Dendrimers

NANO52 Foothill College

Overview
What are dendrimers? How are they formed? What are their properties? What are the applications? How do you characterize them?

Dendrimers Building Blocks of Nanotechnology

http://www.chemistry.ohio-state.edu/cgi-bin/brochure?Faculty=parquett

Dendrimers consist of a series of chemical shells built on a small core molecule. Each shell consists of two chemicals, always in the same order and is called a generation

http://nano.med.umich.edu/Dendrimers.html#dendrimer_introduction

http://www.ninger.com/dendrimer/

Dendrimer Components

http://www3.interscience.wiley.com/cgi-bin/fulltext/106558159/PDFSTART

Dendrimers vs. Proteins

Similarities Main Difference Proteins are polymers made from 20 different monomers, while dendrimers are polymers made from two monomers.

Size
Weight Well defined chemical structure (known bonding structure) 3 dimensional position of each atom is difficult to determine - yet a consistent specific 3 dimensional structure exists Difficult to perform chemical analysis Easy for cell to uptake

http://nano.med.umich.edu/Dendrimers.html

Light Harvesting Dendrimers

http://www3.interscience.wiley.com/cgi-bin/fulltext/106558159/PDFSTART

Organic Light Emitting Diodes (OLEDs)

http://www3.interscience.wiley.com/cgi-bin/fulltext/106558159/PDFSTART

Dendrimer Applications
"The future of dendritic macromolecules lies in large part with cleverly designed syntheses that can deliver the structures best-suited for interesting applications," Frchet says. "Our group is deeply involved not only in mission-oriented synthesis but also in learning more about the properties of dendrimers that take full advantage of their precise nanometer size, high functionality, and regular structural features."

This light-harvesting dendrimer performs some functions of artificial photosynthesis. White light is gathered through chain-ends that behave like antennae and funneled into a chromophore in the dendrimer's core that then emits a single color of amplified light

http://www.lbl.gov/Science-Articles/Research-Review/Magazine/2001/Fall/features/02Dendrimers.html

Catalysis

http://perceco2.chem.upenn.edu/~percec/inthenews/denx.html

http://www3.interscience.wiley.com/cgi-bin/fulltext/106558159/PDFSTART

Supramolecular Architectures

A schematic illustration of supramolecular architectures of self-assembled extended amphiphilic dendrons, developed at Cornell by Ulrich Wiesner, professor of materials science and engineering , and his research team. The illustration shows (A) cubic micelles, (B) two-dimensional lamellar layers, (C) hexagonally arranged cylindrical columns and (D) three-dimensional continuous cubic structures.
Cornell Center for Materials ResearchCopyright Cornell University http://www.news.cornell.edu/releases/Sept04/Wiesner.supermolecules.deb.html

Bio-Therapeutic Dendrimers

http://www.fda.gov/nanotechnology/powerpoint_conversions/chbsa-nanotech-presentation06-05_files/images/image5.png

Dendrimers Fighting the Spread of Diseases

The dendrimers (blue and red) in VivaGel interact with protein structures (yellow) on the surface of HIV, blocking the interaction of HIV (purple) with healthy human cells (pink) that results in HIV infection.

The dendrimer (blue and red) attaches to multiple receptors (pink) on cell membranes or other biological structures such as a virus.

Illustrations courtesy of Starpharma Pooled Development, Ltd

http://www.smalltimes.com/document_display.cfm?document_id=6691

Drug Delivery

http://www.davidwang.homestead.com/files/Drug_delivery.pdf
http://www.umich.edu/news/?Releases/2004/Mar04/r032304

Dendrimer Conjugates

http://www3.interscience.wiley.com/cgi-bin/fulltext/106558159/PDFSTART

Dendrimers

www.dendritch.com

Dendrimer Generations
Dendrimers are synthesized in generations, as shown in this animated graphic from Dendritech. Poly(amido amine) (PAMAM) dendrimers represent an exciting new class of macromolecular architecture called "dense star" polymers. Unlike classical polymers, dendrimers have a high degree of molecular uniformity, narrow molecular weight distribution, specific size and shape characteristics, and a highlyfunctionalized terminal surface. The manufacturing process is a series of repetitive steps starting with a central initiator core. Each subsequent growth step represents a new "generation" of polymer with a larger molecular diameter, twice the number of reactive surface sites, and approximately double the molecular weight of the preceding generation.

Dendrimer Structure

Dendrimers (Arborols)

Synthesis to 2nd generation Arborol - http://en.wikipedia.org/wiki/Dendrimer

Dendrimers (Arborols)

Dendrimer Superstructures
Dendrimers are repetitively branched molecules. [1] [2] The name comes from the Greek word "" (pronounced dendron), which translates to "tree". Synonymous terms for dendrimer include arborols and cascade molecules. However, dendrimer is currently the internationally accepted term. A dendrimer is typically symmetric around the core, and often adopts a spherical three-dimensional morphology. The word dendron is also encountered frequently. A dendron usually contains a single chemically addressable group called the focal point. The difference between dendrons and dendrimers is illustrated in figure one, but the terms are typically encountered interchangeably.[3]

http://www.gade.uni-hd.de/research.php

Bioactive Dendrimers
Dendrimers can be functionalized for surface activity., such as attaching to cells, and using a quantum dot interior core for imaging. Dendrimers can contain metal atoms including gold which can absorb radiation at a particular wavelength, and used in cancer treatment. The relatively short lifetime of a dendrimer enures that it wont bioaccumulate in the body, or concentrate potentially toxic cadmium (CdS quantum dots).
http://pubs.acs.org/doi/abs/10.1021/nl202220q and http://www.ncbi.nlm.nih.gov/pubmed/21864902

Gene Delivery via Dendrimer

The ability to deliver pieces of DNA to the required parts of a cell includes many challenges. Current research is being performed to find ways to use dendrimers to traffic genes into cells without damaging or deactivating the DNA. To maintain the activity of DNA during dehydration, the dendrimer/DNA complexes were encapsulated in a water soluble polymer, and then deposited on or sandwiched in functional polymer films with a fast degradation rate to mediate gene transfection. Based on this method, PAMAM dendrimer/DNA complexes were used to encapsulate functional biodegradable polymer films for substratemediated gene delivery. Research has shown that the fast degrading functional polymer has great potential for localized transfection.

http://en.wikipedia.org/wiki/Dendrimers

Organic Synthesis

Dendrimers have been prepared via click chemistry, employing Diels-Alder reactions,thiolyne reactions and azide-alkyne reactions.An example is the synthesis of certain polyphenylene dendrimers is shown in this figure http://en.wikipedia.org/wiki/Dendrimer

Divergent Synthesis

The dendrimer is assembled from a multifunctional core, which is extended outward by a series of reactions, commonly a Michael reaction. Each step of the reaction must be driven to full completion to prevent mistakes in the dendrimer, which can cause trailing generations (some branches are shorter than the others). Such impurities can impact the functionality and symmetry of the dendrimer, but are extremely difficult to purify out because the relative size difference between perfect and imperfect dendrimers is very small.

http://en.wikipedia.org/wiki/Dendrimers

Supramolecular Dendrimers
Supramolecular systems are rarely designed from first principles. Rather, chemists have a range of well-studied structural and functional building blocks that they are able to use to build up larger functional architectures. Many of these exist as whole families of similar units, from which the analog with the exact desired properties can be chosen. The molecule shown here is a combination of traditional organic synthetic compounds using significant steric hinderence to achieve a particular shape/conformation.

http://en.wikipedia.org/wiki/Dendrimers

Summary
Dendrimers are branching structures Multiple molecular/synthetic generations Resemble macromolecules (proteins)
Can have an active inner core

Related to supramolecular structures Applications in medicine/ drug delivery

References
Wikipedia (dendrimers) Dendritech - http://www.dendritech.com/ NCBI => molecules and PubMed FDA www.fda.gov Institute for Molecular Manufacturing (IMM)