Cross‐Linked Protein Crystals With an Intense Nonconventional Full‐Color Photoluminescence Originating From Through‐Space Intermolecular Interaction

ABSTRACT The emergence of nonconventional luminescent materials (NLMs) has attracted significant attention due to their sustainable synthesis and tunable optical properties. Yet, establishing a clear structure–emission relationship remains a challenge. In this work, we report a previously unknown cl...

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Main Authors: Renbin Zhou, Xiaoli Lu, Xuefeng Zhou, Xuejiao Liu, Shanmin Wang, Tymish Y. Ohulchanskyy, Da‐Chuan Yin, Junle Qu
Format: Article
Language:English
Published: Wiley 2025-07-01
Series:Aggregate
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Online Access:https://doi.org/10.1002/agt2.70070
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author Renbin Zhou
Xiaoli Lu
Xuefeng Zhou
Xuejiao Liu
Shanmin Wang
Tymish Y. Ohulchanskyy
Da‐Chuan Yin
Junle Qu
author_facet Renbin Zhou
Xiaoli Lu
Xuefeng Zhou
Xuejiao Liu
Shanmin Wang
Tymish Y. Ohulchanskyy
Da‐Chuan Yin
Junle Qu
author_sort Renbin Zhou
collection DOAJ
description ABSTRACT The emergence of nonconventional luminescent materials (NLMs) has attracted significant attention due to their sustainable synthesis and tunable optical properties. Yet, establishing a clear structure–emission relationship remains a challenge. In this work, we report a previously unknown class of NLMs: cross‐linked protein crystals that exhibit intense photoluminescence (PL) in the visible range (425–680 nm). We systematically investigated seven natural protein crystals (concanavalin, catalase, lysozyme, hemoglobin, α‐chymotrypsin, pepsin, and β‐lactoglobulin) cross‐linked with glutaraldehyde and demonstrated that cross‐linking induces broadband emission that is absent in natural crystals. Focusing on polymorphic lysozyme crystals (tetragonal, orthorhombic, and monoclinic), we found excitation‐dependent fluorescence with lifetimes in the nanosecond range and quantum yields up to 20% (in the monoclinic phase under 450 nm excitation). Single‐ and two‐photon spectroscopy, as well as pressure‐ and solvent‐modulated PL studies, confirm that the emission is due to intermolecular through‐space interactions (TSI) within the crystal lattice. Compression enhances TSI and redshifts the emission, whereas the solvent (DMSO)‐induced swelling reduces TSI and causes a blue shift, establishing a direct structure–emission correlation. This work establishes protein crystals as programmable NLMs with tunable emission and provides a mechanistic framework for the design of nonconventional luminogens through protein crystal engineering.
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spelling doaj-art-8e160a2cdfa84192a3a241ff031f12592025-08-20T02:40:36ZengWileyAggregate2692-45602025-07-0167n/an/a10.1002/agt2.70070Cross‐Linked Protein Crystals With an Intense Nonconventional Full‐Color Photoluminescence Originating From Through‐Space Intermolecular InteractionRenbin Zhou0Xiaoli Lu1Xuefeng Zhou2Xuejiao Liu3Shanmin Wang4Tymish Y. Ohulchanskyy5Da‐Chuan Yin6Junle Qu7Key Laboratory for Space Bioscience and Biotechnology School of Life Sciences Northwestern Polytechnical University Xi'an Shaanxi ChinaWestlake AI Therapeutics Laboratory Westlake Laboratory of Life Sciences and Biomedicine Hangzhou Zhejiang ChinaDepartment of Physics and Academy for Advanced Interdisciplinary Studies Southern University of Science and Technology Shenzhen Guangdong ChinaKey Laboratory for Space Bioscience and Biotechnology School of Life Sciences Northwestern Polytechnical University Xi'an Shaanxi ChinaDepartment of Physics and Academy for Advanced Interdisciplinary Studies Southern University of Science and Technology Shenzhen Guangdong ChinaCollege of Physics and Optoelectronic Engineering & Key Laboratory of Optoelectronic Devices and Systems of the Ministry of Education and Guangdong Province Shenzhen University Shenzhen Guangdong ChinaKey Laboratory for Space Bioscience and Biotechnology School of Life Sciences Northwestern Polytechnical University Xi'an Shaanxi ChinaCollege of Physics and Optoelectronic Engineering & Key Laboratory of Optoelectronic Devices and Systems of the Ministry of Education and Guangdong Province Shenzhen University Shenzhen Guangdong ChinaABSTRACT The emergence of nonconventional luminescent materials (NLMs) has attracted significant attention due to their sustainable synthesis and tunable optical properties. Yet, establishing a clear structure–emission relationship remains a challenge. In this work, we report a previously unknown class of NLMs: cross‐linked protein crystals that exhibit intense photoluminescence (PL) in the visible range (425–680 nm). We systematically investigated seven natural protein crystals (concanavalin, catalase, lysozyme, hemoglobin, α‐chymotrypsin, pepsin, and β‐lactoglobulin) cross‐linked with glutaraldehyde and demonstrated that cross‐linking induces broadband emission that is absent in natural crystals. Focusing on polymorphic lysozyme crystals (tetragonal, orthorhombic, and monoclinic), we found excitation‐dependent fluorescence with lifetimes in the nanosecond range and quantum yields up to 20% (in the monoclinic phase under 450 nm excitation). Single‐ and two‐photon spectroscopy, as well as pressure‐ and solvent‐modulated PL studies, confirm that the emission is due to intermolecular through‐space interactions (TSI) within the crystal lattice. Compression enhances TSI and redshifts the emission, whereas the solvent (DMSO)‐induced swelling reduces TSI and causes a blue shift, establishing a direct structure–emission correlation. This work establishes protein crystals as programmable NLMs with tunable emission and provides a mechanistic framework for the design of nonconventional luminogens through protein crystal engineering.https://doi.org/10.1002/agt2.70070intermolecular through‐space interactionsnonconventional luminescent materialspolymorphismprotein crystalsstructure–emission relationship
spellingShingle Renbin Zhou
Xiaoli Lu
Xuefeng Zhou
Xuejiao Liu
Shanmin Wang
Tymish Y. Ohulchanskyy
Da‐Chuan Yin
Junle Qu
Cross‐Linked Protein Crystals With an Intense Nonconventional Full‐Color Photoluminescence Originating From Through‐Space Intermolecular Interaction
Aggregate
intermolecular through‐space interactions
nonconventional luminescent materials
polymorphism
protein crystals
structure–emission relationship
title Cross‐Linked Protein Crystals With an Intense Nonconventional Full‐Color Photoluminescence Originating From Through‐Space Intermolecular Interaction
title_full Cross‐Linked Protein Crystals With an Intense Nonconventional Full‐Color Photoluminescence Originating From Through‐Space Intermolecular Interaction
title_fullStr Cross‐Linked Protein Crystals With an Intense Nonconventional Full‐Color Photoluminescence Originating From Through‐Space Intermolecular Interaction
title_full_unstemmed Cross‐Linked Protein Crystals With an Intense Nonconventional Full‐Color Photoluminescence Originating From Through‐Space Intermolecular Interaction
title_short Cross‐Linked Protein Crystals With an Intense Nonconventional Full‐Color Photoluminescence Originating From Through‐Space Intermolecular Interaction
title_sort cross linked protein crystals with an intense nonconventional full color photoluminescence originating from through space intermolecular interaction
topic intermolecular through‐space interactions
nonconventional luminescent materials
polymorphism
protein crystals
structure–emission relationship
url https://doi.org/10.1002/agt2.70070
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