skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.


Title: Textile Functionalization by Porous Protein Crystal Conjugation and Guest Molecule Loading
Protein crystals are versatile nanostructured materials that can be readily engineered for applications in nanomedicine and nanobiotechnology. Despite their versatility, the small size of typical individual protein crystals (less than one cubic mm) presents challenges for macroscale applications. One way to overcome this limitation is by immobilizing protein crystals onto larger substrates. Cotton is composed primarily of cellulose, the most common natural fiber in the world, and is routinely used in numerous material applications including textiles, explosives, paper, and bookbinding. Here, two types of protein crystals were conjugated to the cellulosic substrate of cotton fabric using a 1,1′-carbonyldiimidazole/aldehyde mediated coupling protocol. The efficacy of this attachment was assessed via accelerated laundering and quantified by fluorescence imaging. The ability to load guest molecules of varying sizes into the scaffold structure of the conjugated protein crystals was also assessed. This work demonstrates the potential to create multifunctional textiles by incorporating diverse protein crystal scaffolds that can be infused with a multiplicity of useful guest molecules. Cargo molecule loading and release kinetics will depend on the size of the guest molecules as well as the protein crystal solvent channel geometry. Here, we demonstrate the loading of a small molecule dye into the small pores of hen egg white lysozyme crystals and a model enzyme into the 13-nm pores delimited by “CJ” crystals composed of an isoprenoid-binding protein from Campylerbacter jejuni.  more » « less
Award ID(s):
1506219
PAR ID:
10530141
Author(s) / Creator(s):
; ; ; ; ;
Publisher / Repository:
MDPI
Date Published:
Journal Name:
Crystals
Volume:
13
Issue:
2
ISSN:
2073-4352
Page Range / eLocation ID:
352
Subject(s) / Keyword(s):
protein crystals crosslinking host–guest crystals bioconjugation textile engineering
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. null (Ed.)
    Crosslinked porous protein crystals are a new biomaterial that can be engineered to encapsulate, stabilize, and organize guest molecules, nanoparticles, and biological moieties. In this study, for the first time, the combined interactions of DNA strands with porous protein crystals are quantitatively measured by high-resolution atomic force microscopy (AFM) and chemical force microscopy. The surface structure of protein crystals with unusually large pores was observed in liquid via high-resolution AFM. Force–distance ( F – D ) curves were also obtained using AFM tips modified to present or capture DNA. The modification of AFM tips allowed the tips to covalently bind DNA that was pre-loaded in the protein crystal nanopores. The modified tips enabled the interactions of DNA molecules with protein crystals to be quantitatively studied while revealing the morphology of the buffer-immersed protein crystal surface in detail, thereby preserving the structure and properties of protein crystals that could be disrupted or destroyed by drying. The hexagonal space group was manifest at the crystal surface, as were the strong interactions between DNA and the porous protein crystals in question. In sum, this study furthered our understanding of how a new protein-based biomaterial can be used to bind guest DNA assemblies. 
    more » « less
  2. Abstract Recombinant proteins have emerged as promising building blocks for vesicle self‐assembly because of their versatility through genetic manipulation and biocompatibility. Vesicles composed of thermally responsive elastin‐like polypeptide (ELP) fusion proteins encapsulate cargo during assembly. However, vesicle stability in physiological environments remains a significant challenge for biofunctional applications. Here, incorporation of an unnatural amino acid, para‐azido phenylalanine, into the ELP domain is reported to enable photocrosslinking of protein vesicles and tuning of vesicle size and swelling. The size of the vesicles can be tuned by changing ELP hydrophobicity and ionic strength. Protein vesicles are assessed for their ability to encapsulate doxorubicin and dually deliver doxorubicin and fluorescent protein in vitro as a proof of concept. The resulting photocrosslinkable vesicles made from full‐sized, functional proteins show high potential in drug delivery applications, especially for small molecule/protein combination therapies or targeted therapies. 
    more » « less
  3. The porosity, order, biocompatibility, and chirality of protein crystals has motivated interest from diverse research domains including materials science, biotechnology, and medicine. Porous protein crystals have the unusual potential to organize guest molecules within highly ordered scaffolds, enabling applications ranging from biotemplating and catalysis to biosensing and drug delivery. Significant research has therefore been directed toward characterizing protein crystal materials in hopes of optimizing crystallization, scaffold stability, and application efficacy. In this overview article, we describe recent progress in the field of protein crystal materials with special attention given to applications in nanomedicine and nanobiotechnology. This article is categorized under:Biology‐Inspired Nanomaterials > Protein and Virus‐Based StructuresTherapeutic Approaches and Drug Discovery > Emerging TechnologiesToxicology and Regulatory Issues in Nanomedicine > Toxicology of Nanomaterials 
    more » « less
  4. Abstract Covalent organic frameworks linked by carbon‐carbon double bonds (C=C COFs) are an emerging class of crystalline, porous, and conjugated polymeric materials with potential applications in organic electronics, photocatalysis, and energy storage. Despite the rapidly growing interest in sp2carbon‐conjugated COFs, only a small number of closely related condensation reactions have been successfully employed for their synthesis to date. Herein, we report the first example of a C=C COF, CORN‐COF‐1 (CORN=Cornell University), prepared byN‐heterocyclic carbene (NHC) dimerization. In‐depth characterization reveals that CORN‐COF‐1 possesses a two‐dimensional layered structure and hexagonal guest‐accessible pores decorated with a high density of strongly reducing tetraazafulvalene linkages. Exposure of CORN‐COF‐1 to tetracyanoethylene (TCNE,E1/2=0.13 V and −0.87 V vs. SCE) oxidizes the COF and encapsulates the radical anion TCNE⋅and the dianion TCNE2−as guest molecules, as confirmed by spectroscopic and magnetic analysis. Notably, the reactive TCNE⋅radical anion, which generally dimerizes in the solid state, is uniquely stabilized within the pores of CORN‐COF‐1. Overall, our findings broaden the toolbox of reactions available for the synthesis of redox‐active C=C COFs, paving the way for the design of novel materials. 
    more » « less
  5. Curved aromatic hydrocarbons often display better solubility and more desirable electronic properties in comparison to their flat counterparts. Macrocyclic curved aromatics possess these traits as well as shape-persistent pores ideal for host-guest interactions. A quintessential macrocyclic curved aromatic molecule is the cycloparaphenylene, or [n]CPP. Our group has developed a new class of these carbon nanohoops, called [n+1]CPPs, that incorporate a strained alkyne (“+1”) into the carbon backbone. We have previously shown the [n+1]CPPs to be a promising new class of strain-promoted azide-alkyne cycloaddition click reagents. Herein, we show that the [n+1]CPPs can also be converted into pinwheel-like multi-pore large molecules via a straightforward and high yielding metal-mediated alkyne cyclotrimerization reaction. We provide insight into suitable metals for this transformation, the photophysics of these trimeric molecules, as well as their strain profiles and crystal packing. 
    more » « less