skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Nano-gold corking and enzymatic uncorking of carbon nanotube cups

Abstract

Because of their unique stacked, cup-shaped, hollow compartments, nitrogen-doped carbon nanotube cups (NCNCs) have promising potential as nanoscale containers. Individual NCNCs are isolated from their stacked structure through acid oxidation and subsequent probe-tip sonication. The NCNCs are then effectively corked with gold nanoparticles (GNPs) by sodium citrate reduction with chloroauric acid, forming graphitic nanocapsules with significant surface-enhanced Raman signature. Mechanistically, the growth of the GNP corks starts from the nucleation and welding of gold seeds on the open rims of NCNCs enriched with nitrogen functionalities, as confirmed by density functional theory calculations. A potent oxidizing enzyme of neutrophils, myeloperoxidase (MPO), can effectively open the corked NCNCs through GNP detachment, with subsequent complete enzymatic degradation of the graphitic shells. Lastly, this controlled opening and degradation was further carried out in vitro with human neutrophils. In addition, the GNP-corked NCNCs were demonstrated to function as novel drug delivery carriers, capable of effective (i) delivery of paclitaxel to tumor-associated myeloid-derived suppressor cells (MDSC), (ii) MPO-regulated release, and (iii) blockade of MDSC immunosuppressive potential.

Authors:
 [1];  [1];  [1];  [2];  [1];  [3];  [3];  [1];  [1]
  1. Univ. of Pittsburgh, Pittsburgh, PA (United States)
  2. National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States)
  3. Univ. of Pittsburgh Medical Center, Pittsburgh, PA (United States)
Publication Date:
Research Org.:
National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1186638
Report Number(s):
A-UNIV-PUB-122
Journal ID: ISSN 0002-7863
Grant/Contract Number:  
0954345; R01CA154369; R01ES019304; NIOSH OH008282; HL114453; U19 AI068021
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 137; Journal Issue: 2; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 60 APPLIED LIFE SCIENCES; 59 BASIC BIOLOGICAL SCIENCES; 77 NANOSCIENCE AND NANOTECHNOLOGY

Citation Formats

Zhao, Yong, Burkert, Seth C., Tang, Yifan, Sorescu, Dan C., Kapralov, Alexandr A., Shurin, Galina V., Shurin, Michael R., Kagan, Valerian E., and Star, Alexander. Nano-gold corking and enzymatic uncorking of carbon nanotube cups. United States: N. p., 2014. Web. doi:10.1021/ja511843w.
Zhao, Yong, Burkert, Seth C., Tang, Yifan, Sorescu, Dan C., Kapralov, Alexandr A., Shurin, Galina V., Shurin, Michael R., Kagan, Valerian E., & Star, Alexander. Nano-gold corking and enzymatic uncorking of carbon nanotube cups. United States. https://doi.org/10.1021/ja511843w
Zhao, Yong, Burkert, Seth C., Tang, Yifan, Sorescu, Dan C., Kapralov, Alexandr A., Shurin, Galina V., Shurin, Michael R., Kagan, Valerian E., and Star, Alexander. 2014. "Nano-gold corking and enzymatic uncorking of carbon nanotube cups". United States. https://doi.org/10.1021/ja511843w. https://www.osti.gov/servlets/purl/1186638.
@article{osti_1186638,
title = {Nano-gold corking and enzymatic uncorking of carbon nanotube cups},
author = {Zhao, Yong and Burkert, Seth C. and Tang, Yifan and Sorescu, Dan C. and Kapralov, Alexandr A. and Shurin, Galina V. and Shurin, Michael R. and Kagan, Valerian E. and Star, Alexander},
abstractNote = {Because of their unique stacked, cup-shaped, hollow compartments, nitrogen-doped carbon nanotube cups (NCNCs) have promising potential as nanoscale containers. Individual NCNCs are isolated from their stacked structure through acid oxidation and subsequent probe-tip sonication. The NCNCs are then effectively corked with gold nanoparticles (GNPs) by sodium citrate reduction with chloroauric acid, forming graphitic nanocapsules with significant surface-enhanced Raman signature. Mechanistically, the growth of the GNP corks starts from the nucleation and welding of gold seeds on the open rims of NCNCs enriched with nitrogen functionalities, as confirmed by density functional theory calculations. A potent oxidizing enzyme of neutrophils, myeloperoxidase (MPO), can effectively open the corked NCNCs through GNP detachment, with subsequent complete enzymatic degradation of the graphitic shells. Lastly, this controlled opening and degradation was further carried out in vitro with human neutrophils. In addition, the GNP-corked NCNCs were demonstrated to function as novel drug delivery carriers, capable of effective (i) delivery of paclitaxel to tumor-associated myeloid-derived suppressor cells (MDSC), (ii) MPO-regulated release, and (iii) blockade of MDSC immunosuppressive potential.},
doi = {10.1021/ja511843w},
url = {https://www.osti.gov/biblio/1186638}, journal = {Journal of the American Chemical Society},
issn = {0002-7863},
number = 2,
volume = 137,
place = {United States},
year = {Sun Dec 21 00:00:00 EST 2014},
month = {Sun Dec 21 00:00:00 EST 2014}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 32 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Drug Delivery Systems: Entering the Mainstream
journal, March 2004


Photo-thermal tumor ablation in mice using near infrared-absorbing nanoparticles
journal, June 2004


Macromolecular therapeutics in cancer treatment: The EPR effect and beyond
journal, December 2012


Nano-oncology: drug delivery, imaging, and sensing
journal, January 2006


Targeted nanoparticle-based drug delivery and diagnosis
journal, January 2007


Recent Approaches to Intracellular Delivery of Drugs and dna and Organelle Targeting
journal, August 2006


Functionalized Single-Walled Carbon Nanotubes as Rationally Designed Vehicles for Tumor-Targeted Drug Delivery
journal, December 2008


Targeted Delivery of Amphotericin B to Cells by Using Functionalized Carbon Nanotubes
journal, October 2005


Functionalized Carbon Nanotubes in Drug Design and Discovery
journal, January 2008


Supramolecular Chemistry on Water-Soluble Carbon Nanotubes for Drug Loading and Delivery
journal, August 2007


Incorporation of Hexamethylmelamine inside Capped Carbon Nanotubes
journal, June 2008


Filling Carbon Nanotubes with Particles
journal, May 2005


Cisplatin@US-tube carbon nanocapsules for enhanced chemotherapeutic delivery
journal, February 2012


Highly Stabilized β-Carotene in Carbon Nanotubes
journal, February 2006


Particle Size Analysis in Pharmaceutics: Principles, Methods and Applications
journal, December 2006


Opsonization, biodistribution, and pharmacokinetics of polymeric nanoparticles
journal, January 2006


Synthesis, Characterization, and Manipulation of Nitrogen-Doped Carbon Nanotube Cups
journal, August 2008


Corking Carbon Nanotube Cups with Gold Nanoparticles
journal, July 2012


Nitrogen-Doped Carbon Nanotube Arrays with High Electrocatalytic Activity for Oxygen Reduction
journal, February 2009


Electrocatalytic Activity of Nitrogen-Doped Carbon Nanotube Cups
journal, September 2009


The Effect of Metal Catalyst on the Electrocatalytic Activity of Nitrogen-Doped Carbon Nanotubes
journal, November 2013


Size-controlled short nanobells: Growth and formation mechanism
journal, December 2000


Effect of ball milling on morphology of cup-stacked carbon nanotubes
journal, April 2002


A simple route to short cup-stacked carbon nanotubes by sonication
journal, October 2010


Efficient separation of nitrogen-doped carbon nanotube cups
journal, December 2014


Polysaccharide-decorated nanoparticles
journal, September 2004


Functionalization of Carbon Nanotubes via Cleavable Disulfide Bonds for Efficient Intracellular Delivery of siRNA and Potent Gene Silencing
journal, August 2005


Noncovalent Functionalization of Carbon Nanotubes by Fluorescein−Polyethylene Glycol:  Supramolecular Conjugates with pH-Dependent Absorbance and Fluorescence
journal, March 2007


Near-IR Remote Release from Assemblies of Liposomes and Nanoparticles
journal, February 2009


Carbon nanotubes introduced into the abdominal cavity of mice show asbestos-like pathogenicity in a pilot study
journal, May 2008


Peroxidase-mediated biodegradation of carbon nanotubes in vitro and in vivo
journal, December 2013


Biocompatibility and Toxicological Studies of Carbon Nanotubes Doped with Nitrogen
journal, August 2006


Biodegradation of Single-Walled Carbon Nanotubes through Enzymatic Catalysis
journal, October 2008


Mechanistic Investigations of Horseradish Peroxidase-Catalyzed Degradation of Single-Walled Carbon Nanotubes
journal, December 2009


Carbon nanotubes degraded by neutrophil myeloperoxidase induce less pulmonary inflammation
journal, April 2010


Enzymatic Degradation of Multiwalled Carbon Nanotubes
journal, September 2011


Inside the Neutrophil Phagosome: Oxidants, Myeloperoxidase, and Bacterial Killing
journal, November 1998


Wound Healing Dressings and Drug Delivery Systems: A Review
journal, August 2008


Myeloid-derived suppressor cells: A novel therapeutic target
journal, February 2009


Nitrogen-induced carbon nanobells and their properties
journal, November 2006


Welding of Gold Nanoparticles on Graphitic Templates for Chemical Sensing
journal, February 2012


Understanding Interfaces in Metal–Graphitic Hybrid Nanostructures
journal, December 2012


Surface Chemistry of Gold Nanoparticles Produced by Laser Ablation in Aqueous Media
journal, October 2004


XPS of nitrogen-containing functional groups on activated carbon
journal, January 1995


Enzyme-Catalyzed Oxidation Facilitates the Return of Fluorescence for Single-Walled Carbon Nanotubes
journal, May 2013


Au nanoparticles on graphitic petal arrays for surface-enhanced Raman spectroscopy
journal, September 2010


Surface-Enhanced Raman Scattering of Rhodamine 123 in Silver Hydrosols and in Langmuir–Blodgett Films on Silver Islands
journal, March 2001


Myeloid-derived suppressor cells as regulators of the immune system
journal, March 2009


Regulatory dendritic cells in the tumor immunoenvironment
journal, November 2011


Macrophages, innate immunity and cancer: balance, tolerance, and diversity
journal, April 2010


Tumor- and organ-dependent infiltration by myeloid-derived suppressor cells
journal, July 2011


Origin and pharmacological modulation of tumor-associated regulatory dendritic cells: Dendritic cell polarization in cancer
journal, January 2014


Chemotherapeutic Agents in Noncytotoxic Concentrations Increase Antigen Presentation by Dendritic Cells via an IL-12-Dependent Mechanism
journal, June 2009


Wound Healing Dressings and Drug Delivery Systems: A Review
journal, August 2008


Nano-oncology: drug delivery, imaging, and sensing
journal, January 2006


Regulatory dendritic cells in the tumor immunoenvironment
journal, November 2011


Myeloid-derived suppressor cells: A novel therapeutic target
journal, February 2009


Cisplatin@US-tube carbon nanocapsules for enhanced chemotherapeutic delivery
journal, February 2012


Macrophages, innate immunity and cancer: balance, tolerance, and diversity
journal, April 2010


Polysaccharide-decorated nanoparticles
journal, September 2004


Tumor- and organ-dependent infiltration by myeloid-derived suppressor cells
journal, July 2011


Noncovalent Functionalization of Carbon Nanotubes by Fluorescein−Polyethylene Glycol:  Supramolecular Conjugates with pH-Dependent Absorbance and Fluorescence
journal, March 2007


Enzyme-Catalyzed Oxidation Facilitates the Return of Fluorescence for Single-Walled Carbon Nanotubes
journal, May 2013


Functionalized Single-Walled Carbon Nanotubes as Rationally Designed Vehicles for Tumor-Targeted Drug Delivery
journal, December 2008


Electrocatalytic Activity of Nitrogen-Doped Carbon Nanotube Cups
journal, September 2009


Mechanistic Investigations of Horseradish Peroxidase-Catalyzed Degradation of Single-Walled Carbon Nanotubes
journal, December 2009


Enzymatic Degradation of Multiwalled Carbon Nanotubes
journal, September 2011


Biodegradation of Single-Walled Carbon Nanotubes through Enzymatic Catalysis
journal, October 2008


Synthesis, Characterization, and Manipulation of Nitrogen-Doped Carbon Nanotube Cups
journal, August 2008


Carbon nanotubes introduced into the abdominal cavity of mice show asbestos-like pathogenicity in a pilot study
journal, May 2008


Carbon nanotubes degraded by neutrophil myeloperoxidase induce less pulmonary inflammation
journal, April 2010


Myeloid-derived suppressor cells as regulators of the immune system
journal, March 2009


Oxidative biodegradation of single- and multi-walled carbon nanotubes
journal, January 2011


Low-dose Chemotherapeutic Agents Regulate Small Rho GTPase Activity in Dendritic Cells
journal, January 2008


Nitrogen-Doped Carbon Nanotube Arrays with High Electrocatalytic Activity for Oxygen Reduction
journal, February 2009


Recent Approaches to Intracellular Delivery of Drugs and dna and Organelle Targeting
journal, August 2006


Tumor-Associated Neutrophils: New Targets for Cancer Therapy: Figure 1.
journal, March 2011


Direct Raman imaging techniques for study of the subcellular distribution of a drug
journal, January 2002


Paclitaxel promotes differentiation of myeloid-derived suppressor cells into dendritic cells in vitro in a TLR4-independent manner
journal, January 2012


Works referencing / citing this record:

Characterizing the Cellular Response to Nitrogen-Doped Carbon Nanocups
journal, June 2019


Single wall carbon nanotube (SWCNT)–gold nanorod (AuNR) conjugates via thermally-mild reaction conditions
journal, January 2017


Targeting myeloid regulators by paclitaxel-loaded enzymatically degradable nanocups
journal, January 2018


Dispersibility-Dependent Biodegradation of Graphene Oxide by Myeloperoxidase
journal, May 2015


In vivo degeneration and the fate of inorganic nanoparticles
journal, January 2016


In vitro controlled release of cisplatin from gold-carbon nanobottles via cleavable linkages
journal, December 2015


Characterizing the Cellular Response to Nitrogen-Doped Carbon Nanocups
journal, June 2019