Molecular Level Characterization of the Structure and Interactions in Peptide‐Functionalized Metal–Organic Frameworks

Todorova, Tanya K.; Rozanska, Xavier; Gervais, Christel; Legrand, Alexandre; Ho, Linh Ngoc; Berruyer, Pierrick; Lesage, Anne; Emsley, Lyndon; Farrusseng, David; Canivet, J.; Mellot‐Draznieks, Caroline

doi:10.1002/chem.201603255

Cited by 28 publications

(21 citation statements)

References 93 publications

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“…Such diffusion has been monitored by EPR spectroscopy and the estimate of 13 C- 27 Al dipolar couplings in aluminium-based MOF has demonstrated that the impregnation with a radical solution and the freezing of the sample down to 100 K do not alter the particular MOF's structure [239]. For bulkier PAs, such as TEKPol, or functionalized MOFs, the PAs cannot penetrate the pores and reside on or near the surface of the crystallites [111][112][113]264]. DNP-enhanced 1 H polarization is transported within the microcrystal by spin diffusion among protons of the linker and the solvent.…”

Section: Microporous Materialsmentioning

confidence: 99%

“…Hence, the DNP enhancements for MOFs are in general significantly lower than those achieved for mesoporous materials. Nevertheless, the gain in sensitivity provided by DNP has enabled the detection of insensitive isotopes, such as 15 N in natural abundance [111,113,264] or 195 Pt [112], in MOFs. DNP has also been employed for the characterization of zeolite frameworks [114][115][116]194] and the organic species in its micropores [117,266,267].…”

Section: Microporous Materialsmentioning

confidence: 99%

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Recent developments in MAS DNP-NMR of materials

Rankin

Trébosc

Pourpoint

et al. 2019

Solid State Nuclear Magnetic Resonance

137

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Solid-state NMR spectroscopy is a powerful technique for the characterization of the atomic-level structure and dynamics of materials. Nevertheless, the use of this technique is often limited by its lack of sensitivity, which can prevent the observation of surfaces, defects or insensitive isotopes. Dynamic Nuclear Polarization (DNP) has been shown to improve by one to three orders of magnitude the sensitivity of NMR experiments on materials under Magic-Angle Spinning (MAS), at static magnetic field B0 ≥ 5 T, conditions allowing for the acquisition of high-resolution spectra. The field of DNP-NMR spectroscopy of materials has undergone a rapid development in the last ten years, spurred notably by the availability of commercial DNP-NMR systems. We provide here an in-depth overview of MAS DNP-NMR studies of materials at high B0 field. After a historical perspective of DNP of materials, we describe the DNP transfers under MAS, the transport of polarization by spin diffusion and the various contributions to the overall sensitivity of DNP-NMR experiments. We discuss the design of tailored polarizing agents and the sample preparation in the case of materials. We present the DNP-NMR hardware and the influence of key experimental parameters, such as microwave power, magnetic field, temperature and MAS frequency. We give an overview of the isotopes, which have been detected by this technique, and the NMR methods, which have been combined with DNP. Finally, we show how MAS DNP-NMR has been applied to gain new insights into the structure of organic, hybrid and inorganic materials with applications in fields, such as health, energy, catalysis, optoelectronics etc.

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Section: Microporous Materialsmentioning

confidence: 99%

Section: Microporous Materialsmentioning

confidence: 99%

Recent developments in MAS DNP-NMR of materials

Rankin

Trébosc

Pourpoint

et al. 2019

Solid State Nuclear Magnetic Resonance

137

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“…In addition to SPPS, microwave‐assisted postsynthetic methods have recently been reported on grafting oligopeptides onto MOF backbones under microwave irradiation, yielding enantiopure peptides anchored within MOF cavities . Simulation work was also carried out to study the conformation of peptides when grafted in MOF hosts; which specific conformational selection is identified as a result of strong host‐guest interactions …”

Section: Incorporation Of Small Biomoleculesmentioning

confidence: 99%

Integration of Biomolecules with Metal–Organic Frameworks

Zhuang

Young

Tsung

2017

Small

148

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Owing to the progressive development of metal-organic-frameworks (MOFs) synthetic processes and considerable potential applications in last decade, integrating biomolecules into MOFs has recently gain considerable attention. Biomolecules, including lipids, oligopeptides, nucleic acids, and proteins have been readily incorporated into MOF systems via versatile formulation methods. The formed biomolecule-MOF hybrid structures have shown promising prospects in various fields, such as antitumor treatment, gene delivery, biomolecular sensing, and nanomotor device. By optimizing biomolecule integration methods while overcoming existing challenges, biomolecule-integrated MOF platforms are very promising to generate more practical applications.

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“…Due to the aggregation effect of bare NMOFs, proper surface modification is needed to improve the water dispersibility or various further functionalization of NMOFs for biomedical applications. NMOFs can be coated with silica, 27 peptides, 28 , 29 proteins, 26 , 30 polymers, 31 etc. Although great progress has been made, functionalization on the surface of NMOFs and further conjugation with molecular probes is still very challenging.…”

Section: Introductionmentioning

confidence: 99%