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

This content will become publicly available on May 20, 2020

Title: Synthesis and characterization of polylactide‐PAMAM “Janus‐type” linear‐dendritic hybrids

Abstract

In this report, we introduce a facile and comprehensive synthetic methodology for the preparation of polyester-polyamidoamine (PAMAM) (i.e., polyester: polylactide [PLA] (hydrophobic) and polyamidoamine, PAMAM [hydrophilic]) polymers. A library of PLA-PAMAM linear dendritic block copolymers (LDBCs) in which both l and d, l polylactide were employed in mass ratios of 30:70, 50:50, 70:30, and 90:10 (PLA:PAMAM) were synthesized and analyzed. When placed in aqueous media, the immiscibility of the hydrophilic and hydrophobic segments leads to nanophase-segregation exhibited as the formation of aggregates (e.g., vesicles, worms, and/or micelles). By employing both stereochemical configurations of PLA, the differentiation in mass ratios of PLA-PAMAM aided in elucidating the structure–property relationships of the LDBC system and provided a means toward the control of nanoparticle morphology. Transmission electron microscopy and dynamic light scattering afford the size and shape of the nanoparticles with diameters ranging from 10.6 for low mass ratios to 122.4 nm for high mass ratios of PLA-PAMAM and positive zeta-potential values between +24 mV and +48.2 mV. Moreover, small-angle X-ray scattering (SAXS) studies were employed to obtain more detailed information on the morphological assemblies constructed via direct dissolution. Such insights provide a pathway toward nanomaterials with unique morphologies and tunable properties deemed relevantmore » in the development of next generation biomaterials.« less

Authors:
 [1];  [1];  [2];  [1];  [1];  [1];  [1];  [2];  [3];  [1];  [1];  [4];  [3];  [2]; ORCiD logo [1]
  1. Univ. of Mississippi, Oxford, MS (United States)
  2. Louisiana State Univ., Baton Rouge, LA (United States)
  3. Tulane Univ., New Orleans, LA (United States)
  4. Argonne National Lab. (ANL), Lemont, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); Experimental Program to Stimulate Competitive Research (EPSCoR); Northwestern Univ.; Materials Research Science and Engineering Center (NU-MRSEC); National Science Foundation (NSF)
OSTI Identifier:
1559534
Alternate Identifier(s):
OSTI ID: 1514742
Grant/Contract Number:  
AC02-06CH11357; SC0012432
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Polymer Science. Part A, Polymer Chemistry
Additional Journal Information:
Journal Volume: 57; Journal Issue: 13; Journal ID: ISSN 0887-624X
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; amphiphiles; block copolymers; drug delivery systems; nanoparticles; self‐assembly

Citation Formats

Chandrasiri, Indika, Abebe, Daniel G., Gupta, Sudipta, Williams, Jon Steven Dal, Rieger, William D., Simms, Briana L., Yaddehige, Mahesh Loku, Noh, YeRim, Payne, Molly E., Fortenberry, Alexander W., Smith, Adam E., Ilavsky, Jan, Grayson, Scott M., Schneider, Gerald J., and Watkins, Davita L. Synthesis and characterization of polylactide‐PAMAM “Janus‐type” linear‐dendritic hybrids. United States: N. p., 2019. Web. doi:10.1002/pola.29409.
Chandrasiri, Indika, Abebe, Daniel G., Gupta, Sudipta, Williams, Jon Steven Dal, Rieger, William D., Simms, Briana L., Yaddehige, Mahesh Loku, Noh, YeRim, Payne, Molly E., Fortenberry, Alexander W., Smith, Adam E., Ilavsky, Jan, Grayson, Scott M., Schneider, Gerald J., & Watkins, Davita L. Synthesis and characterization of polylactide‐PAMAM “Janus‐type” linear‐dendritic hybrids. United States. doi:10.1002/pola.29409.
Chandrasiri, Indika, Abebe, Daniel G., Gupta, Sudipta, Williams, Jon Steven Dal, Rieger, William D., Simms, Briana L., Yaddehige, Mahesh Loku, Noh, YeRim, Payne, Molly E., Fortenberry, Alexander W., Smith, Adam E., Ilavsky, Jan, Grayson, Scott M., Schneider, Gerald J., and Watkins, Davita L. Mon . "Synthesis and characterization of polylactide‐PAMAM “Janus‐type” linear‐dendritic hybrids". United States. doi:10.1002/pola.29409.
@article{osti_1559534,
title = {Synthesis and characterization of polylactide‐PAMAM “Janus‐type” linear‐dendritic hybrids},
author = {Chandrasiri, Indika and Abebe, Daniel G. and Gupta, Sudipta and Williams, Jon Steven Dal and Rieger, William D. and Simms, Briana L. and Yaddehige, Mahesh Loku and Noh, YeRim and Payne, Molly E. and Fortenberry, Alexander W. and Smith, Adam E. and Ilavsky, Jan and Grayson, Scott M. and Schneider, Gerald J. and Watkins, Davita L.},
abstractNote = {In this report, we introduce a facile and comprehensive synthetic methodology for the preparation of polyester-polyamidoamine (PAMAM) (i.e., polyester: polylactide [PLA] (hydrophobic) and polyamidoamine, PAMAM [hydrophilic]) polymers. A library of PLA-PAMAM linear dendritic block copolymers (LDBCs) in which both l and d, l polylactide were employed in mass ratios of 30:70, 50:50, 70:30, and 90:10 (PLA:PAMAM) were synthesized and analyzed. When placed in aqueous media, the immiscibility of the hydrophilic and hydrophobic segments leads to nanophase-segregation exhibited as the formation of aggregates (e.g., vesicles, worms, and/or micelles). By employing both stereochemical configurations of PLA, the differentiation in mass ratios of PLA-PAMAM aided in elucidating the structure–property relationships of the LDBC system and provided a means toward the control of nanoparticle morphology. Transmission electron microscopy and dynamic light scattering afford the size and shape of the nanoparticles with diameters ranging from 10.6 for low mass ratios to 122.4 nm for high mass ratios of PLA-PAMAM and positive zeta-potential values between +24 mV and +48.2 mV. Moreover, small-angle X-ray scattering (SAXS) studies were employed to obtain more detailed information on the morphological assemblies constructed via direct dissolution. Such insights provide a pathway toward nanomaterials with unique morphologies and tunable properties deemed relevant in the development of next generation biomaterials.},
doi = {10.1002/pola.29409},
journal = {Journal of Polymer Science. Part A, Polymer Chemistry},
number = 13,
volume = 57,
place = {United States},
year = {2019},
month = {5}
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on May 20, 2020
Publisher's Version of Record

Save / Share:

Works referenced in this record:

Colloidal particles for cellular uptake and delivery
journal, January 2009

  • Hu, Ling; Mao, Zhengwei; Gao, Changyou
  • Journal of Materials Chemistry, Vol. 19, Issue 20
  • DOI: 10.1039/b815958k

Effects of lithium bromide on the gel-permeation chromatography of polyester-based polyurethanes in dimethylformamide
journal, June 1977


DLS and zeta potential – What they are and what they are not?
journal, August 2016


Block Copolymer Assembly via Kinetic Control
journal, August 2007


Dendrimers and dendritic polymers in drug delivery
journal, January 2005


Characterization of Polystyrenes of Extremely High Molecular Weights
journal, May 1980


Dendrimers as macroinitiators for anionic ring-opening polymerization. Polymerization of ɛ-caprolactone
journal, May 1994

  • Gitsov, Ivan; Ivanova, Pavlina T.; Fréchet, Jean M. J.
  • Macromolecular Rapid Communications, Vol. 15, Issue 5
  • DOI: 10.1002/marc.1994.030150501

Emerging concepts in dendrimer-based nanomedicine: from design principles to clinical applications
journal, July 2014

  • Kannan, R. M.; Nance, E.; Kannan, S.
  • Journal of Internal Medicine, Vol. 276, Issue 6
  • DOI: 10.1111/joim.12280

Effects of particle size and surface charge on cellular uptake and biodistribution of polymeric nanoparticles
journal, May 2010


An overview of the recent developments in polylactide (PLA) research
journal, November 2010


A Simple and Universal Gel Permeation Chromatography Technique for Precise Molecular Weight Characterization of Well-Defined Poly(ionic liquid)s
journal, March 2013

  • He, Hongkun; Zhong, Mingjiang; Adzima, Brian
  • Journal of the American Chemical Society, Vol. 135, Issue 11
  • DOI: 10.1021/ja4012645

Principles of nanoparticle design for overcoming biological barriers to drug delivery
journal, September 2015

  • Blanco, Elvin; Shen, Haifa; Ferrari, Mauro
  • Nature Biotechnology, Vol. 33, Issue 9
  • DOI: 10.1038/nbt.3330

Self-Assembly of Janus Dendrimers into Uniform Dendrimersomes and Other Complex Architectures
journal, May 2010


Guanidine and Amidine Organocatalysts for Ring-Opening Polymerization of Cyclic Esters
journal, December 2006

  • Lohmeijer, Bas G. G.; Pratt, Russell C.; Leibfarth, Frank
  • Macromolecules, Vol. 39, Issue 25
  • DOI: 10.1021/ma0619381

Independent effect of polymeric nanoparticle zeta potential/surface charge, on their cytotoxicity and affinity to cells
journal, May 2015

  • Shao, Xiao-Ru; Wei, Xue-Qin; Song, Xu
  • Cell Proliferation, Vol. 48, Issue 4
  • DOI: 10.1111/cpr.12192

Amphiphilic block copolymers for drug delivery
journal, July 2003

  • Adams, Monica L.; Lavasanifar, Afsaneh; Kwon, Glen S.
  • Journal of Pharmaceutical Sciences, Vol. 92, Issue 7
  • DOI: 10.1002/jps.10397

Synthesis and Properties of Star-Shaped Polylactide Attached to Poly(Amidoamine) Dendrimer
journal, May 2003

  • Cai, Qing; Zhao, Youliang; Bei, Jianzhong
  • Biomacromolecules, Vol. 4, Issue 3
  • DOI: 10.1021/bm034051a

Effect of Chain Length and Unsaturation on Elasticity of Lipid Bilayers
journal, July 2000


Polymeric micelle stability
journal, February 2012


Self-Sorting and Coassembly of Fluorinated, Hydrogenated, and Hybrid Janus Dendrimers into Dendrimersomes
journal, September 2016

  • Xiao, Qi; Rubien, Jack D.; Wang, Zhichun
  • Journal of the American Chemical Society, Vol. 138, Issue 38
  • DOI: 10.1021/jacs.6b08069

Biocompatible and biodegradable polymersomes as delivery vehicles in biomedical applications
journal, January 2012

  • Liu, Gong-Yan; Chen, Chao-Jian; Ji, Jian
  • Soft Matter, Vol. 8, Issue 34
  • DOI: 10.1039/c2sm25721a

Thermo-responsive block copolymers with multiple phase transition temperatures in aqueous solutions
journal, March 2015


Simulating Induced Interdigitation in Membranes
journal, September 2004


Tweaking dendrimers and dendritic nanoparticles for controlled nano-bio interactions: potential nanocarriers for improved cancer targeting
journal, September 2015


Organocatalytic Ring-Opening Polymerization
journal, December 2007

  • Kamber, Nahrain E.; Jeong, Wonhee; Waymouth, Robert M.
  • Chemical Reviews, Vol. 107, Issue 12
  • DOI: 10.1021/cr068415b

Polymeric Systems for Controlled Drug Release
journal, November 1999

  • Uhrich, Kathryn E.; Cannizzaro, Scott M.; Langer, Robert S.
  • Chemical Reviews, Vol. 99, Issue 11
  • DOI: 10.1021/cr940351u

Equilibrium Chain Exchange Kinetics of Diblock Copolymer Micelles:  Tuning and Logarithmic Relaxation
journal, June 2006

  • Lund, Reidar; Willner, Lutz; Richter, Dieter
  • Macromolecules, Vol. 39, Issue 13
  • DOI: 10.1021/ma060328y

Structural and thermodynamic aspects of the cylinder-to-sphere transition in amphiphilic diblock copolymer micelles
journal, January 2011

  • Lund, Reidar; Pipich, Vitaliy; Willner, Lutz
  • Soft Matter, Vol. 7, Issue 4
  • DOI: 10.1039/c0sm00894j

Mechanism for Rapid Self-Assembly of Block Copolymer Nanoparticles
journal, September 2003


Organic Catalysis for Ring-Opening Polymerization
journal, November 2012


Particle size distribution from small-angle X-ray scattering data
journal, August 1985


Synthesis and characterization of multi-functional linear-dendritic block copolymer for intracellular delivery of antitumor drugs
journal, August 2013


Synthesis and properties of novel linear-dendritic block copolymers. Reactivity of dendritic macromolecules toward linear polymers
journal, October 1993

  • Gitsov, Ivan; Wooley, Karen L.; Hawker, Craig J.
  • Macromolecules, Vol. 26, Issue 21
  • DOI: 10.1021/ma00073a014

New Paradigms for Organic Catalysts: The First Organocatalytic Living Polymerization
journal, July 2001


“Janus” dendrimers: syntheses and properties
journal, January 2012

  • Caminade, Anne-Marie; Laurent, Régis; Delavaux-Nicot, Béatrice
  • New J. Chem., Vol. 36, Issue 2
  • DOI: 10.1039/C1NJ20458K

Polymersome Formation from AB 2 Type 3-Miktoarm Star Copolymers
journal, October 2009

  • Yin, Haiqing; Kang, Sun-Woong; Bae, You Han
  • Macromolecules, Vol. 42, Issue 19
  • DOI: 10.1021/ma901701w

Dendrimers for drug delivery
journal, January 2014

  • Caminade, Anne-Marie; Turrin, Cédric-Olivier
  • J. Mater. Chem. B, Vol. 2, Issue 26
  • DOI: 10.1039/C4TB00171K

Self-assembly of amphiphilic Janus dendrimers into uniform onion-like dendrimersomes with predictable size and number of bilayers
journal, June 2014

  • Zhang, S.; Sun, H. -J.; Hughes, A. D.
  • Proceedings of the National Academy of Sciences, Vol. 111, Issue 25
  • DOI: 10.1073/pnas.1402858111

Initiators for the stereoselective ring-opening polymerization of meso-lactide
journal, January 2011

  • Buffet, Jean-Charles; Okuda, Jun
  • Polymer Chemistry, Vol. 2, Issue 12
  • DOI: 10.1039/c1py00206f

Nika : software for two-dimensional data reduction
journal, March 2012


A Small-Angle Neutron and X-ray Contrast Variation Scattering Study of the Structure of Block Copolymer Micelles:  Corona Shape and Excluded Volume Interactions
journal, January 2003

  • Pedersen, Jan Skov; Svaneborg, Carsten; Almdal, Kristoffer
  • Macromolecules, Vol. 36, Issue 2
  • DOI: 10.1021/ma0204913

PAMAM Dendrimers: Destined for Success or Doomed to Fail? Plain and Modified PAMAM Dendrimers in the Context of Biomedical Applications
journal, January 2015

  • Labieniec-Watala, Magdalena; Watala, Cezary
  • Journal of Pharmaceutical Sciences, Vol. 104, Issue 1
  • DOI: 10.1002/jps.24222

Impact of PEGylated Nanoparticles on Tumor Targeted Drug Delivery
journal, December 2018


Linear–dendritic block copolymers: The state of the art and exciting perspectives
journal, January 2011


Syntheses of biodegradable (multi) block copolymers, star-shaped polyesters and networks via ring-expansion polymerization
journal, October 2002

  • Kricheldorf, Hans R.
  • Polymers for Advanced Technologies, Vol. 13, Issue 10-12
  • DOI: 10.1002/pat.237

Predicting the Size and Properties of Dendrimersomes from the Lamellar Structure of Their Amphiphilic Janus Dendrimers
journal, December 2011

  • Peterca, Mihai; Percec, Virgil; Leowanawat, Pawaret
  • Journal of the American Chemical Society, Vol. 133, Issue 50
  • DOI: 10.1021/ja208762u

Poly(amidoamine) (PAMAM) dendrimers: from biomimicry to drug delivery and biomedical applications
journal, April 2001


Dendrimers and supramolecular chemistry
journal, April 2002

  • Frechet, J. M. J.
  • Proceedings of the National Academy of Sciences, Vol. 99, Issue 8
  • DOI: 10.1073/pnas.082013899

PEGylated PAMAM dendrimers: Enhancing efficacy and mitigating toxicity for effective anticancer drug and gene delivery
journal, October 2016


Supramolecular Architectures of Dendritic Amphiphiles in Water
journal, December 2015


Nanoprecipitation process: From encapsulation to drug delivery
journal, October 2017

  • Martínez Rivas, Claudia Janeth; Tarhini, Mohamad; Badri, Waisudin
  • International Journal of Pharmaceutics, Vol. 532, Issue 1
  • DOI: 10.1016/j.ijpharm.2017.08.064

Soft Interaction in Liposome Nanocarriers for Therapeutic Drug Delivery
journal, June 2016

  • Lombardo, Domenico; Calandra, Pietro; Barreca, Davide
  • Nanomaterials, Vol. 6, Issue 7
  • DOI: 10.3390/nano6070125

Review of Matrix-Assisted Laser Desorption Ionization-Imaging Mass Spectrometry for Lipid Biochemical Histopathology
journal, June 2015

  • Yalcin, Emine B.; de la Monte, Suzanne M.
  • Journal of Histochemistry & Cytochemistry, Vol. 63, Issue 10
  • DOI: 10.1369/0022155415596202

The effect of particle design on cellular internalization pathways
journal, August 2008

  • Gratton, S. E. A.; Ropp, P. A.; Pohlhaus, P. D.
  • Proceedings of the National Academy of Sciences, Vol. 105, Issue 33, p. 11613-11618
  • DOI: 10.1073/pnas.0801763105

The role of surface charge in cellular uptake and cytotoxicity of medical nanoparticles
journal, November 2012


Effects of Vesicle Size and Shape on Static and Dynamic Light Scattering Measurements
journal, September 2003

  • Pencer, Jeremy; Hallett, F. Ross
  • Langmuir, Vol. 19, Issue 18
  • DOI: 10.1021/la0345439

Disulfide Cross-Linked Phosphorylcholine Micelles for Triggered Release of Camptothecin
journal, June 2013

  • McRae Page, Samantha; Martorella, Molly; Parelkar, Sangram
  • Molecular Pharmaceutics, Vol. 10, Issue 7
  • DOI: 10.1021/mp400114n

Polylactide-Based Amphiphilic Block Copolymers: Crystallization-Induced Self-Assembly and Stereocomplexation
journal, October 2018

  • Noack, Sebastian; Schanzenbach, Dirk; Koetz, Joachim
  • Macromolecular Rapid Communications, Vol. 40, Issue 1
  • DOI: 10.1002/marc.201800639

Biomedical applications of biodegradable polymers
journal, May 2011

  • Ulery, Bret D.; Nair, Lakshmi S.; Laurencin, Cato T.
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 49, Issue 12
  • DOI: 10.1002/polb.22259

Effects of Size and Surface Charge of Polymeric Nanoparticles on <i>in Vitro</i> and <i>in Vivo</i> Applications
journal, January 2016

  • Sadat, Sams M. A.; Jahan, Sheikh Tasnim; Haddadi, Azita
  • Journal of Biomaterials and Nanobiotechnology, Vol. 07, Issue 02
  • DOI: 10.4236/jbnb.2016.72011

Analytical strategy for the molecular weight determination of random copolymers of poly(methyl methacrylate) and poly(methacrylic acid)
journal, June 2010

  • Giordanengo, Rémi; Viel, Stéphane; Hidalgo, Manuel
  • Journal of the American Society for Mass Spectrometry, Vol. 21, Issue 6
  • DOI: 10.1016/j.jasms.2010.02.007

Concerning the ring-opening polymerization of lactide and cyclic esters by coordination metal catalysts
journal, June 2010