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Antifreeze glycoprotein (AFGP) is an O-glycoprotein that displays antifreeze activity through depression of the freezing point of water. GalNAc is a core sugar structure of AFGP, and contributes to induce antifreeze activity of this glycoprotein. However, the general functional role that this sugar plays at the molecular level is still unknown. To elucidate this, it is essential to determine the relationship between structure and activity of O-GalNAcylated AFGP using homogeneous glycoproteins. Thus, the total synthesis of homogeneous O-GalNAcylated AFGP was conducted by using a unique peptide derivative: peptidyl-N-pivaloylguanidine. It was found that peptidyl-N-pivaloylguanidine is an "unreactive" peptide in peptide coupling reactions but is interconvertible with a "reactive" peptide-α-thioester by means of a simple treatment under buffer condition at pH=7 to 8. The unique switchable reactivity of peptidyl-N-pivaloylguanidine enabled an efficient sequential peptide coupling strategy. By using this strategy, various lengths of homogeneous O-GalNAcylated AFGP were synthesized, including one that was 120 amino acids in length, with 40 O-GalNAcylation sites. The structural analysis by circular dichroism spectroscopy and evaluation of the antifreeze activity of the synthetic AFGP(GalNAc)s revealed that the simple O-glycosylation with GalNAc is essential for both structural and functional basis of AFGP to exhibit antifreeze activity.
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http://dx.doi.org/10.1002/chem.201702243 | DOI Listing |
ACS Appl Mater Interfaces
September 2025
Department of Materials Science and Engineering, Gwangju Institute of Science and Technology (GIST), Gwangju 61005, Republic of Korea.
Cyclic peptides (CPs) are versatile building blocks whose conformational constraints foster ordered supramolecular architectures with potential in biomedicine, nanoelectronics, and catalysis. Herein, we report the development of biomimetic antifreeze materials by conjugating CPs bearing ice-binding residues to 4-arm polyethylene glycol (PEG) via click chemistry. The concentration-dependent self-assembly of these CP-PEG conjugates induces programmable morphological transitions, forming nanotube networks above the critical aggregation concentration (CAC) and two-dimensional nanosheet networks near the CAC.
View Article and Find Full Text PDFInt J Biol Macromol
September 2025
College of Pharmacy, Guangxi University of Chinese Medicine, Nanning 530200, China. Electronic address:
Conductive hydrogels have emerged as promising materials for flexible wearable electronics; however, their facile fabrication remains challenging. This study presents an antifreeze, antibacterial, and conductive hydrogel constructed from biomacromolecules sodium carboxymethylcellulose (CMCNa) and polyvinyl alcohol (PVA). The hydrogel was synthesized via a simple one-pot method in an ethylene glycol/water (EG/H₂O) binary solvent system, incorporating lithium chloride (LiCl) and clove essential oil (CEO), followed by a single freeze-thaw cycle.
View Article and Find Full Text PDFJ Phys Chem B
September 2025
Department of Chemistry and Biochemistry, University of California San Diego, La Jolla, California 92093, United States.
Cold-adapted organisms frequently express antifreeze proteins (AFPs) that facilitate their survival at low temperatures, with some especially potent insect AFPs exhibiting β-solenoid structures with ice-binding threonine ladders. β-solenoids exist in nature in numerous forms and emerging protein design technologies may afford opportunities to diversify them further, suggesting the possibility of developing a variety of new AFPs by installing a threonine ladder on non-AFP natural or designed β-solenoids. However, early attempts at such engineering, combined with differences observed between AFPs and structurally similar ice-nucleating proteins, have raised a critical question: Will a threonine ladder show essentially the same behavior regardless of the β-solenoid scaffold that hosts it, or does the specific solenoid scaffold significantly affect a threonine ladder's structural characteristics (and thus potentially alter its suitability for ice binding)? We set out to address this question by creating distinct variants of a simplified model β-solenoid for analysis structure prediction and molecular dynamics simulations.
View Article and Find Full Text PDFJ Food Sci
September 2025
College of Food Science and Technology, Zhejiang University of Technology, Hangzhou, China.
In this work, a natural zwitterionic, betaine with varied dosages (4%, 6%, 8%, 10%, and 12%, w/v) was used to improve the freeze-thaw stability of frozen surimi gels. Specifically, Group 8B-S (8% betaine, w/v) increased gel strength and storage modulus of frozen surimi gels by 25.03% and 26.
View Article and Find Full Text PDFFront Plant Sci
August 2025
State Key Laboratory of Aridland Crop Science, College of Agronomy, Gansu Agricultural University, Lanzhou, China.
Introduction: The cold tolerance of winter rapeseed cultivars is critically important for winter survival and yield formation in northern area. BrAFP1, an antifreeze protein in , is hypothesized to stabilize membranes and inhibit ice crystal formation.
Methods: we cloned the promoter from the cold-tolerant cultivar Longyou 7 (L7) and constructed the expression vector to investigate the impact of membrane state changes on BrAFP1 expression and the cold tolerance in winter rapeseed.