silk

Silk may change the way we think about high technology, material science, medicine, and global health. Silk offers limitless possibilities.

silk

sustainable

natural material using only renewable resources

biodegradable with a clock

can be programmed to dissolve instantaneously or remain stable for years

implantable in the human body

can integrate with living tissue with no inflammatory response

technological edible

can be used in microelectronic, photonic, and nanotechnological applications

safe to consume or for food contact

Programmably biodegradable orthopedic hardware and implants doped with drugs to simultaneously heal and repair
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Drug storage and delivery systems

Smart conformal sensors incorporating antennas, transistors, or displays

Small-diameter silk tubes are strong and durable enough to replace small veins and arteries

Silk can replicate nanoscale topographies and thus store information like a DVD and exhibit optical properties

Molded items made of silk dissolve harmlessly in the environment

Silk is a natural fiber that has been cultivated in Far East Asia for over 5,000 years. The Chinese domesticated Bombyx mori caterpillars and harvested their cocoons in order to produce silk fiber to be used in luxurious textiles. As the material gained popularity in Europe and the Middle East, it eventually lent its name to the Silk Road, the network of trade routes that connected Asia to Europe, arguably making silk the worlds first globalized industry. Today, silk is still produced from the cocoons of these insects for use in textiles from haute couture to home dcor to parachutes. It is even used as surgical sutures. The global silk industry accounts for multiple tens of billions of dollars of trade worldwide.
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5,000-year-old
material?

How do you reinvent a

The Bombyx mori caterpillar serves as the inspiration for the reinvention of silk.

Silk starts as a liquid in the caterpillars gland and is turned into a fiber as it exits the body and makes contact with air. The fiber, besides possessing an alluring luster, is also unusually strong. In fact, silk is the strongest natural fiber available, comparable to technical fibers like Kevlar.

Silk starts as a liquid in the caterpillars gland

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The caterpillar is seen here spinning a silk fiber. It spins a single, one-kilometer long silk fiber into a cocoon for protection.

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Each silk cocoon is composed of water and two different proteins. The fibers are made of fibroin protein, and they are held together by a sticky glue-like protein called sericin that is widely used in cosmetics. In order to use silk in vivo, sericin is removed to avoid an inflammatory response.

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Sericin and fibroin proteins comprising a silk fiber

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The Reinvention of Silk Reverse engineering: from cocoon back to liquid silk
The reinvention of silk involves going back to the gland. With simple processing, silk cocoons are boiled and dissolved, and pure fibroin protein is extracted. The end result of this simple process is a silk solution similar to what the Bombyx mori caterpillar has in its gland.

The silk solution is the foundation of future opportunities.

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1. raw materials

2. boil with a salt and wash to remove the sericin (glue-like protein described on page 14)

3. dissolve the silk in a second salt bath

4. remove the silk by dialysis

Product: a biocompatible solution of pure silk fibroin and water

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Biodegradable and biocompatible

All of the material formats of silk fibroin are biocompatible and biodegradable. Therefore, over a programmable period of time, they are slowly reintegrated in living tissue or the environment without any pernicious effects. This means that, in principle, all of the materials shown can be implanted in the body or used in the environment without the need for their retrieval, removal, or disposal.

subdermis

silk device

muscle layers

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Optical silk
Silk fibroin proteins have a way of self-organizing and assembling into a crystalline matrix as the water in the solution evaporates. The image here of silk solution poured onto a DVD demonstrates one of the technological attributes of silk namely the ability to replicate nanoscale topographies: as the silk dries, it becomes a transparent film that replicates the information contained on the DVD.
Steps 1. pour 2. wait for self-assembly 3. detach

Product: a biocompatible protein film that stores information

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Optical silk

Like a DVD, the information contained in silk film can be read out optically and projected. Here, an image embedded in silk is projected on a wall.

TED 2011, Long Beach, California

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The ability to generate high-quality films made entirely of silk allows for the creation of optical components composed of pure, biocompatible protein.

Some examples of these components made in silk to date are: microlenses, lenticular arrays, diffraction gratings, microprisms, photonic crystals, resonators, and phase masks with ultimate feature resolution of less than 10 nanometers (10,000 times smaller than the diameter of a human hair)

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By changing the topography of the silk film at such small scales, light can be manipulated to generate 3D images. The hologram shown here is written on a 6x8-inch silk film and enclosed in an acrylic display case.

Liquid silk can be made into optical fibers to guide light. Thanks to silk's strength and its capacity to be conductive, fluorescent, and drug-eluting, other possibilities include manufacturing technologically enhanced silk fibers for next-generation textile applications.

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Implantable optics
Small microprism arrays made out of silk can be made into reflective materials that function like the ones inlaid in garments and footwear. However, unlike synthetic polymers, silk reflective materials can be implanted in living tissue. The image below shows silk reflective tape after one month of implantation under the skin. Much like a runner is seen at night, ordinarily hard-to-image subdermal layers of tissue can be seen better thanks to the presence of the reflective tape that conforms to the curvilinear nature of living tissue. With time, the silk mirror integrates into the tissue with no need to retrieve it.
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An example of transforming silk into a common optical material is shown here.

silk reflective tape

Smart Sensors
The addition of small quantities of non-toxic metals (such as gold) or semiconductors makes silk capable of technological transformations enabling antennas, sensors, transistors, or displays.

A silk antenna conforms to the surface of the banana, wirelessly transmitting information of its ripeness by transducing gas emission and skin pH/sugar content.
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The interface properties of silk allow technological components such as transistors to be included on silk films to make mostly resorbable devices (top) or to make unusual electronics and electrodes that wrap and conform to irregular surfaces (bottom).

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Medical devices
Liquid silk can be converted into small-diameter tubes that are strong and durable enough to replace small veins and arteries. There is no comparable biocompatible material with as much mechanical strength at such small diameters (only a few millimeters).

The same silk solution can be used to build bigger mechanical parts, like orthopedic hardware.

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Silk solution can be used to make larger implants, such as the bone replacement shown here that doubles as a mechanical support and a tissue scaffold to promote natural bone and tissue regeneration.

The gears, nuts, and bolts shown here and on the previous page have high mechanical strength and are made of only protein and water.

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Consumer applications
The ability to make shaped solid objects out of water and protein like the silk cups shown here means unprecedented opportunities for sustainability. After being used, objects made of silk harmlessly break down and reintegrate into the environment. This opportunity is of particular importance considering that more than 100 million non-degradable cups and bottles fill our landfills every day.

What is in our landfills?

plastic bottles styrofoam coffee cups
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60,000,000 per day 70,000,000 per day

Edible technology
Silk is edible and routinely consumed in the eastern parts of the world. This comestible trait applies to the materials presented here. This material property, coupled with the technological attributes, allows us to think of sensing technology, such as smart labels or packaging, to be interfaced directly and consumed along with food products. The images show metamaterial gold antennas overlayed on an apple and an egg. The edible and optical properties of the silk material may also spell novel applications in toys and as an artistic medium.

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A cocoon for biological materials

Perhaps the most remarkable trait of the silk material is that, just like the cocoon protects the worm, silk provides protection for biological compounds. The self-assembly of the protein provides a storage environment for biological dopants that are mixed into the liquid silk. When the material solidifies, the biological components are preserved.
Steps 1. pour 2. add things like vaccines, antibodies, or enzymes 3. wait for self-assembly 4. detach

things

Product: preserved biological compounds

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By mixing biological dopants such as vaccines, antibodies, or enzymes in the silk solution, all the materials remain biologically active/interactive. For example, in addition to repairing a fractured bone, these screws, nuts, and bolts can simultaneously deliver drugs to promote healing. Similarly, silk microneedle arrays can contain a drug, preserve it, and deliver it. Or, drugs can be stored in your wallet without the need for refrigeration. This opens up new options for vaccine storage and transportation.

To demonstrate this, we have stored penicillin in a silk film for two months at 60 degrees Celsius (140 degrees F) without loss of efficacy. Similar storage has been demonstrated with glucose oxidase, tetracyclenes, lipase, and monoclonal antibodies.
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A material with tunable degradation

Additionally, by controlling the conditions of protein self-assembly, the materials can be programmed to degrade instantaneously (allowing for the recuperation of what was preserved within) or to remain stable for years. Silk materials are ideally suited for drug delivery applications, thanks to their controllable dissolution rates.

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Silk film programmed to degrade instantaneously

Silk film programmed to remain stable

1 minute

3 minutes

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The unusual combination of material properties could lead to the reinvention of current technology, the invention of new applications, and new solutions to contemporary problems.

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The amazing versatility of silk provides opportunities for the future that span multiple disciplines. Our vision is to use this wondrous material as an inspiration for reinventing technology and everyday materials, while improving global health and fostering opportunities for a sustainable world.

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CHEMICAL SYNTHESIS CLONING SUSTAINABLE FARMING MICROECONOMIES REFORESTATION GENETIC EXPRESSION

SAFETY/SECURITY

BIOMEDICAL

CONSUMER GOODS

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build your own silk gadget

Choose material format

Functionalize with dopant? NO (undoped) YES (doped)

micro and nanoparticles sponges and scaffolds films and conformal coatings reversible and permanent adhesives finers and ropes

organic dopant
proteins (enzymes, antibodies) drugs / vaccines cells*

inorganic dopant
quantum dots laser dyes metals nanoparticles

blocks

*cell doping only compatible with certain material formats

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Pick desired fabrication approach

Program degradation time

soft lithography microfluidic printing inkjet printing (2D and 3D) nanoimprinting (low pressure, RT) optical lithography active device transfer shape molding spin-coating electrospinning laser micromachining plasma etching metal deposition/transfer water-vapor annealing slow ambient drying methanol annealing low-T heating

instantaneous days weeks months

Implantable/ Edible RFID

Drug Eluting Wound Dressing Mats Communicating Therapeutic Orthopedic Hardware

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build your own silk gadget... what can you think of?

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antibiotic glue holographic vaccines dissolvable radios electronic tissues holographic antibodies living transistors printable lasers edible sensors functional drinking cups antibiotic sutures social fabric vaccine sheets melting microlenses protein CDs, DVDs implantable fiber optics brain implants implantable heaters invisibility cloaks blood optics underwater adhesives nuts and bolts smart burn healing long-lasting surgical fillers new sustainable plastics

About the authors

Fiorenzo Omenetto
is a Professor of Biomedical Engineering and also holds an appointment in the Department of Physics at Tufts University. His research is focused on interdisciplinary themes that span nonlinear optics, nanostructured materials (such as photonic crystals and photonic crystal fibers), biomaterials, optofluidics, and biopolymerbased photonics. He has published over 100 papers and peer review contributions across these various disciplines. Since moving to Tufts at the end of 2005, he has proposed and pioneered (with DLK) the use of silk as a material platform for photonics, optoelectronics, and high-technology applications. The platform has recently been featured in MITs Technology Review magazine as one of the 2010 TR10 top ten technologies likely to change the world and as an idea for 2011 by Wired UK. Prof. Omenetto was recently named one of the top 50 people in tech by Fortune magazine and a Guggenheim Fellow.

David Kaplan
is the Stern Professor of Biomedical Engineering at Tufts University and holds appointments in Chemical Engineering and the School of Medicine. He is the leading expert in the fundamental and applied aspects of silk fibroin obtained from silkworms. He has published over 375 papers in the areas of silk, biomaterials, tissue engineering, drug delivery, biosensors, medical devices, clinical medicine, and most recently, biocompatible electronics. Prof. Kaplan holds the Stern Family Endowed Professorship of Bioengineering and is the Chair of the Department of Biomedical Engineering, with secondary appointments as Professor, Tufts Sackler School of Biomedical Sciences, and Professor, Tufts School of Dental Medicine. He is Director of the Tufts Bioengineering & Biotechnology Center and the Tufts NIH P41 Tissue Engineering Resource Center, and is an appointed Associate Editor of the journal Biomacromolecules.
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Tufts University, Kaplan Lab, Omenetto Lab, Gary Leisk, Tim Lo, Eleanor Pritchard, Keleigh Sanford, Jason Amsden, Hu (Tiger) Tao, Scott Sahagian, John Rogers, Natalie Wolchover, Michael Lovett, Eunseok Gil, Peter Domachuk, Graham Tilburey, Xiaoqin Wang, Konstantinos Tsioris, Brian Lawrence, Tom Dabrowski, Jason Bressner, Lauren Klinker, Mark Brenckle, Sean Siebert, Mia Yang, Majonico, Carmen Preda, Baxxellus, Jon Kluge, Jonathan Levitt, the Omenetto family, Alex Mitropoulos, Mamma Milva, Mark Cronin-Golomb, Dae-Hyeong Kim, Jennifer Lewis, Sara Parker, Luca Dal Negro, Svetlana Boriskina, Ashwin Gopinath, Sylvanus Lee, Richard Averitt, Roberto Zamboni, Michele Muccini, Valentina Benfenati, James Grote, Linda Abriola, Juan Enriquez, Lindala, Giuseppe Pastorelli, Elena Lucco Borlera, Cristina Buonerba, Tufts Tech Transfer, Rajesh Naik, Mitchell Zakin, Hugh Delong, Jon Mogford, the Chalkin family, Mario D'Amato, Charlie Mendoza, Nick Puccia, Dave Gaull, Rosie Friedman, and too many others to mention........................................................................................
Photo credits All images by Fiorenzo Omenetto except by Florian Vincent, p.15, James Duncan Davidson / TED, p. 25, Dae-Hyeong Kim, p. 33
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thank you

Further reading

First demonstration of silkbased metamaterial antennas for sensing

Advanced Materials, 2010

Innovation with a material of the past Long Beach, 2011

Silk interfaces to the brain for in vivo EEG measurement

Nature Materials, 2010

Top 10 technologies likely to change the world

MIT Technology Review, 2010

Low-temperature, low- pressure nanoimprinting on silk films

Advanced Materials, 2010

Optical waveguides made from inkjet-printed silk

Advanced Materials, 2009

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2010
Omenetto F, Kaplan D, From Silk Cocoon to Medical Miracle, Scientific American Volume: 303 Issue: 5 Pages: 76-77 Published: NOV 2010 Omenetto, F. G., and D. L. Kaplan. New Opportunities for an Ancient Material. Science 329, no. 5991: 528-31, 101, (2010) Hu Tao, Andrew C. Strikwerda, Mengkun Liu, Jessica P. Mondia, Evren Ekmekci, Kebin Fan, David L. Kaplan, Willie J. Padilla, Xin Zhang, Richard D. Averitt, and Fiorenzo G. Omenetto, Performance enhancement of terahertz metamaterials on ultrathin substrates for sensing applications , Applied Physics Letters, 97!!(26), 261909!, ! DEC 27 2010 Tao, H., J. J. Amsden, A. C. Strikwerda, K. Fan, D. L. Kaplan, X. Zhang, R. D. Averitt, F. G. Omenetto. 2010. Metamaterial silk composites at terahertz frequencies. Advanced Materials July 21 Epub ahead of print [PMID 20665563] (cover story) Mondia, J.P., Amsden, J.J., Lin, D., Dal Negro, L., Kaplan, D. L., Omenetto, F. G., Rapid Nanoimprinting of Doped Silk Films for Enhanced Fluorescent Emission, Advanced Materials, 22, 41, 4596-4599, 2010 ! Hu Tao, Sean M. Siebert, Mark A. Brenckle, Richard D. Averitt, Mark Cronin-Golomb, David L. Kaplan, Fiorenzo G. Omenetto, Gold Nanoparticle-Doped Biocompatible Silk Films as a Path to Implantable Thermal-electrically Wireless Powering Devices, Applied Physics Letters, Volume: 97 Issue: 12, 123702 Published: SEP 20 2010 Kim, R.H, D.H. Kim, J. Xiao, B. Hoon Kim, S. Park, B. Panilaitis, R. Ghaffari, J. Yao, M. Li, Z. Liu, V. Malyarchuk, D. G. Kim, A. Le, R. G. Nuzzo, D. L. Kaplan, F. G. Omenetto, Y. Huang, Z. Kang, J. A. Rogers, Waterproof AlInGaP Optoelectronics on Flexible Tubing, Sutures, Gloves and Other Unusual Substrates, With Application Examples in Biomedicine and Robotics, Nature Materials, Volume: 9 !!Issue: 11 Pages: 929-937 Published: NOV 2010 Benfenati, V., S. Toffanin, R. Capelli, L. M. Camassa, S. Ferroni, D. L. Kaplan, F. G. Omenetto, M. Muccini, R. Zamboni. (2010) A silk platform that enables electrophysiology and targeted drug delivery in brain astroglial cells. Biomaterials Aug 3, Epub ahead of print [PMID 20688390] Gil, E. S., B. B. Mandal, S. H. Park, J. K. Marchant, F. G. Omenetto, and D. L. Kaplan. Helicoidal multi-lamellar features of RGD-functionalized silk biomaterials for corneal tissue engineering. Volume: 31 Issue: 31 Pages: 7883-7891 Published: NOV 2010 Zhang Z, Li HF, Li P, Cronin-Golomb, M, Omenetto, F. G. and Liu Z., Supercontinuum trap stiffness measurement using a confocal approach, Optics Express, Volume: 18 Issue: 25 Pages: 26499-26504 Published: DEC 6 2010 Omenetto, F. G., D. L. Kaplan. 2010. SnapShot: Silk Biomaterials. Biomaterials 23:6119-6120 [PMID: 20593549 Kim, D. H., J. Viventi, J. J. Amsden, J. L. Xiao, L. Vigeland, Y. S. Kim, J. A. Blanco, B. Panilaitis, E. S. Frechette, D. Contreras, D. L. Kaplan, F. G. Omenetto, Y. G. Huang, K. C. Hwang, M. R. Zakin, B. Litt, and J. A. Rogers. Dissolvable Films of Silk Fibroin for Ultrathin Conformal Bio-Integrated Electronics. Nature Materials 9, no. 6: 511-17, (2010) (cover story)

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2009

Lee, S. Y., J. J. Amsden, S. V. Boriskina, A. Gopinath, A. Mitropolous, D. L. Kaplan, F. G. Omenetto, and L. Dal Negro. Spatial and Spectral Detection of Protein Monolayers with Deterministic Aperiodic Arrays of Metal Nanoparticles. Proceedings of the National Academy of Sciences of the United States of America 107, no. 27: 12086-90, (2010) Amsden, J. J., P. Domachuk, A. Gopinath, R. D. White, L. Dal Negro, D. L. Kaplan, and F. G. Omenetto. Rapid Nanoimprinting of Silk Fibroin Films for Biophotonic Applications. Advanced Materials 22, no. 15: 1746-+, (2010) (cover story) Lu, S. Z., X. Q. Wang, Q. Lu, X. H. Zhang, J. A. Kluge, N. Uppal, F. Omenetto, and D. L. Kaplan. Insoluble and Flexible Silk Films Containing Glycerol. Biomacromolecules 11, no. 1: 143-50, (2010) Lu, Q., X. Q. Wang, X. Hu, P. Cebe, F. Omenetto, and D. L. Kaplan. Stabilization and Release of Enzymes from Silk Films. Macromolecular Bioscience 10, no. 4: 359-68, (2010) Tsioris, K., G. E. Tilburey, A. R. Murphy, P. Domachuk, D. L. Kaplan, and F. G. Omenetto. Functionalized-Silk-Based Active Optofluidic Devices. Advanced Functional Materials 20, no. 7: 1083-89, (2010) Lawrence, B. D., S. Wharram, J. A. Kluge, G. G. Leisk, F. G. Omenetto, M. I. Rosenblatt, and D. L. Kaplan. Effect of Hydration on Silk Film Material Properties. Macromolecular Bioscience 10, no. 4: 393-403, (2010) Gil, E. S., S. H. Park, J. Marchant, F. Omenetto, and D. L. Kaplan. Response of Human Corneal Fibroblasts on Silk Film Surface Patterns. Macromolecular Bioscience 10, no. 6: 664-73, (2010) Domachuk, P., K. Tsioris, F. G. Omenetto, and D. L. Kaplan. Bio-Microfluidics: Biomaterials and Biomimetic Designs. Advanced Materials 22, no. 2: 249-60, (2010) Boriskina, S. V., S. Y. K. Lee, J. J. Amsden, F. G. Omenetto, and L. Dal Negro. Formation of Colorimetric Fingerprints on Nano-Patterned Deterministic Aperiodic Surfaces. Optics Express 18, no. 14: 14568-76, (2010) Manocchi, A. K., P. Domachuk, F. G. Omenetto, and H. M. Yi. Facile Fabrication of Gelatin-Based Biopolymeric Optical Waveguides. Biotechnology and Bioengineering 103, no. 4 (2009): 725-32. (cover story) Lu, S. Z., X. Q. Wang, Q. Lu, X. Hu, N. Uppal, F. G. Omenetto, and D. L. Kaplan. Stabilization of Enzymes in Silk Films. Biomacromolecules 10, no. 5 (2009): 1032-42. Parker, S. T., P. Domachuk, J. Amsden, J. Bressner, J. A. Lewis, D. L. Kaplan, and F. G. Omenetto. Biocompatible Silk Printed Optical Waveguides. Advanced Materials 21, no. 23 (2009): (cover story) Lawrence, B. D., J. K. Marchant, M. A. Pindrus, F. G. Omenetto, and D. L. Kaplan. Silk Film Biomaterials for Cornea Tissue Engineering. Biomaterials 30, no. 7 (2009): 1299-308. Kim, D. H., Y. S. Kim, J. Amsden, B. Panilaitis, D. L. Kaplan, F. G. Omenetto, M. R. Zakin, and J. A. Rogers. Silicon Electronics on Silk as a Path to Bioresorbable, Implantable Devices. Applied Physics Letters 95, no. 13 (2009), 133701: Domachuk, P., H. Perry, J. J. Amsden, D. L. Kaplan, and F. G. Omenetto. Bioactive Self-Sensing Optical Systems. Applied Physics Letters 95, no. 25 (2009), 253702: Domachuk, P., N. Wolchover, M. Cronin-Golomb, and F. G. Omenetto. Effect of Hollow-Core Photonic Crystal Fiber Microstructure on Transverse Optical Trapping. Applied Physics Letters 94, no. 14 (2009): Amsden, J. J., H. Perry, S. V. Boriskina, A. Gopinath, D. L. Kaplan, L. Dal Negro, and F. G. Omenetto. Spectral Analysis of Induced Color Change on Periodically Nanopatterned Silk Films. Optics Express 17, no. 23 (2009): 21271-79. Amsden, J. J., A. Gopinath, L. Dal Negro, D. L. Kaplan, F. G. Omenetto, and Ieee. Silk Fibroin Biosensor Based on Imprinted Periodic Nanostructures. In 2009 Conference on Lasers and Electro-Optics and Quantum Electronics and Laser Science Conference, 201-02. New York: IEEE, 2009. Adato, R., A. A. Yanik, J. J. Amsden, D. L. Kaplan, F. G. Omenetto, M. K. Hong, S. Erramilli, and H. Altug. Ultra-Sensitive Vibrational Spectroscopy of Protein Monolayers with Plasmonic Nanoantenna Arrays. Proceedings of the National Academy of Sciences of the United States of America 106, no. 46 (2009): 19227-32.

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