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.

Explore Research Products in the PAR
It may take a few hours for recently added research products to appear in PAR search results.


  • NSF Public Access
  • Search Results
  • Synthesis of Carbohydrate-Grafted Glycopolymers Using a Catalyst-Free, Perfluoroarylazide-Mediated Fast Staudinger Reaction
Title: Synthesis of Carbohydrate-Grafted Glycopolymers Using a Catalyst-Free, Perfluoroarylazide-Mediated Fast Staudinger Reaction
Glycopolymers have gained increasing importance in investigating glycan-lectin interactions, as drug delivery vehicles and in modulating interactions with proteins. The synthesis of these glycopolymers is still a challenging and rigorous exercise. In this regard, the highly efficient click reaction, copper (I)-catalyzed alkyne-azide cycloaddition, has been widely applied not only for its efficiency but also for its tolerance of the appended carbohydrate groups. However, a significant drawback of this method is the use of the heavy metal catalyst which is difficult to remove completely, and ultimately toxic to biological systems. In this work, we present the synthesis of carbohydrate-grafted glycopolymers utilizing a mild and catalyst-free perfluorophenyl azide (PFPA)-mediated Staudinger reaction. Using this strategy, mannose (Man) and maltoheptaose (MH) were grafted onto the biodegradable poly(lactic acid) (PLA) by stirring a PFAA-functionalized PLA with a phosphine-derivatized Man or MH in DMSO at room temperature within an hour. The glycopolymers were characterized by 1H-NMR, 19F-NMR, 31P-NMR and FTIR.  more » « less
Award ID(s):
1808671
PAR ID:
10093339
Author(s) / Creator(s):
; ;
Date Published:
Journal Name:
Molecules
Volume:
24
Issue:
1
ISSN:
1420-3049
Page Range / eLocation ID:
157
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. ; ; (, Journal of Polymer Science)
    Abstract Poly(lactic acid) (PLA) is a commercially available bio‐based polymer that is a potential alternative to many commodity petrochemical‐based polymers. However, PLA's thermomechanical properties limit its use in many applications. Incorporating polymer‐grafted cellulose nanocrystals (CNCs) is one potential route to improving these mechanical properties. One key challenge in using these polymer‐grafted nanoparticles is to understand which variables associated with polymer grafting are most important for improving composite properties. In this work, poly(ethylene glycol)‐grafted CNCs are used to study the effects of polymer grafting density and molecular weight on the properties of PLA composites. All CNC nanofillers are found to reinforce PLA above the glass transition temperature, but non‐grafted CNCs and CNCs grafted with short PEG chains (<2 kg mol−1) are found to cause significant embrittlement, generally resulting in less than 3% elongation‐at‐break. By grafting higher molecular weight PEG (10 kg mol−1) onto the CNCs at a grafting density where the polymer chains are predicted to be in the semi‐dilute polymer brush conformation (~0.1 chains nm−2), embrittlement can be avoided. 
    more » « less
  2. ; ; ; (, Biotechnology and Bioengineering)
    Abstract Chemoenzymatic approaches using carbohydrate‐active enzymes (CAZymes) offer a promising avenue for the synthesis of glycans like oligosaccharides. Here, we report a novel chemoenzymatic route for cellodextrins synthesis employed by chimeric CAZymes, akin to native glycosyltransferases, involving the unprecedented participation of a “non‐catalytic” lectin‐like domain or carbohydrate‐binding modules (CBMs) in the catalytic step for glycosidic bond synthesis using β‐cellobiosyl donor sugars as activated substrates. CBMs are often thought to play a passive substrate targeting role in enzymatic glycosylation reactions mostly via overcoming substrate diffusion limitations for tethered catalytic domains (CDs) but are not known to participate directly in any nucleophilic substitution mechanisms that impact the actual glycosyl transfer step. This study provides evidence for the direct participation of CBMs in the catalytic reaction step for β‐glucan glycosidic bonds synthesis enhancing activity for CBM‐based CAZyme chimeras by >140‐fold over CDs alone. Dynamic intradomain interactions that facilitate this poorly understood reaction mechanism were further revealed by small‐angle X‐ray scattering structural analysis along with detailed mutagenesis studies to shed light on our current limited understanding of similar transglycosylation‐type reaction mechanisms. In summary, our study provides a novel strategy for engineering similar CBM‐based CAZyme chimeras for the synthesis of bespoke oligosaccharides using simple activated sugar monomers. 
    more » « less
  3. ; ; ; ; ; (, Journal of Applied Physiology)
    To determine whether acute exposure to moderate hypoxia alters central and peripheral fatigue and to test whether carbohydrate ingestion impacts fatigue characteristics, 12 trained runners completed three running trials lasting 1 h each at 65% of normoxic maximum oxygen uptake. The first trial was performed in normoxia [inspired O 2 fraction ([Formula: see text]) = 0.21], and the last two trials were completed in hypoxia ([Formula: see text] = 0.15). Participants ingested a placebo drink in normoxia (NORM-PLA), a placebo drink in hypoxia (HYP-PLA), or a carbohydrate solution in hypoxia (HYP-CHO). HYP conditions were randomized. Peripheral [change in potentiated quadriceps twitch force (ΔQ tw,pot )] and central [change in voluntary activation (ΔVA)] fatigue were assessed via preexercise-to-postexercise changes in magnetically evoked quadriceps twitch. In HYP, blood was drawn to determine the ratio of free-tryptophan (f-TRP) to branched-chain amino acids (BCAA). After exercise, peripheral fatigue was reduced to a similar degree in normoxia and hypoxia (ΔQ tw,pot  = −4.5 ± 1.3% and −4.0 ± 1.5% in NORM-PLA and HYP-PLA, respectively; P = 0.61). Central fatigue was present after normoxic and hypoxic exercise but to a greater degree in HYP-PLA compared with NORM-PLA (ΔVA: −4.7 ± 0.9% vs. −1.9 ± 0.7%; P < 0.01). Carbohydrate ingestion did not influence central fatigue (ΔVA in HYP-CHO: −5.7 ± 1.2%; P = 0.51 vs. HYP-PLA). After exercise, no differences were observed in the ratio of f-TRP to BCAA between HYP-PLA and HYP-CHO ( P = 0.67). Central fatigue increased during prolonged running exercise in moderate hypoxia although the ratio of f-TRP to BCAA remained unchanged. Ingesting carbohydrates while running in hypoxia did not influence fatigue development. NEW & NOTEWORTHY Hypoxic exposure influences the origin of exercise-induced fatigue and the rate of fatigue development depending on the severity of hypoxia. Our data suggest that moderate hypoxia increases central, but not peripheral, fatigue in trained runners exercising at 65% of normoxic maximum oxygen uptake. The increase in central fatigue was unaffected by carbohydrate intake and occurred although the ratio of free tryptophan to branched-chain amino acids remained unchanged. 
    more » « less
  4. ; ; ; (, ChemSusChem)
    Abstract A simple and environmentally benign technology for synthesizing ultrasmall CuInanoparticles (NPs) on the surface of the food additive hydroxypropyl methylcellulose (HPMC) and their application in completely organic solvent‐free tandem alkyne‐azide cycloaddition reactions were reported. The NP catalyst was thoroughly characterized by high‐angle annular dark‐field scanning transmission electron microscopy, high‐resolution transmission electron microscopy, energy‐dispersive X‐ray spectroscopy, and X‐ray photoelectron spectroscopy analysis for its morphology, particle size distribution, chemical composition, and oxidation state analyses. The NP catalyst was highly efficient, affording products in 10–45 min. All products were obtained in high purity by simple filtration, obviating organic solvents from the reaction set‐up to product isolation. The methodology is general and scalable as validated by a broad substrate scope. 
    more » « less
  5. ; (, ChemPlusChem)
    Abstract Electrospray deposition of copper salt‐containing microdroplets onto the liquid surface of an electrically grounded reaction mixture leads to the formation of Cu nanoclusters, which then catalyze the azide‐alkyne cycloaddition (AAC) reaction to form triazoles. This method of in situ nanocatalyst preparation provided 17 times higher catalytic activity compared to that in the conventional catalytic reaction. The gentle landing of the Cu‐containing droplets onto the liquid surface forms a thin film of catalyst which promotes the heterogeneous AAC reaction while showing diffusion‐controlled kinetics. UV‐vis spectral characterization confirms that the catalyst is comprised of Cu nanoclusters. This unique catalytic strategy was validated using several substrates and the corresponding products were confirmed by tandem mass spectrometry (MS/MS) analysis. 
    more » « less
  • Citation Formats
  • MLA
  • APA
  • Chicago
  • BibTeX
  • Save / Share this Record
  • Send to Email