, structural characterization, gas adsorption, and CO2 capture properties of variously functionalized IRMOF-74-III compounds (IRMOF-74-III-CH3, -NH2, -CH2NHBoc, -CH2NMeBoc, -CH2NH2, and -CH2NHMe). Cross-polarization magic angle spinning (13)C NMR spectra showed that CO2 binds chemically to IRMOF-74-III-CH2NH2 and -CH2NHMe to make carbamic species. Carbon dioxide isotherms and breakthrough experiments show that IRMOF-74-III-CH2NH2 is especially efficient at taking up CO2 (3.2 mmol of CO2 per gram at 800 Torr) and, more significantly, removing CO2 from wet nitrogen gas streams with breakthrough time of 610 ± 10 s g(-1) and full preservation of the IRMOF structure
Seven Post-synthetic Covalent Reactions in Tandem Leading to Enzyme-like Complexity within MetalOrganic Framework Crystals
Seven Post-synthetic Covalent Reactions in Tandem Leading to Enzyme-like Complexity within Metal–Organic Framework Crystals
The design of enzyme-like
complexity within metal–organic
frameworks (MOFs) requires multiple reactions to be performed on a
MOF crystal without losing access to its interior. Here, we show that
seven post-synthetic reactions can be successfully achieved within
the pores of a multivariate MOF, MTV-IRMOF-74-III, to covalently incorporate
tripeptides that resemble the active sites of enzymes in their spatial
arrangement and compositional heterogeneity. These reactions build
up H<sub>2</sub>N-Pro-Gly-Ala-CONHL and H<sub>2</sub>N-Cys-His-Asp-CONHL
(where L = organic struts) amino acid sequences by covalently attaching
them to the organic struts in the MOFs, without losing porosity or
crystallinity. An enabling feature of this chemistry is that the primary
amine functionality (−CH<sub>2</sub>NHBoc) of the original
MOF is more reactive than the commonly examined aromatic amines (−NH<sub>2</sub>), and this allowed for the multi-step reactions to be carried
out in tandem within the MOF. Preliminary findings indicate that the
complexity thus achieved can affect reactions that were previously
accomplished only in the presence of enzymes
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The Chemistry of CO2 Capture in an Amine-Functionalized Metal-Organic Framework under Dry and Humid Conditions.
The use of two primary alkylamine functionalities covalently tethered to the linkers of IRMOF-74-III results in a material that can uptake CO2 at low pressures through a chemisorption mechanism. In contrast to other primary amine-functionalized solid adsorbents that uptake CO2 primarily as ammonium carbamates, we observe using solid state NMR that the major chemisorption product for this material is carbamic acid. The equilibrium of reaction products also shifts to ammonium carbamate when water vapor is present; a new finding that has impact on control of the chemistry of CO2 capture in MOF materials and one that highlights the importance of geometric constraints and the mediating role of water within the pores of MOFs