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: Biocompatible photoinduced CuAAC using sodium pyruvate
Sodium pyruvate, a natural intermediate produced during cellular metabolism, is commonly used in buffer solutions and media for biochemical applications. Here we show the use of sodium pyruvate (SP) as a reducing agent in a biocompatible aqueous photoinduced azide–alkyne cycloaddition (CuAAC) reaction. This copper( i )-catalyzed 1,3-dipolar cycloaddition is triggered by SP under UV light irradiation, exhibits oxygen tolerance and temporal control, and provides a convenient alternative to current CuAAC systems, particularly for biomolecular conjugations.  more » « less
Award ID(s):
2000391
PAR ID:
10340012
Author(s) / Creator(s):
; ; ; ; ; ; ;
Date Published:
Journal Name:
Chemical Communications
Volume:
57
Issue:
95
ISSN:
1359-7345
Page Range / eLocation ID:
12844 to 12847
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. A photoinduced reversible addition-fragmentation chain-transfer (photo-RAFT) polymerization technique in the presence of sodium pyruvate (SP) and pyruvic acid derivatives was developed. 
    more » « less
  2. Aseries of novel 1,4-disubstituted 1,2,3-triazoles were synthesized from an (R)-carvone terminal alkyne derivative via a Cu (I)-catalyzed azide–alkyne cycloaddition reaction using CuSO4,5H2O as the copper (II) source and sodium ascorbate as a reducing agent which reduces Cu (II) into Cu (I). All the newly synthesized 1,2,3-triazoles 9a–h were fully identified on the basis of their HRMS and NMR spectral data and then evaluated for their cell growth inhibition potential by MTS assay against HT-1080 fibrosarcoma, A-549 lung carcinoma, and two breast adenocarcinoma (MCF-7 and MDA-MB-231) cell lines. Compound 9d showed notable cytotoxic effects against the HT-1080 and MCF-7 cells with IC50 values of 25.77 and 27.89 µM, respectively, while compound 9c displayed significant activity against MCF-7 cells with an IC50 value of 25.03 µM. Density functional calculations at the B3LYP/6-31G* level of theory were used to confirm the high reactivity of the terminal alkyne as a dipolarophile. Quantum calculations were also used to investigate the mechanism of both the uncatalyzed and copper (I)-catalyzed azide–alkyne cycloaddition reaction (CuAAC). The catalyzed reaction gives complete regioselectivity via a stepwise mechanism streamlining experimental observations. The calculated free-energy barriers 4.33 kcal/mol and 29.35 kcal/mol for the 1,4- and 1,5-regioisomers, respectively, explain the marked regioselectivity of the CuAAC reaction. 
    more » « less
  3. Abstract Photoinduced initiators for continuous activator regeneration atom transfer radical polymerization (PICAR ATRP) using sodium pyruvate and blue light (λmax = 456 nm) is reported. Water‐soluble oligo(ethylene oxide) methyl ether methacrylate (OEOMA500) was polymerized under biologically relevant conditions. Polymerizations were conducted with 1000 ppm (with respect to the monomer) concentrations of CuBr2, tris(2‐pyridylmethyl)amine, and 1000 ppm or less FeCl3as a cocatalyst in water. Well‐defined polymers with up to 90% monomer conversion, high molecular weights (Mn > 190,000), and low dispersity (1.14 < Ð < 1.19) were synthesized in less than 60 min. The polymerization rate and dispersity were tuned by varying the concentration of sodium pyruvate (SP), iron, and supporting halide, as well as light intensity. The Cu/Fe dual catalysis provided oxygen tolerance enabling rapid, well‐controlled, aqueous PICAR ATRP of OEOMA500without deoxygenation. 
    more » « less
  4. Abstract Nitrous oxide (N2O) is a climate-active gas with emissions predicted to increase due to agricultural intensification. Microbial reduction of N2O to dinitrogen (N2) is the major consumption process but microbial N2O reduction under acidic conditions is considered negligible, albeit strongly acidic soils harbornosZgenes encoding N2O reductase. Here, we study a co-culture derived from acidic tropical forest soil that reduces N2O at pH 4.5. The co-culture exhibits bimodal growth with aSerratiasp. fermenting pyruvate followed by hydrogenotrophic N2O reduction by aDesulfosporosinussp. Integrated omics and physiological characterization revealed interspecies nutritional interactions, with the pyruvate fermentingSerratiasp. supplying amino acids as essential growth factors to the N2O-reducingDesulfosporosinussp. Thus, we demonstrate growth-linked N2O reduction between pH 4.5 and 6, highlighting microbial N2O reduction potential in acidic soils. 
    more » « less
  5. The investigation aimed to determine whether altering metal microstructure by introducing special grain boundaries through annealing could reduce the corrosion damage observed in the presence of pyruvate. Oxygen-free pure copper coupons were annealed at 325°C, 475°C and 950°C for varying durations to optimize the formation of ∑3 special boundaries. Samples annealed at 475°C for 30 min had the highest yield of such boundaries, thus, were selected for testing. Annealed and as-received, untreated, copper specimens were exposed under stagnant conditions to an aqueous oxic solution of sodium pyruvate for 30 days. Microscopy, spectroscopy, and electrochemical methods were employed to characterize the specimens prior to and following pyruvate exposure. Pyruvate caused localized corrosion of copper seen as micro pitting, irrespective of the specimen treatment. Reduced pitting severity and a decrease in the corrosion rate by 32 % were recorded for annealed coupons when compared to as-received ones. It is proposed that the difference in thickness and morphology of the oxide layer between annealed and as-received coupons, evidenced through electrochemical techniques, is the likely contributor to the improved corrosion resistance of annealed coupons. 
    more » « less