Biomacromolecules 2002, 3, 1233-1239 1233

Electrospinning Bombyx mori Silk with Poly(ethylene oxide)

Hyoung-Joon Jin,† Sergey V. Fridrikh,‡ Gregory C. Rutledge,‡ and David L. Kaplan*,†

Department of Chemical & Biological Engineering, Bioengineering Center, Tufts University, 4 Colby Street,
Medford, Massachusetts 02155, and Department of Chemical Engineering, Massachusetts Institute of
Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139
Received May 30, 2002; Revised Manuscript Received July 25, 2002

Electrospinning for the formation of nanoscale diameter fibers has been explored for high-performance
filters and biomaterial scaffolds for vascular grafts or wound dressings. Fibers with nanoscale diameters
provide benefits due to high surface area. In the present study we explore electrospinning for protein-based
biomaterials to fabricate scaffolds and membranes from regenerated silkworm silk, Bombyx mori, solutions.
To improve processability of the protein solution, poly(ethylene oxide) (PEO) with molecular weight of
900 000 was blended with the silk fibroin. A variety of compositions of the silk/PEO aqueous blends were
successfully electrospun. The morphology of the fibers was characterized using high-resolution scanning
electron microscopy. Fiber diameters were uniform and less than 800 nm. The composition was estimated
by X-ray photoelectron spectroscopy to characterize silk/PEO surface content. Aqueous-based electrospining
of silk and silk/PEO blends provides potentially useful options for the fabrication of biomaterial scaffolds
based on this unique fibrous protein.

Introduction solutions of metastable lyotropic phases that are then forced

Electrospinning for the formation of fine fibers has been
actively explored recently for applications such as high-per-
formance filters1,2 and biomaterial scaffolds for cell growth,
vascular grafts, wound dressings, or tissue engineering.2-6
These applications benefit from the high surface area of the
fibers. In this electrostatic technique, a strong electric field
is generated between a polymer solution contained in a glass
syringe with a capillary tip and a metallic collection screen.
When the voltage reaches a critical value, the charge
overcomes the surface tension of the deformed drop of
suspended polymer solution formed on the tip of the syringe,
and a jet is produced. The electrically charged jet thins under
electrohydrodynamic forces,7 and under certain operating
conditions undergoes a series of electrically induced bending
instabilities during passage to the collection screen that results
in extensive stretching.8-12 This stretching process is ac-
companied by the rapid evaporation of the solvent and results
in a reduction in the diameter of the jet.10,13-16 The dry fibers
accumulated on the surface of the collection screen form a
nonwoven mesh of nanometer to micrometer diameter fibers
even when operating with aqueous solutions at ambient
temperature and pressure. The electrospinning process can
be adjusted to control fiber diameter to some extent by
varying the charge density and polymer solution concentra-
tion, while the duration of electrospinning controls the
thickness of the deposited mesh.10-17
Protein fiber spinning in nature, such as for silkworm and
spider silks, is based on the formation of concentrated
† Tufts University.
‡ Massachusetts Institute of Technology.
10.1021/bm025581u CCC: $22.00
Published on Web 08/28/2002
through small spinnerets into air.18 The fiber diameters
produced in these natural spinning processes range from tens
of micrometers in the case of silkworm silk to micrometers
to submicrometers in the case of spider silks.18 The produc-
tion of fibers from protein solutions has typically relied upon
the use of wet or dry spinning processes.19,20 Electrospinning
offers an alternative approach to protein fiber formation that
can potentially generate very fine fibers. This would be a
useful feature based on the potential role of these types of
fibers in some applications such as biomaterials and tissue
engineering.5,6,21 Electrospinning has been utilized to generate
nanometer diameter fibers from type I collagen,5,6 recom-
binant elastin protein,21 and silklike protein.22-24 Zarkoob et
al.25 have also reported that silkworm silk from Bombyx mori
cocoons and spider dragline silk from Nephila claVipes silk
can be electrospun into nanometer diameter fibers if first
solubilized in hexafluoro-2-propanol (HFIP).
Silk is a well described natural fiber produced by the
silkworm, B. mori, which has been used traditionally in the
form of threads in textiles for thousands of years. This silk
contains a fibrous protein termed fibroin (both heavy and
light chains) that forms the thread core and gluelike proteins
termed sericin that surround the fibroin fibers to cement them
together. The fibroin is a highly insoluble protein containing
up to 90% of the amino acids glycine, alanine, and serine
leading to antiparallel β-pleated sheet formation in the
fibers.26 Recent interest in the use of reprocessed silks such
as fibroin in biotechnological materials and in biomedical
applications originate from the unique mechanical properties
of these fibers as well as their biocompatibility.18,27
© 2002 American Chemical Society
1234 Biomacromolecules, Vol. 3, No. 6, 2002 Jin et al.

In the present study, we sought to develop silk electro-

spinning approaches that would address two major goals.
First, we wanted to avoid problems encountered with
conformational transitions of silkworm fibroin during solu-
bilization and reprocessing from aqueous solution to generate
new fibers and films. This problem derives from the
formation of insoluble β-sheets. This process can result in
embrittled materials that become difficult to utilize in
subsequent studies. To overcome this problem we determined
that blending would be a suitable option and we report on
the incorporation of poly(ethylene oxide) (PEO) with silk
in the electrospinning process. Second, we wanted to enhance
the potential biocompatibility of the electrospun silk fibers
by avoiding the use of organic solvents that can pose
problems when the processed materials are exposed to cells
in vitro or in vivo. Thus, we desired to develop an all-aqueous
process for silk electrospinning in combination with PEO.
PEO is well-documented as a biocompatible polymer29-31 Figure 1. Viscosities of silk/PEO blends in water.
and has been successfully blended with collagen in electro-
spinning.6,28

Experimental Section

Materials. Cocoons of B. mori silkworm silk were kindly

supplied by M. Tsukada, Institute of Sericulture, Tsukuba,
Japan. PEO with an average molecular weight of 9 × 105
(Aldrich) was used in blending.
Preparation of Regenerated B. mori Silk Fibroin
Solutions. B. mori silk fibroin was prepared as follows as a
modification of our earlier procedure.32 Cocoons were boiled
for 30 min in an aqueous solution of 0.02 M Na2CO3 and
then rinsed thoroughly with water to extract the gluelike
sericin proteins. The extracted silk was then dissolved in 9.3
M LiBr solution at 60 °C yielding a 20% (w/v) solution.
This solution was dialyzed in water using a Slide-a-Lyzer
dialysis cassette (Pierce, MWCO 2000). The final concentra-
tion of aqueous silk solution was 3.0-7.2 wt %, which was
determined by weighing the remaining solid after drying.
HFIP silk solution (1.5 wt %) was prepared by dissolving
the lyophilized aqueous silk solution in HFIP.
Preparation of Spinning Solutions. Silk/PEO blends in
water were prepared by adding PEO (900 000 g/mol) directly
into the silk aqueous solutions generating 4.8-8.8 wt % silk/
PEO solutions. Silk solutions in HFIP (1.5 wt %) and PEO
(4.0 wt %) solution in water, respectively, were also prepared
as controls for comparisons with the blends. Silk solutions
in HFIP were prepared by dissolving the lyophilized silk
fibroin in HFIP at room temperature. The viscosity and
conductivity of the solutions were measured with a Couette
viscometer (Bohlin V88), with a shear rate from 24.3 to 1216
per second, and a Cole-Parmer conductivity meter (19820)
at room temperature, respectively.
Electrospinning. Electrospinning was performed with a
steel capillary tube with a 1.5 mm inside diameter tip
mounted on an adjustable, electrically insulated stand as
described earlier.13 The capillary tube was maintained at a
high electric potential for electrospinning and mounted in
the parallel plate geometry. The capillary tube was connected
to a syringe filled with 10 mL of a silk/PEO blend or silk
Figure 2. Scanning electron micrograph of electrospun fibers (blend
5) (background) and sericin extracted native Bombyx mori silk fibers
(foreground). (Scale bar ) 50 µm.)
solution. A constant volume flow rate was maintained using
a syringe pump, set to keep the solution at the tip of the
tube without dripping. The electric potential, solution flow
rate, and the distance between the capillary tip and the
collection screen were adjusted so that a stable jet was
obtained. By variation of the distance between the capillary
tip and the collection screen, either dry or wet fibers were
collected on the screen.
Scanning Electron Microscopy (SEM). Images of elec-
trospun fibers were obtained with a LEO Gemini 982 field
emission gun scanning electron microscope. Average fiber
diameters were determined by measuring 50 fibers selected
randomly from each electrospun blend.
FT-IR. Infrared spectra were measured with an attenuated
total reflectance Fourier transform (ATR-FTIR) (Bruker
Equinox 55) spectrophotometer. Each spectrum was acquired
in transmittance mode on a ZnSe ATR crystal cell by
accumulation of 256 scans with a resolution of 4 cm-1 and
a spectral range of 4000-600 cm-1.
X-ray Photoelectron Spectroscopy (XPS). A Surface
Science, Inc., model SSX-100 X-ray photoelectron spec-
trometer was used to analyze the surface of the silk films to
estimate the surface density of protein versus PEO. Survey
Electrospinning Silk Biomacromolecules, Vol. 3, No. 6, 2002 1235

Figure 3. Scanning electron micrographs of electrospun fibers: (a) blend 1 (10 µm), (b) blend 2 (5 µm), (c) blend 3 (2 µm), (d) blend 4 (5 µm),
(e) blend 5 (2 µm), (f) blend 6 (2 µm), and (g) blend 7 (20 µm). Numbers in parentheses are scale bars.
1236 Biomacromolecules, Vol. 3, No. 6, 2002 Jin et al.

Table 1. Characteristics of Silk, PEO, Silk/PEO Blend Solutions, Spinning Conditions, and Fiber Features
initial concn of PEO ratio to silk total concn conductivity applied field av fiber diameter
silk solutions (%) (PEO/silk) (%) (µS) strength (kV/cm) (nm) ((std dev)
silk 7.2 7.2 240.0
blend 1 7.2 1/3 8.8 (1.6a) 216.5 0.50 840 ( 80
blend 2 7.2 1/4 8.3 (1.1a) 191.9 0.60 740 ( 150
blend 3 6.3 1/4 7.3 (1.0a) 185.0 0.60 700 ( 100
blend 4 6.0 1/3 7.4 (1.4a) 209.0 0.53 730 ( 50
blend 5 5.3 1/3 6.6 (1.3a) 182.2 0.55 720 ( 100
blend 6 4.1 1/2 5.8 (1.7a) 175.1 0.55 850 ( 60
blend 7 3.0 2/3 4.8 (1.8a) 154.3 0.55 880 ( 50
PEO 4.0 61.3 0.60 410 ( 90
a Weight percent of added PEO.

scans (spot 1000 µm, resolution 4, window 1000 eV) were
performed using a flood gun (charge neutralizer) setting of
5 eV and nickel wire mesh held over the sample to prevent
charging of the sample surface.
Results and Discussion
Preparation of Silk/PEO Blend Solutions. Under shear
conditions the amount of β-sheet precipitate formed from
aqueous fibroin solutions is affected by the solution tem-
perature, fibroin concentration, and stirrer rotation speed.33
Therefore, in the present study, all blend systems were gently
mixed at low temperature, 4 °C in water. This procedure
was used to maintain low shear in the concentrated fibroin
solution to avoid premature induction of crystallization.34
Shear and elongation play important roles in the natural
process of silk fiber formation.35 Despite these precautions,
the silk fibroin solutions used in the present experiments
exhibited the formation of some β-sheet precipitates36 even
at low concentration, 3 wt % silk, during stirring at room
temperature for blending.
If the silk solutions were stored at room temperature, there
was a rapid increase in viscosity and subsequent conversion
to a gel state. The formation of the gel state when PEO was
added into the solutions was much quicker than gel formation
for the silk solutions. The gelation time for the silk solutions
was usually 4-6 days at room temperature, which was
dependent upon concentration, versus 6-18 h for the various
blends with PEO. The blend solutions were frozen to reduce
the induction of crystallization. However, crystallization of
silk fibroin in the blend solutions nonetheless occurred due
to fluctuations in solution temperature when returning the
materials to ambient temperature. To overcome these dif-
ficulties, all blend solutions were mixed and stored at 4 °C
before electrospinning.
Properties of Silk/PEO Solutions. Aqueous silk solutions
without PEO did not electrospin; no fibers were formed
because the viscosity and surface tension of the solution were
not high enough to maintain a stable drop at the end of the
capillary tip. Higher concentrations of silk in water to
increase the viscosity of the solution resulted in gel forma-
tion. A stable drop at the end of the capillary tip was achieved
once the PEO was added to the silk solution at the ratios
shown in Table 1. However, adding PEO at concentrations
above 2 wt % led to the formation of opaque heterogeneous
solutions. Therefore blending with PEO and silk was
confined to a maximum of 1.8 wt % PEO (Table 1). The
viscosity of pure silk solution was much lower than the other
solutions, even at 7.2% as shown (Figure 1). The jet breaks
up into droplets as a result of surface tension in the case of
low viscosity liquids.7,11 For high viscosity liquids the jet
does not break up but travels to the grounded target.
Therefore, jet breakup depends on viscosity so that lower
viscosity solutions break up into droplets more readily.11,17,23
A small portion of PEO in the silk solution increased the
viscosity of the blends, and the viscosity of silk/PEO blend
solutions depended on the amount of PEO. The external
electric field was an important process parameter during
spinning (Table 1). High electric fields can cause hysteresis
between the onset and disruption of a stable jet and low plate
separations can be problematic for getting the submicrometer
fibers formed by a fluid instability following a jet.13 The
conductivities of silk and silk/PEO blend solutions were
higher than thoes of pure PEO solutions at room temperature
(Table 1). With their higher conductivity, the silk/PEO blend
solutions exhibited stable jet behavior at lower field strength
(less than 0.6 kV/cm).
Fiber Formation and Morphology of Electrospun Silk/
PEO. The addition of PEO to silk solutions generated a
viscosity and surface tension suitable for electrospinning. An
aluminum foil was used as the collection screen. The distance
between the tip and the collector was 20 cm, and flow rate
of all fluids was 0.02-0.05 mL/min. Before all solutions
were electrospun, Teflon was sprayed on the collection screen
to facilitate removal of the mat. As the potential difference
between the capillary tip and the aluminum foil counter
electrode was gradually increased 10-12 kV (E ) 0.5-0.6
kV/cm), the drop at the end of the capillary tip elongated
from a hemispherical shape into a cone shape, often referred
to as a Taylor cone. The applied voltages resulted in a jet
being initiated near the end of the capillary tip. Prior to
deposition on the collector, the jet showed a fluid instability,
the rapidly whipping jet, that leads to accelerated solidifica-
tion of the fluid jet and the formation of submicrometer
diameter solid fibers.8-13
The morphology and diameters of the electrospun fibers
were examined using high-resolution low-voltage SEM. All
silk/PEO blend solutions produced fine uniform fibers with
less than 800 nm (100 average fiber diameters (Table 1).
The fiber diameter is compared between sericin extracted
natural silkworm silk and the electrospun fibers (blend 5) in
Figure 2. The diameters of electrospun fibers were 40 times
Electrospinning Silk Biomacromolecules, Vol. 3, No. 6, 2002 1237

Table 2. XPS Results from the Surfaces of Electrospun Silk, PEO, and Silk/PEO Blends
O1 N1s C1s
binding energy binding energy binding energy silk/PEO
element (eV) atom % (eV) atom % (eV) atom % O1s/C1s N1s/C1s (mol/mol)
silka 530.3 24.7 398.4 18.9 284.6 56.4 0.44 0.33 100/0 (100/0)b
blend1 530.9 27.1 398.5 15.3 284.6 57.6 0.47 0.26 79/21 (75/25)
blend2 530.9 26.5 398.6 15.0 284.6 58.5 0.45 0.26 79/21 (80/20)
blend3 531.1 25.2 398.9 16.4 284.6 58.4 0.43 0.28 85/15 (80/20)
blend4 530.8 28.4 398.6 13.8 284.6 57.8 0.49 0.24 73/27 (75/25)
blend5 530.5 26.4 398.4 15.8 284.6 57.8 0.46 0.27 82/18 (75/25)
blend6 530.7 26.4 398.4 14.2 284.6 59.4 0.44 0.24 73/27 (67/33)
blend7 531.1 29.2 398.5 10.1 284.6 60.7 0.48 0.17 51/49 (60/40)
PEO 531.2 37.4 284.6 62.6 0.60 0/100 (0/100)
a For comparison, silk electrospun from HFIP (1.5 wt %). b In parentheses, blend composition (wt %) in solution.

smaller than the diameters of the native fibers after extraction

of sericin. Although a systematic study to determine the
optimal electrical field and concentration for these blend
electrospun fibers with regard to fiber diameter was not
completed, it appeared that the thickness of the electrospun
blend fibers was relatively independent of the concentration
of the silk and PEO dissolved in water electrospun under
these conditions. The individual electrospun fibers appeared
to be randomly distributed in the nonwoven mat. Micro-
graphs of the electrospun fibers from a silk/PEO solution in
water are shown in Figure 3.
XPS was used to estimate the surface composition of the
mats. Table 2 shows the respective peak intensities of O1s,
C1s, or N1s of PEO, silk fibroin, and silk/PEO blends from
electrospun mats. The ratios of N1s/C1s and O1s/C1s of the
silk mat were 0.33 and 0.44, respectively. In the case of the
silk/PEO mats, N1s/C1s decreased to 0.17 at minimum and
O1s/C1s increased to 0.49 at maximum. On the basis of these Figure 4. FTIR-ATR spectra of electrospun mat from silk/PEO (blend
ratios, we can estimate the fiber composition as shown in 5). Solid line is as spun; dotted line is after methanol/water (90/10
Table 2. The compositions reflect the solution composition v/v) treatment.
used in the spinning process. Since silk is relatively
hydrophobic, we anticipated a lower content of silk at the fiber, the conformation of the fibroin dramatically changes
fiber surface where spin from water. However, this was not to a semicrystalline structure, consisting of approximately
the case, perhaps due to the electrospinning process itself or 55% β-sheet crystallites dispersed throughout an amorphous
the small diameters of the fibers to limit hydrophobic/ or less-crystalline matrix.36 In the electrospun fibers from
hydrophilic partitioning. aqueous silk/PEO blend solutions, no β-sheet structure was
Solvent Treatment of Electrospun Mats. The mat was apparent even though the chains were elongated during
contacted with 90/10 (v/v) methanol/water for 10 min to electrospinning. Further study of these transitions should
induce crystallization of silk. The structural changes after provide additional options for control of solubility, mechan-
methanol treatment were observed by ATR-FTIR. As shown ical properties, and likely biological responses to these
in Figure 4, the structure of the fibroin protein in the nanometer diameter fibers.
electrospun fibers was predominantly random coil or silk I.
This amorphous structure promotes solubility in water.37,38 Conclusions
After methanol treatment, the structure changed to predomi-
nantly β-sheet (Figure 4), thus exhibiting behavior tradition- Electrospinning fibers from B. mori fibroin was studied
ally seen with reprocessed silkworm silk. This observation with a focus on blending with PEO and all aqueous
suggests that the electrospinning process preserves the ability processing. To improve the processibility of silk solutions
of this protein to self-organize into its native structure. Figure for electrospinning, while maintaining biocompatibility, PEO
5 shows scanning electron micrographs of electrospun fibers with molecular weight of 900 000 was successfully blended
after methanol treatment. After methanol treatment, the with the aqueous solution of fibroin. Successful formation
surface of fibers showed roughness apparently caused by of electrospun mats with less than 1 µm diameter fiber was
phase separation between silk fibroin and PEO, possibly due found, with the composition reflective of the solution
to extraction of the PEO in the methanol.39 In the aqueous concentrations. Traditional silk fibroin conformational transi-
solution of the silk gland, fibroin has a random coil tions were induced with methanol treatment of the fibers,
conformation. Usually, once this fibroin is spun into a cocoon suggesting that native structural features of the silk were
1238 Biomacromolecules, Vol. 3, No. 6, 2002 Jin et al.

Figure 5. Scanning electron micrographs of electrospun fibers after methanol treatment: (a) blend 1 (2 µm), (b) blend 2 (5 µm), (c) blend 3 (2
µm), (d) blend 4 (5 µm), (e) blend 5 (5 µm), (f) blend 6 (2 µm), and (g) blend 7 (10 µm). Numbers in parentheses are scale bars.
Electrospinning Silk
preserved in the electrospinning process. These results open
new directions in the fabrication of silk-based biomaterial
scaffolds for biomedical applications.
Acknowledgment. We thank the NIH (R01 DE13405-
01) and the DoD (Air Force) for support of this program
and Regina Valluzzi (Tufts University) for valuable help with
SEM and FT-IR characterization.
References and Notes
(1) Doshi, J.; Reneker, D. H. Electrospinning Process and Applications
of Electrospun Fibers. J. Electrostat. 1995, 35, 151-160.
(2) Bognitzki, M.; Czado, W.; Frese, T.; Schaper, A.; Hellwig, M.;
Steinhart, M.; Greiner, A.; Wendorff, J. H. Nanostructured fibers
via electrospinning. AdV. Mater. 2001, 13, 70-72.
(3) Stitzel, J. D.; Pawlowski, K. J.; Bowlin, G. L.; Wnek, G. E.; Simpson,
D. G.; Bowlin, G. L. Arterial smooth muscle cell proliferation on a
novel biomimicking, biodegradable vascular graft scaffold. J. Bio-
mater. Appl. 2001, 16, 22-33.
(4) Boland, E. D.; Bowlin, G. L.; Simpson D. G.; Wnek, G. E.
Electrospinning of tissue engineering scaffolds. Polym. Mater.: Sci.
Eng. 2001, 85, 51-52.
(5) Matthews, J. A.; Simpson, D. G.; Wnek, G. E.; Bowlin G. L.
Electrospinning of Collagen Nanofibers. Biomacromolecules 2002,
3, 232-238.
(6) Huang, L.; Nagapudi, K.; Apkarian, R. P.; Chaikof E. L. Engineered
Collagen-PEO Nanofibers and Fabrics. J. Biomater. Sci., Polym. Ed.
2001, 12, 979-93.
(7) Hohman, M. M.; Shin, M.; Rutledge, G. C.; Brenner, M. P.
Electrospinning and electrically forced jets. II. Applications. Phys.
Fluids 2001, 13, 2221-2236.
(8) Baumgarten, P. K. J. Colloid Interface Sci. 1971, 36, 71.
(9) Reneker, D. H.; Yarin, A. L.; Fong, H.; Koombhongse, S. Bending
instability of electrically charged liquid jets of polymer solutions in
electrospinning. J. Appl. Phys. 2000, 87, 4531-4547.
(10) Shin Y. M.; Hohman M. M.; Brenner M. P.; Rutledge G. C.
Electrospinning: A whipping fluid jet generates submicron polymer
fibers. Appl. Phys. Lett. 2001, 78, 1149-1151.
(11) Hohman, M. M.; Shin M.; Rutledge G.; Brenner M. P. Electro-
spinning and electrically forced jets. I. Stability theory. Phys. Fluids
2001, 13, 2201-2220.
(12) Yarin, A. L.; Koombhongse, S.; Reneker, D. H. Bending instability
in electrospinning of nanofibers. J. Appl. Phys. 2001, 89, 3018-
3026.
(13) Shin, Y. M.; Hohman, M. M.; Brenner M. P.; Rutledge G. C.
Experimental Characterization of Electrospinning: the Electrically
Forced Jet and Instabilities. Polymer 2001, 42 9955-9967.
(14) Fong H.; Chun I.; Reneker D. H. Beaded nanofibers formed during
electrospinning. Polymer 1999, 40, 4585-4592.
(15) Jaeger R.; Schönherr, H.; Vancso, G. J. Chain packing in electro-
spun poly(ethylene oxide) visualized by atomic force microscopy.
Macromolecules 1996, 29, 7634-7636.
(16) Deitzel J. M.; Kleinmeyer, J. D.; Hirvonen J. K.; Tan N. C. B.
Controlled deposition of electrospun poly(ethylene oxide) fibers.
Polymer 2001, 42, 8163-8170.
(17) Deitzel J. M.; Kleinmeyer J.; Harris D.; Tan N. C. B. The effect of
processing variables on the morphology of electrospun nanofibers
and textiles. Polymer 2001, 42, 261-272.
(18) Bunning, T. J.; Jiang, H.; Adams, W. W.; Crane, R. L.; Farmer, B.;
Kaplan, D.; Application of Silk. In Silk Polymers; Material Science
and Biotechnology; Kaplan, D. L., Adams, W. W., Farmer, B., Viney,
C., Eds.; ACS Symposium Series 544; Oxford University Press:
Charlottesville, VA, 1993; pp 351-358.
(19) Martin, D. C.; Tao, J.; Buchko, C. J. Processing and Characterization
of Protein Polymers. In Protein-Based Materials; McGrath, K.,
Kaplan, D., Eds.; Birkhauser: Boston, MA, 1997; pp 339-370.
Biomacromolecules, Vol. 3, No. 6, 2002 1239
(20) Hudson, S. M. The Spinning of Silk-like Proteins into Fibers. In
Protein-Based Materials; McGrath, K., Kaplan, D., Eds.; Birk-
hauser: Boston, MA, 1997; pp 313-337.
(21) Huang, L.; McMillan, R. A.; Apkarian, R. P.; Pourdeyhimi, B.;
Conticello, V. P.; Chaikof, E. L. Generation of synthetic elastin-
mimetic small diameter fibers and fiber networks. Macromolecules
2000, 33, 2989-2997.
(22) Anderson, J. P.; Nilsson, S. C.; Rajachar, R. M.; Logan, R.;
Weissman, N. A.; Martin, D. C. Biomolecular materials by design.
In BioactiVe Silk-like Protein Polymer Films on Silicon DeVices;
Alper, M., Bayley, H., Kaplan, D., Navia, M., Eds.; Materials
Research Society: Pittsburgh, PA, 1994; Vol. 330, pp 171-177.
(23) Buchko C. J.; Chen L. C.; Shen Y.; Martin D. C. Processing and
microstructural characterization of porous biocompatible protein
polymer thin films. Polymer 1999, 40, 7397-7407.
(24) Buchko, C. J.; Kozloff K. M.; Martin D. C. Surface characterization
of porous, biocompatible protein polymer thin films. Biomaterials
2001, 22, 1289-1300.
(25) Zarkoob, S.; Reneker, D. H.; Eby, R. K.; Hudson, S. D.; Ertley, D.;
Adams, W. W. Generation of synthetic elastin-mimetic small diameter
fibers and fiber networks. Polym. Prepr. (Am. Chem. Soc., DiV.
Polym. Chem.) 1998, 39, 244-245.
(26) Asakura, T.; Kaplan, D. L. Silk Production and Processing. In
Encylopedia of Agricultural Science; Arntzen, C. J., Ritter, E. M.,
Eds.; Academic Press: New York, 1994; Vol. 4, pp 1-11.
(27) Kaplan, D. L.; Mello, C. M.; Arcidiacono, S.; Fossey, S.; Senecal,
K.; Muller, W. Silk. In Protein-Based Materials; McGrath, K.,
Kaplan, D., Eds.; Birkhauser: Boston, MA, 1997; pp 103-131.
(28) Huang, L.; Apkarian, R. P.; Chaikof E. L. High-Resolution Analysis
of Engineered Type I Collagen Nanofibers by Electron Microscopy.
Scanning 2001, 23, 372-75.
(29) Kim, S. W. Nonthrombogenic Treatments and Stragegies. In Bio-
materials Science: An introduction to Materials in Medicine; Ratner,
B. D., Hoffman, A. S., Schoen, F. J., Lemons, J. E., Eds.; Academic
Press: New York, 1996; pp 297-308.
(30) Alcantar, N. A.; Aydil, E. S.; Israelachvili, J. N. Poly(ethylene glycol)-
coated biocompatible surfaces. J. Biomed. Mater. Res. 2000, 51, 343-
351.
(31) Griffith, L. G. Polymeric Biomaterials, Acta Mater. 2000, 48, 263-
277.
(32) Sofia, S.; McCarthy, M. B.; Gronowicz G.; Kaplan, D. L. Function-
alized silk-based biomaterials for bone formation. J. Biomed. Mater.
Res. 2001, 54, 139-148.
(33) Trabbic, K. A.; Yager, P. Comparative Structural Characterization
of Naturally- and Synthetically-Spun Fibers of Bombyx mori Fibroin.
Macromolecules 1998, 31, 462-471.
(34) Willcox, P. J.; Gido S. P.; Muller W.; Kaplan D. L. Evidence of a
Cholesteric Liquid Crystalline Phase in Natural Silk Spinning Process.
Macromolecules 1996, 29, 5106-5110.
(35) Inoue, S.-I.; Magoshi J.; Tanaka, T.; Magoshi, Y.; Becker, M. Atomic
Force Microscopy: Bombyx mori Silk Fibroin Molecules and Their
Higher Order Structure. J. Polym. Sci., Part B: Polym. Phys. 2000,
38, 1436-1439.
(36) Kobayashi, M.; Tanaka, T.; Inoue, S.; Tsuda, H.; Magoshi, J.;
Magoshi, Y.; Becker, M. A. Rheological Behavior of Silk Fibroin
Aqueous Solution: Gel-Sol Transition and Fiber Formation. Polym.
Prepr. 2001, 42, 294-295.
(37) Valluzzi, R.; Szela, S.; Avtges, P.; Kirschne, D.; Kaplan, D.
Methionine Redox Controlled Crystallization of Biosynthetic Silk
Spidroin. J. Phys. Chem. B 1999, 103, 11382-11392.
(38) Wilson, D.; Valluzzi, R.; Kaplan, D. Conformational Transitions in
Model Silk Peptides. Biophys. J. 2000, 78, 2690-2701.
(39) Vandermiers, C.; Damman, P.; Dosiere, M. Static and quasielastic
light scattering from solutions of poly(ethylene oxide in methanol).
Polymer 1998, 39, 5627-5631.
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