Full Paper

Impact of Solvent on Electrospinning of Zein

and Analysis of Resulting Fibersa

Gordon W. Selling,* Atanu Biswas, Alpa Patel, Dennis J. Walls,

Christopher Dunlap, Yen Wei

Zein fibers have been produced by electrospinning from acetic acid, aqueous methanol,
ethanol and isopropyl alcohol. Alcohol solutions produced fibers that were predominantly
ribbons. Fibers spun from acetic acid solution have a round morphology with a narrower
distribution of diameters when spun under suitable conditions. The IR spectra of electrospun
fibers display increased absorbance at 1 650 cm
1 relative to starting material, indicative of
increased a-helical structure. Raman spectra of fibers spun from acetic acid solution had
spectral differences, having increased absorbance at 680, 750 and 860 cm
1, versus fibers spun
from alcoholic solvents suggesting different tertiary structure within the fiber, which may
result from different structures in solution. Polarized Raman spectroscopy taken parallel and
perpendicular to the fiber axis displayed no differences, suggesting similar secondary
and tertiary structures in these directions. All of the
fibers had some degree of birefringence demonstrat-
ing the presence of orientation. The smaller fibers
were highly birefringent throughout the fiber, while
the larger fibers had orientation at the surface
only. Quality fibers could not be produced from
N,N-dimethylformamide, acetone/water, acetic acid/
water, 8 M urea/water or 10% NaOH/water zein
solutions.

G. W. Selling, A. Biswas Introduction

Plant Polymer Research, National Center for Agricultural
Utilization Research, Agricultural Research Service, United States
Department of Agriculture, 1815 N. University St., Peoria,
IL 61604-3902, USA
Fax: (þ1) 309-681-6338, (þ1) 309-681-6681;
E-mail: sellingg@ncaur.usda.gov
A. Patel, Y. Wei
Drexel University, Department of Chemistry, 3141 Chestnut Street
Philadelphia, PA 19104-2875, USA
D. J. Walls
E.I. du Pont de Nemours and Co. Inc., Experimental Station,
200 Powder Mill Road, Wilmington DE 19803, USA
C. Dunlap
Crop Biprotection Research, National Center for Agricultural
Utilization Research, Agricultural Research Service, United States
Department of Agriculture, 1815 N. University St., Peoria, IL
61604-3902 USA
Zein, the major storage protein of corn and a by-product
of the bio-ethanol industry, was used extensively in the
fibers industry through the early 1960’s. These textile
manufacturers lost market share when less expensive
petroleum-based products became available.[1,2] Today
zein is predominantly used to coat tablets or food.[3] Efforts
are being expended to develop economical routes to
provide industrial quantities of zein.[4,5] Developing a
technology that will allow zein to re-enter the fibers
market will improve the economics of the bio-ethanol
a
Names are necessary to report factually on available data; however,
the USDA neither guarantees nor warrants the standards of the
product, and the use of the name by the USDA implies no approval
of the product to the exclusion of others that may also be suitable.

Macromol. Chem. Phys. 2007, 208, 1002–1010

1002 ß 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/macp.200700056
Impact of Solvent on Electrospinning of Zein and Analysis of Resulting Fibers
industry and allow precious non-renewable feed stocks to
be used in this market.
Historically, in order for a zein textile fiber to retain
properties during fabric processing, it was cross-linked
with formaldehyde.[6] Commercial use of formaldehyde
requires significant investment to be performed safely.
Other chemistries are being explored as an alternative to
formaldehyde to improve the properties of zein based
materials,[7–9] which could result in a suitable technology
for use in making fibers. While these new routes may
improve the physical properties of zein, making fibers
using the chemically modified zein may be difficult.
Traditional synthetic fiber spinning techniques, such as
wet, dry, melt or reaction spinning, in the lab may require
significant investment. Electrospinning is a versatile
technique that can easily produce fibers in a laboratory
setting.[10–12] Very small amounts of polymer (gram
quantities or less) can be used to produce fibers using
this technique. In electrospinning a high voltage is applied
to a spinneret so that the spinning solution becomes
charged. When sufficient voltage is applied to the
spinneret, the small drop at the tip becomes highly
charged and the drop will elongate in shape taking on a
conical shape (called a Taylor cone). The shape is caused by
electrostatic repulsion within the droplet as well as the
Columbic force caused by the applied electric field between
the spinneret and the grounded target. When these forces
are sufficient to overcome the solution’s surface tension
and viscoelasticity, a jet of polymer solution will be forced
from the Taylor cone and speed to the grounded target
(Figure 1). As the jet moves towards the target, it
undergoes chaotic stretching and whipping, and the
solvent will begin to evaporate. If the polymer and its
solution properties are appropriate, i.e. suitable molecular
weight, chain entanglements, extensional viscosity etc.,
fibers will form. However, if these attributes are not
appropriate, electrospraying will result. If the required
Figure 1. Electrospinning set-ups using metered flow (A) and
gravitational flow (B) – 1: syringe pump; 2: syringe containing
protein solution; 3: plastic shield; 4: high voltage variable power
supply; 5: needle (spinneret), 6: polymer jet and spinning fiber; 7:
grounded target; 8: ground wires; 9: electrode immersed in
protein solution; 10: pipette containing protein solution.
Macromol. Chem. Phys. 2007, 208, 1002–1010
ß 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
attributes are intermediate then fibers may form, but they
will have beads of polymer along their length.
Electrospinning has been demonstrated on various
proteins such as collagen,[13] wheat gluten,[14] fibrogen[15]
and zein.[16,17] Zein was electrospun using 80% ethanol
(EtOH)/water as the solvent. In this work zein gave
electrospun ribbon fibers having diameters of 1 to 2 mm
when spun above 21% protein at a potential of 15 kV and a
distance of 10 cm between the target and the spinneret.
These fibers were not suitable for textile or non-textile
applications as they would be weak and subject to
dramatic property changes with changes in humidity.
While cross-linking zein fiber mats after production with
hexamethylene diisocyanate gave some improvements,[17]
this reagent is highly toxic and the post-fiber production
step may be cost-prohibitive. Depending on the chemistry
to be used to improve zein fiber properties, 80% EtOH/
water may not be a suitable solvent to chemically modify
the zein. Low molecular weight carboxylic acids and
amides are classic primary solvents for zein.[1] Common
two component solvent systems include low molecular
weight alcohols with water, acetone with water, 8 M urea
in water and 10% sodium hydroxide in water.[1] Solvent
systems other than 80% EtOH/water may have attributes
that may be attractive to chemists for derivatization of
zein. It has been shown that the morphology of spun fibers
can change with solvent.[18] This paper reports our efforts
in determining how changes in solvent effect the
electrospinning and the resulting morphology of zein.
Solvents evaluated were 60–90% EtOH/water, 60–80%
isopropyl alcohol (IPA)/water, 80% methanol (MeOH)/
water, 60% acetone/water, acetic acid (AcOH), dimethyl-
formamide (DMF), 8 M urea in water and 10% sodium
hydroxide in water.
Experimental Part
Materials and Equipment
Zein was obtained from Freeman Industries, LLC (Tuckahoe, NY)
Lot# 40004081 (FZ4081; % protein 89.5, % fat 3.0, % ash 0.6, % water
4.4). All solutions were prepared on a weight to weight basis.
Deionized water was used throughout. All reagents were of
reagent grade and used as received (Sigma-Aldrich, St. Louis, MO).
The Power Supply was a Gamma Model ES50P-10W (Gamma High
Voltage Research, Inc., Ormond Beach, FL). The syringe pump was a
KDS 100 Series (KD Scientific, Holliston, MA) using 5 mL syringes
with 100 long flat tipped 17 gauge needles. A quick connector,
DR18-250-C (Panduit, Corp., Tinley Park, IL) was used to connect
the hot wire from the power supply to the needle. The target
was a 1200 square sheet of 1/800 thick copper, held upright in a
non-conductive material, covered in aluminum foil. If optical
microscopy was desired on a particular sample, a microscope slide
was taped to the foil so that fiber could deposit on the slide.
Eighteen gauge stranded wire fitted with an alligator clip was
www.mcp-journal.de 1003

used for connecting the target to ground. Optical microscopy,
using plain or polarizing light, was performed using an Olympus
CX31-P microscope (Center Valley, PA) fitted with a 10 eyepiece,
using 4, 10, 20 and 40 strain-free objectives and a polarizing
intermediate attachment. Microscope pictures were taken using
an Olympus DP12 camera (Center Valley, PA). Infrared spectra
were obtained on a Thermo Nicolet Avatar 370 FTIR where the
samples were tested in KBr pellets. Scanning electron microscopy
(SEM) was performed after sputter coating the fibers with Au-Pd or
Pt and then examined by either a JEOL 6400 V (JEOL USA, Inc.,
Peabody, MA) or a Phillips XL-30 ESEM, (Eindhoven, The Nether-
lands). Surface tension was measured using an FTA4000 video
drop shape analysis system (First Ten Angstroms Inc, Portsmouth,
VA) using a 22 gauge blunt tip needle. Viscosity was measured on
a TA Instruments AR 2000 controlled-stress rheometer using a
60 mm acrylic parallel plate using a peltier plate for temperature
control. Viscosities were measured at shear rates of 1 through
100 s
1 at 25 8C. Raman spectroscopy was obtained using a
LabRam HR Raman microscopy (Horiba Jobin Jvon, Edison, NJ)
Interfacial Tension Measurements
The pendant drop method was used to determine the interfacial
tension of the protein/solvent solutions. The images were
analyzed using the Laplace-Young equation with the manufac-
turer’s software. Measurements were performed at 22 8C. The
values reported represent an equilibrium surface tension deter-
mined 10 s after drop formation. The reported values are the
average of a minimum of 3 separate measurements. Error is
reported at one standard deviation.
Raman Spectroscopy
Raman measurements were made using excitation at 785 nm
through a 100 long working distance objective (Leica, Bannock-
burn, IL). Power levels at the sample were maintained at 1 mW.
The polarization measurements were made by aligning the
polarization of the laser either parallel or perpendicular to the axis
of the fiber with the use of a 1/2 wave plate. The collected Raman
scatter was polarization-analyzed with a polarizer oriented in the
same direction as the incident laser polarization relative to the
fiber. A quarter wave plate was inserted into the collection optical
pathway to minimize differences in instrument response
associated with differences in polarization of the collected
radiation.
Preparation of Electrospun Fibers
Concentrations of solutions are on a weight basis where the
amount of zein used was based on its dry weight. For example, to
7.76 g of AcOH was added 2.23 g (2 g dry protein) of zein resulting
in a 20% zein solution in AcOH. This solution was allowed to stir
for a minimum of 15 min. There were two methods used to
prepare fibers, using a syringe pump to supply solution or by using
a pipette and gravity flow.
Macromol. Chem. Phys. 2007, 208, 1002–1010
1004 ß 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
G. W. Selling, A. Biswas, A. Patel, D. J. Walls, C. Dunlap, Y. Wei
Syringe Pump
When using a syringe pump, the desired amount of solution was
added to a 5 mL syringe. The syringe was placed on the syringe
pump and then the tip was slid through a hole, of a size to allow
the end of the syringe to pass through it, in a supported 3/800
polyacrylate sheet. The polyacrylate sheet was used to insure that
electricity does not arc back to the syringe pump. A 17 gauge
1 inch needle with a flat tip having a quick disconnect terminal
attached to it was threaded onto the syringe. The hot wire from
the power supply was attached to the quick disconnect terminal.
The copper target was covered with a sheet of aluminum foil, and
an alligator clip was attached to the target so that both the foil and
the copper were in contact and then the ground wire were
attached to the ground on the power supply. The distance from the
target to the needle tip was set to the desired distance and
the syringe pump was set to the desired flow rate. The power
supply was then turned on and set to the desired voltage.
Gravity Flow
When using gravity to supply the protein solution, approximately
2 mL of the desired protein solution was placed in a glass pipette.
An electrode, to which was attached the hot wire from the power
supply, was slid into the pipette making contact with the solution.
The same procedure (vide supra) was then used in preparing the
target and setting the voltage. The distance from the pipette tip to
the target was 11 cm.
For both procedures, at times while spinning the needle or
pipette may plug as the solvent evaporated from the spinning
solution. When this occurred, the power supply was turned off,
and the tip was wiped clean. Spinning was then continued until
the desired amount of fiber was produced.
Results and Discussion
Spinning Performance
Detailed results from electrospinning zein using various
solvents can be found in Table 1. When the concentration
of zein in 60% EtOH/water solution is above 20% protein
(Sample A) production changed from electrospraying to
electrospinning. The Sample A fibers still had many beads
along the fiber. Spinning continuity improves as the
concentration is further increased. The fibers produced
from 27–30% protein solutions using EtOH/water as
solvent (Samples B–H) have ribbon morphologies. Using
the same zein concentration and spinning conditions, it
was found that the amount of water present in the EtOH
did not affect the fiber morphology (Figure 2a–d) as long as
the zein was soluble (60–90% EtOH, Samples B–E).
Sample F ribbons have a diameter of 1–8 mm, with the
majority between 1 and 2 mm (Figure 3a). When Sample F
fibers were examined by optical microscopy using two
orthogonal polarizing filters (cross-polars), they were
birefringent (Figure 3b normal lighting and 3c polarizing
filters crossed). When the sample is rotated, the fibers will
DOI: 10.1002/macp.200700056
Impact of Solvent on Electrospinning of Zein and Analysis of Resulting Fibers

Table 1. Spinning conditions and fiber properties of various zein formulations.

Sample % Zein Solvent Potential Distance Syringe pump Fiber Fiber

flow rate Morphology Diameter

kV cm mL  hS1 or mm
gravity flow
Small Average High

A 20 60% 20 10 Gravity Ribbon 0.6 2.3 2.8

EtOH/water w/beads
B 27 60% 20 10 Gravity Ribbon 1.1 1.6 2.9
EtOH/water
C 27 70% 20 10 Gravity Ribbon 0.6 1.6 2.9
EtOH/water
D 27 80% 20 10 Gravity Ribbon 0.5 2.1 4.3
EtOH/water
E 27 90% 20 10 Gravity Ribbon 1.1 1.9 2.3
EtOH/water
F 30 80% 10 10 Gravity Ribbon 1.5 2.1 8.0
EtOH/water
G 27 80% 20 10 8 Ribbon 1.1 2.5 3.7
EtOH/water
H 27 90% 20 10 8 Ribbon 1.0 2.9 4.3
EtOH/water
I 27 60% 20 10 8 Ribbon 1.0 2.3 6.2
IPA/water
J 27 80% 20 10 8 Ribbon 1.4 3.3 6.4
IPA/water
K 30 80% 20 10 8 Ribbon 1.5 3.2 4.0
IPA/water
L 30 80% 20 10 8 Ribbon 1.4 3.5 4.4
MeOH/water
M 27 60% 20 10 8 Electrospray
Acetone/water
N 27 60–90% 20 10 8 Electrospray
AcOH/ water
O 20–23 AcOH 20 10 8 Electrospray
P 27 AcOH 20 10 8 Rounda) 0.4 1.0 1.6
Q 30 AcOH 20 10 8 Rounda) 1.1 2.8 4.0
R 30 AcOH 20 10 4 Ribbon & 1.0 2.2 4.1
Rounda)
S 30 AcOH 20 10 12 Rounda) 1.7 4.0 5.6
T 30 AcOH 10 10 8 Rounda) 1.5 2.2 4.4
a)
U 30 AcOH 30 10 8 Round 1.5 2.8 4.6
V 30 AcOH 40 10 8 Ribbonb) 1.2 2.4 4.4
b)
W 30 AcOH 20 5 12 Ribbon 1.3 4.1 10.1
X 30 AcOH 20 20 12 Rounda) 2.1 2.7 3.5

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 G. W. Selling, A. Biswas, A. Patel, D. J. Walls, C. Dunlap, Y. Wei

Table 1. (Continued)

Sample % Zein Solvent Potential Distance Syringe pump Fiber Fiber

flow rate Morphology Diameter

kV cm mL  hS1 or mm
gravity flow
Small Average High

Y 30 AcOH 30 10 12 Rounda) 1.5 2.9 3.6

Z 27 DMF 20 11 Gravity Electrospray
AA 27 DMF 20 10 8 Electrospray
BB 30 DMF 20 10 8 Electrospray
CC 35 DMF 20 11 Gravity Round w/beads 0.3 0.5 0.8
DD 40 DMF 20 10 8 Would not spin
EE 20 8M urea 20 10 8 Electrospray
FF 10 10% 20 10 8 Electrospray
NaOH

a)
Improved spinning continuity relative to alcoholic solvents; b)Poorer spinning continuity relative to other AcOH items.

increase or diminish in brightness with rotation. Birefrin-
gence was observed on the edges of electrospun wheat
gluten fibers.[14] In the centers of the largest fibers (8 mm)
the retardation color was approximately 70  20 nm when
the fiber was at maximum brightness. This gives a
birefringence of 0.009  0.002 by using Equation (1) and
assuming a fiber thickness of 8.0  1.0 mm.[19] These fibers
had higher birefringence at their edges, with retardation
colors approaching 175  20 nm. Given that it is very
difficult to determine the thickness of an edge, we could
not calculate the birefringence at that point. The smaller
fibers (1 mm) were birefringent throughout their
diameter and had a retardation color corresponding to a
retardation of approximately 220  20 nm, giving a
birefringence of 0.22  0.03 assuming a fiber thickness
of 1.0  0.15 mm. This level of birefringence demonstrates a
high degree of polymer orientation. Replacing EtOH with
either IPA or MeOH (Samples I – L) did not significantly
change the fiber morphology or spinning performance as
long as the zein was soluble at concentrations of 20% or
higher.
Retardation ðnmÞ
Birefringence ¼ (1)
Sample Thickness ðnmÞ

When acetone was used in place of EtOH to dissolve the

Figure 2. SEM analysis of Sample B–E fibers at 2 000.
zein, as in a 60% acetone/water solution (Sample M),
electrospraying resulted. The surface tension of a 60%
acetone/water solution will be approximately 32 dyn 
cm
1[20] which is slightly higher than that of 90% EtOH/
water (27.6  0.3 dyn  cm
1) which may have a negative
impact on spinning. The dielectric constant for the
acetone/water solution will be approximately 28[21] versus
approximately 37 for 90% EtOH/water.[22] Given that
higher polarity has been implicated in poorer spinning, the
lower dielectric constant may actually be beneficial to
spinning continuity.[23] The bulk viscosity of the acetone/
water solution was similar to that of the EtOH/water
solution. The extensional viscosity of the solution will also
play a role in the ability of a solution to form fibers and
these investigations will be undertaken on this solution
and others. It is not certain which factor(s) is playing a
major role in the inability to spin zein from this solution.

Macromol. Chem. Phys. 2007, 208, 1002–1010

1006 ß 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/macp.200700056
Impact of Solvent on Electrospinning of Zein and Analysis of Resulting Fibers
Figure 3. SEM and optical microscopic analyses of Sample F fibers. a: SEM picture taken at
500. b: Optical microscope picture taken using normal lighting at 200. c: Same sample
using cross-polarizing filters at 200.
When AcOH was used in place of EtOH, as in 60–90%
AcOH/water solutions (Samples N), electrospraying
resulted. However, when glacial AcOH was used to
produce a zein solution at 27–30% protein (Samples
P–Y), it spun very well. The spinning continuity of the
glacial AcOH solution was much better than that obtained
when using EtOH/water solutions. This may be due to the
lower vapor pressure of the AcOH which would reduce
the amount of solvent that was evaporating at the needle
tip. The viscosity of a 27% zein AcOH solution was found to
be 1.0 Pa  s while this same concentration in 80% EtOH
gave a viscosity of 0.4 Pa  s (both conducted at a shear
rate of 1 s
1). These viscosities are very similar, so that
the differences observed in spinning performance can
not be attributed to bulk viscosity differences. It may
also be influenced by the lower surface tension of the
AcOH solution, 22.3  0.3 dyn  cm
1 for AcOH zein
solution (versus 25.2  0.3 dyn  cm
1 for AcOH) and
25.2  0.4 dyn  cm
1 for 90% EtOH/water zein solution
(versus 27.6  0.3 dyn  cm
1 for 90% EtOH/water). Glacial
AcOH also has the lowest dielectric constant at 6.2 which
may reduce the elongational forces imposed during
spinning.[23] With the addition of water to AcOH, the
dielectric constant would increase and the forces imposed
on the solution may increase to the point that the fiber
integrity may not be maintained.[23]
When spinning from AcOH where the potential was
between 10 and 20 kV the fibers produced were
predominantly round with few ribbons present. Sample
Figure 4. SEM and optical microscopy analyses of Sample P fibers. a: SEM picture taken at pure DMF) than the other organic
2 000. b: Optical microscope picture taken using normal lighting at 200. c: Same solvents. When this higher surface
sample using cross-polarizing filters at 200.
Macromol. Chem. Phys. 2007, 208, 1002–1010
ß 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
P provided round fibers with a rela-
tively narrow distribution of dia-
meters ranging from 0.4–1.6 mm
(Figure 4a). The influence of solvent
on a fiber’s morphology using other
polymers has been observed pre-
viously.[24,25] Sample P fibers produced
from glacial AcOH solutions were
also birefringent throughout the fiber
cross-section having a retardation
color of 200  20 nm, giving a bire-
fringence value of 0.22  0.03 assum-
ing a fiber thickness of 1.0  0.2 mm. (Figure 4b normal
lighting and 4c polarizing filters crossed).
With this change in morphology on changing solvents,
additional work was carried out investigating how
spinning conditions affect the morphology of zein fibers
produced from AcOH solutions. At a zein concentration of
20–23% in AcOH, Sample O, electrospraying resulted. This
may be a result of changes in extensional viscosity[26] or
reduced polymer chain entanglements[27] so that the
threadline can not withstand the forces imposed during
spinning. The morphology of fibers (Samples Q–T) pro-
duced with potentials of 10–20 kV at 30% protein were
similar to those fibers produced at 27% protein. The fibers
were predominantly round with slightly larger dimen-
sions; with average diameters of 2.8 mm and a range of
1.1 to 5.6 mm. As the voltage was increased from 30 to
40 kV at 30% protein (Samples U, V and Y) the fibers had
more ribbon character, with diameters of 1.5 to 4.6 mm,
with average diameters of 2.8 mm. When the distance to
the target was reduced to 5 cm and potential set to 20 kV
(Sample W) spinning continuity was poorer than other
items and the fibers had more ribbon character. Produc-
tivity had little impact on fiber morphology (compare
Samples P, R and S). Optimum spinning conditions using
AcOH as solvent were 27–30% protein, 20 kV, 10 cm
distance, and 8–12 mL  h
1.
Zein is soluble in DMF, and when solutions of 27–30%
protein were spun (Samples Z–BB), using gravity flow
or metered flow, electrospraying resulted (Figure 5a).
When the protein concentration was
increased to 35% protein (Sample CC),
there was a mix of beads and very fine
fibers (0.25–0.75 mm) (Figure 5b).
Further increasing the concentration to
40% (Sample DD) produced a solution
that did not spin or electrospray at the
applied potential. DMF zein solutions
have higher surface tension (31.7  0.2
dyn  cm
1 vs. 36.7  0.8 dyn  cm
1 for
tension is combined with the higher
www.mcp-journal.de 1007
 G. W. Selling, A. Biswas, A. Patel, D. J. Walls, C. Dunlap, Y. Wei

from the basic solution may be due to the low protein

concentration, high surface tension or protein degradation.
These solvent systems are not suitable for electro-
spinning zein.

Infrared Analysis
With the observation of birefringence in the electrospun
fibers, orientation must be present. To determine if this
Figure 5. SEM analysis of electrospun zein fibers of Samples BB
orientation effects other attributes of zein, the IR spectra
and CC at 2 000.
was measured of spun fiber and starting material. The
spun fiber was frozen in liquid nitrogen, ground and then
viscoelasticity obtained at protein concentrations of 35%
had its IR spectra recorded. Shown in Figure 7 is the
or higher, solution will not jet from the tip of the needle at
carbonyl region of the IR spectra of ground spun fiber
the potentials used (higher potentials could not be used as
(Sample G) and starting material. The spectra have been
electrical arcs formed from the needle tip to the syringe
normalized by integrating the entire curve and then
pump in spite of the plastic shield).
determining the contribution for each absorbance at
Zein is soluble in 8 M urea and highly basic water
2 cm
1 intervals. The carbonyl peaks are significantly
solutions. Industrially these solutions may have certain
different indicative of a change in structure that occurs
advantages over organic solvent based systems depending
during the electrospinning process. The increase in
on the desired chemical process. When a 20% zein solution
absorbance at 1 650 cm
1 is indicative of an increase
in 8 M urea (higher concentrations were not soluble) was
in alpha helical character.[28,29] Electrospinning has
spun (Sample EE) electrospraying resulted. These condi-
previously been shown to alter the secondary structure
tions gave reasonably good electrospinning of zein in 80%
of silk.[30] The birefringence observed and the increased
EtOH/water. The high surface tension of this aqueous
alpha helical character observed may be a result of
system (61.5  0.9 dyn  cm
1) will play a major role in the
structural changes that take place under the shear present
inability to form fibers. The Sample EE droplets ranged in
during spinning.
size from 20 to 450 mm. When the zein solution was
electrosprayed onto a glass slide and the resulting droplets
were examined using an optical microscope using cross-
Raman Spectroscopy
polars, the droplets were highly birefringent (Figure 6a
and 6b). This would be due to the high concentration of Raman spectra has been used to define the differences in
urea, with crystallization of urea during drying. When a the environment around certain amino acid residues such
10% zein (higher concentrations were not soluble) solution as tryptophan or tyrosine.[31–34] With the differences
in 10% NaOH was spun at the same conditions (Sample FF), observed in degree of birefringence and morphology
electrospraying resulted. Droplet sizes were of a similar between fibers produced from 80% EtOH/water (Sample
size as those from the urea solution, however, the droplets G) and AcOH (Sample P) we examined the Raman spectra
were not birefringent. The inability to obtain fibers of the generated fibers. The Raman spectra for Samples G

Figure 6. Optical microscopy analyses of Sample EE. a: Electro-

sprayed zein under normal lighting at 200, droplets 60 mm in
diameter. b: Same sample and conditions using cross-polars,
second order retardation color of sky blue observed (photo in Figure 7. IR spectra of zein as supplied (– – –) and ground
gray scale). electrospun Sample G zein fiber ( ).

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1008 ß 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/macp.200700056

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DOI: 10.1002/macp.200700056