polymers

Article
White-Light Emission of Dye-Doped Polymer
Submicronic Fibers Produced by Electrospinning
Monica Enculescu * ID
, Alexandru Evanghelidis ID
and Ionut Enculescu
Group of Functional Nanostructures, National Institute of Materials Physics, Atomistilor 405A, P.O. Box MG-7,
077125 Magurele-Bucharest, Romania; alex.evanghelidis@infim.ro (A.E.); encu@infim.ro (I.E.)
* Correspondence: mdatcu@infim.ro; Tel.: +40-21-3690185




Received: 31 May 2018; Accepted: 2 July 2018; Published: 4 July 2018


Abstract: Lighting and display technologies are evolving at tremendous rates nowadays; new
device architectures based on new, microscopic building blocks are being developed. Besides
high light-emission efficiencies, qualities including low cost, low environmental impact, flexibility,
or lightweightness are sought for developing new types of devices. Electrospun polymer fibers
represent an interesting type of such microscopic structures that can be employed in developing new
functionalities. White-light-emitting fiber mats were prepared by the electrospinning of different
dye-doped polymer solutions. Two approaches were used in order to obtain white-light emissions:
the overlapping of single-dye-doped electrospun fiber mats, and the electrospinning of mixtures of
different ratios of single-dye-doped polymer solutions. Scanning electron microscopy (SEM) was used
to investigate the morphologies of the electrospun fibers with diameters ranging between 300 nm
and 1 µm. Optical absorption and photoluminescence (PL) were evaluated for single-dye-doped
submicronic fiber mats, for overlapping mats, and for fiber mats obtained from different compositions
of mixtures. Depending on the ratios of the mixtures of different dyes, the luminance was balanced
between blue and red emissions. Commission Internationale de L’Eclairage (CIE) measurements
depict this fine-tuning of the colors’ intensities, and the right composition for white-light emission of
the submicronic fiber mats was found.

Keywords: electrospinning; dye-doped polymer; submicronic fibers; white-light emission;

tunable luminescence

1. Introduction
The electrospinning technique is a simple procedure to obtain polymeric and subsequently
metallic, semiconducting, or ceramic fibers from solutions or melts [1–4]. The process was proven
to be a low-cost, flexible, and scalable method to produce microfibers and nanofibers. Differently
arranged (randomly or aligned) fibers with various morphologies can be obtained depending on the
geometry of the electrospinning set-up [5–8]. A fine control of the electrospinning process parameters
consequently results in a fine-tuning of the fibers’ properties [9,10], such as dimension, morphology
(including nanostructuring), and composition (including doping with different compounds).
Polymer microfibers and nanofibers produced by the electrospinning technique are in high
demand because of their multiple applications, particularly in the biomedical field [11–16].
Besides medical applications, the polymer electrospun fibers are used also for filters [17,18],
for cosmetics [18], in the clothing and textile industry [19,20], for electrical conductors [21], and for
sensor devices [22]. For optical applications, such polymeric fibers are used for ultrafast photonics [23],
for random lasers [24], for up-conversion [25], for white-light-emitting diodes [26], for dye-sensitized
solar cells [27], for their nonlinear properties [28], and for optical fibers [29].

Polymers 2018, 10, 737; doi:10.3390/polym10070737 www.mdpi.com/journal/polymers

Polymers 2018, 10, 737 2 of 18

Functionalization of the polymer nanofibers may be done using nanoparticle addition or further
chemical or electrochemical deposition of various compounds on the surface of the electrospun
nanofibers [21,30,31]. Bundles of such nanofibers were proven to be able to mimic human muscle
movements [32,33].
Interesting optical properties of the polymer fibers may be achieved by the electrospinning of
dye-doped polymeric solutions [34,35]. Dyes are fluorescent chemical compounds that can re-emit
light upon light excitation. Typically, they contain several combined aromatic groups or planar or
cyclic molecules [36]. Dyes are commercially available and have been used in many applications,
particularly in spectroscopy and medicine. Fluorescent dyes are mainly used in life sciences for
non-destructive tracking or analysis of biological molecules [37,38], but they find a wide use in the
industry for textile dyeing and as optical brighteners in laundry detergents [39,40], advanced cosmetic
formulations [41], safety equipment and clothing, fine arts and design (posters and paintings) [42],
synergists for insecticides, and experimental drugs [43]. Organic light-emitting diodes (OLEDs)
and solar panels that collect more light (wavelengths) also have a more commercially available use
nowadays. Dye-doped polymers have been studied in detail from the point of view of emission tuning
with morphology and with composition [44–46].
By combining the wavelengths of dyes’ emissions that cover the entire visible spectral domain,
white-light-emitting fibers can be produced. Up to 19% of worldwide electricity is consumed by
lighting; therefore, increased efforts are being made to reduce the electricity dedicated to illumination,
such as through the race to replace incandescent bulbs with less-energy-consuming LED lights [47–49].
Light adjusts people’s daily rhythms, and improving lighting can improve people’s well-being (at
home) and productivity (in the workplace) [50]. In order to understand how to make this improvement,
we have to understand how the human eye and light work. Because humans are trichromats (having
in the middle part of the retina three types of cones—the color receptor cells: blue, green, and red),
the perceived colors from the visible spectrum are made by mixing various percentages of blue, green,
and red [51].
Sunlight has been researched since the beginning of optical science, and numerous efforts have
been made for its standardization [52]. The complexity of daylight does not reside only in the mixture
of the various colors, but also in the fact that there are changes in the intensities of different components
depending on the season, month, place, and even time of day; that is, the morning hours’ light is
an intense light suited for working, containing an enhanced blue-green component, while the light
at dawn is a soothing light with an increased orange-red component. Thus, although commercial
LEDs emit differently from sunlight, we perceive white light (of different types) when we use artificial
lighting [53].
White-light-emitting low-dimensional structures have a wide range of applications, ranging from
spectroscopic lab-on-a-chip sensing devices to IT and communications [54,55]. Numerous types of
low-dimensional structures possessing white emission have been developed using different approaches
and methods of preparation [56,57]. One can differentiate between these structures either by type
of materials (ranging from polymers to oxides or composites) or by morphology and dimensions
(ranging from zero-dimensional quantum dots to quasi one-dimensional fibers or complex-shaped
structures) [58,59]. By tuning the composition and shape, one can easily define an application field in
which these intrinsic properties can be exploited.
The aim of this study is to present a simple and straightforward method to produce
white-light-emitting structures. Thus, electrospinning was employed to fabricate submicrometric
dye-doped polymer fiber mats. The photoemission of these submicronic fiber-based architectures
could be tuned depending on the mode in which the doping was performed. As a consequence of
the intensities’ values corresponding to each dyes’ emission maxima in the visible spectral domain,
different types of white lighting could be obtained, including sun-like distributions. Two approaches
were studied and are described in the paper, mats obtained by combining three single-dye-doped
types of fibers and mats of fibers obtained by electrospinning mixtures of solutions doped with several
Polymers 2018, 10, 737 3 of 18

dyes simultaneously. In both cases, high luminescence tunability was obtained, and white light was
Polymers 2018, 10, x FOR PEER REVIEW 3 of 17
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employed
employed in ainwide range of applications in inwhich one cancanexploit thethe
fibrous structure ofofthethe building
employed
employed in in aa wide
aawide
wide range
range
range
of applications
ofofof
applications
applications ininin
which
which
which one
one
one cancan exploit
exploit
exploit the
the
fibrous
fibrous
fibrous
structure
structure
structure ofofof
the the
employed
blocks, ranging
building
employed in
blocks,
in a wide wide
from
rangingrange
biological
range from applications
probes
biological
of biological
applications to
probes which
to
in which one can
high-surface-area/low-cost exploit
high-surface-area/low-cost the
one can exploit the fibrous fibrous
lighting structure
lighting devices.
devices.
structure the
Being
the based
Being
ofBeing
building
building blocks,
blocks, ranging
ranging fromfrombiological probes
probes tototo high-surface-area/low-cost
high-surface-area/low-cost lighting
lighting devices.
devices. Being
onbuilding
based
polymer
building onblocks,
polymer
fibers,
blocks, ranging
fibers,
rangingthe from
the biological
structures
structures
from haveprobes
have
biological have the
probes the high-surface-area/low-cost
advantages
advantages
toadvantages of
ofbeing
being
high-surface-area/low-cost lightweightlighting
lightweight and
lighting devices.
highly
and
devices. Being
flexible,
highly
Being flexible,
based
based on on polymer
polymer fibers,
fibers, thethe structures
structures have the theadvantages ofofof being
being lightweight
lightweight and and highly
highly flexible,
flexible,
based
enabling
based on
enabling polymer
ontheirtheir
polymer fibers,
integration
integration the
fibers, theinto structures
into
into have
different
different
structures have the
types
types
theof advantages
of devices
of devices
advantages for being
which
offor
being lightweight
whichthese these
lightweight and
characteristicshighly are
characteristics
and highly flexible,
sought.
are sought.
flexible,
enabling
enabling their
their integration
integration into different
different types
types offibersdevices
devices forfor which
which thesethese characteristics
characteristics are
are sought.
sought.
enabling
The
enabling their
their integration
electrospinningintegration into
into different
technique allows
different types
such
types of
of devicesto
devices befor
for which
which these
fabricated characteristics
simply
these and are
are sought.
inexpensively
characteristics sought. andensures
The
The electrospinning
The electrospinning
electrospinning technique
technique
technique allows
allows
allows such
such
such fibers
fibers
fibers to
to tobe
be fabricated
be fabricated
fabricated simply
simply
simply and
and and inexpensively
inexpensively
inexpensively and
and and
The
The electrospinning
ensures they
electrospinning are technique
readily
technique allows
scalable.allows such
Moreover,
such fibers
the to be
structures
fibersstructures
toare fabricated
be all are
fabricatedall simply
organic,
simply and
with inexpensively
low environmental
and environmental
inexpensively and
and
theyensures
are
ensures they
readily
they areare readily
scalable.
readily scalable.
Moreover,
scalable. Moreover,
the
Moreover, thethe
structures
structures areareallall
organic, organic,
organic,with with
low
with low low environmental
environmental impact.
ensures
impact.they
ensures they are are readily
readily scalable.
scalable. Moreover,
Moreover, the the structures
structures are are all all organic,
organic, with with lowlow environmental
environmental
impact.
impact.
impact.
2. impact.
Experimental Details
2. Experimental
2. Experimental Details Details
2.2.Experimental
Experimental Details
Details
For obtaining
2. Experimental
For obtaining
obtaining
the
Details dye-doped
the dye-doped
dye-doped polymer
polymersubmicronic
submicronic
polymer submicronic
fibers,
fibers, we
we used
we used
used poly(methyl
poly(methyl
poly(methyl methacrylate)
methacrylate)
methacrylate)
(PMMA) For with the fibers,
For
For
(PMMA)
(PMMA) witha aaMw
obtaining
For obtaining
obtaining
with
the
Mw
Mw
the of
the of of 300,000
dye-doped
dye-doped
300,000 and
dye-doped
300,000
and
polymer
polymer
and chemical
chemical
polymer
chemical
formula
submicronic
submicronic
formula
submicronic
formula of
of
of
(C55(C
fibers,
fibers,
fibers,
(C OOwe 5HO
2we
2we
H 8)n
8)n
Hat8 )n
used
2used
used
at
at a concentration
poly(methyl
poly(methyl
aapoly(methyl
concentration
concentration 12.5 of
methacrylate)
methacrylate)
of 12.5
methacrylate)
of wt12.5
wt %. wt %.
%.
(PMMA) with
Dimethylformamide
(PMMA) with
Dimethylformamide a aMwMw of of 300,000
(DMF;
300,000
(DMF; and
and
anhydrous,chemical
anhydrous, chemical formula
99.8%)
99.8%) formula of
wasof
was chosen(C
chosen(C5O2H8)n as
chosen
5 O H
as2the
2 the8 )natat aaconcentration
the
solvent. solvent.
concentration
The polymer
polymer of
The of12.5
12.5
solutionwt
polymerwt %. %.
wassolution
(PMMA) with a Mw of
Dimethylformamide 300,000
(DMF; and chemical
anhydrous, 99.8%) formula
was of (C5as O H 8)n at a concentration
solvent. The ofsolution
12.5 wt was %.
Dimethylformamide
was prepared
Dimethylformamide
prepared at at
at room room (DMF;
(DMF;
room temperature
temperature anhydrous,
temperature
anhydrous,
and stirred99.8%)
and 99.8%)
stirred was
stirredwas
overnight. chosen
overnight.
chosen asas
Blue-green-the
the solvent.
Blue-green-
solvent. The
The polymer
andpolymer
and orange-red-emitting
orange-red-emitting solution
orange-red-emitting
solution waswere dyes
was
dyes was
Dimethylformamide
prepared (DMF; anhydrous, and 99.8%) was chosen
overnight. as the solvent.
Blue-green- and The polymer solution dyes were
prepared
prepared
used at
atroom
room
as dopants
dopants temperature
temperature
in order
order and
and
for the
the stirred
stirred
emitted overnight.
overnight. Blue-green-
Blue-green-
lights’ wavelengths
wavelengths andand
to and orange-red-emitting
cover orange-red-emitting dyes
dyes were
were
were
usedusedused
prepared
asasas
asroom
at
dopants
dopants temperature
inininorder
in order
for for
the
andfor the emitted
stirred
emitted
emitted
overnight.
lights’
lights’
lights’
wavelengths
wavelengths
Blue-green-
tototo
covercover aa large
large area within
to cover
orange-red-emitting
aalarge areaarea awithin
within the
the
largedyes area
the visible
werewithin the
visible
visible
used
spectrum.
visible dopants
spectrum. Thus, order
the
Thus, for
polymer
the the emitted
polymersolutions lights’
were
solutions wavelengths
doped
were with
doped cover
coumarin
with large
7
coumarin area
(C7), within
7coumarin
(C7), the visible
6
coumarin (C6),
used as dopants
spectrum.Thus,
spectrum.
in order
Thus,thethepolymer for the emitted
polymersolutionssolutionswerelights’ wavelengths
weredoped dopedwith to
withcoumarincover a large
coumarin7 7(C7), area within
(C7),coumarin the
coumarin6 6(C6), (C6), 6 (C6),
visible
spectrum.
fluorescein
spectrum. Thus,
(F),
Thus, the
rhodamine
the polymer
polymer 6G solutions
(Rh 6G),
solutions were
sulforhodamine
were doped
doped with
B (SRh
with coumarin
B),
coumarinand 77 (C7),
sulforhodamine
(C7), coumarin
coumarin 101 66 (C6),
(SRh 101).
(C6),
fluorescein
fluorescein
fluorescein
(F),
(F), (F), rhodamine
rhodamine
rhodamine 6G
6G(Rh
(Rh
(Rh6G),
6G),
6G), sulforhodamine
sulforhodamine
sulforhodamine B (SRh
Bdye
(SRh
BB),
(SRhB),
and
B),
and and sulforhodamine
sulforhodamine
sulforhodamine 101101(SRh(SRh101 (SRh 101).
101).
101).
fluorescein
The chemical
fluorescein (F),
(F), rhodamine
formula
rhodamine and 6G
6G (Rh
optical
(Rh 6G),
6G), sulforhodamine
properties of
sulforhodamine each B
B (SRh
(SRh used B),
B), and
for
and sulforhodamine
doping are
sulforhodamine listed 101
in
101 (SRh
Table
(SRh 101).
1. The
101).
The
The chemical
The chemical
chemical formula
formula and and optical
optical properties
properties of
of each
each dye
dye used
used for
for doping
doping are
are listed
listed inin Table
Table 1. 1.
TheThe dyes
The
dyes
The
dyes
chemical
had
chemical
−had
3 M−3 10formula
10
formula
−3
−3formula
M
and
and optical properties
and optical
M concentrations
concentrations optical inproperties
in the polymer
the polymer
properties
ofofeach
of each
dye
dye
solutions.
each
used
dyeAll
solutions. Allfor
used
used
All
for dopingcompounds
for doping
chemical
chemicaldoping
are
are listed inin
are listed
compoundslisted in
Table
were
were
Table
Table
1.1.The
1. The
purchased
The
purchased
had
dyes 10
had 10 concentrations
−3M concentrations in the polymer solutions. chemical compounds were purchased from
dyes
from
dyes
from
had
had 10
10−3 M
Sigma-Aldrich
Sigma-Aldrich M concentrations
concentrations
(St. Louis,inin
(St. Louis, in
the
MO,
MO,
the polymer
polymer
USA)
theUSA)
polymer andsolutions.
and
solutions.
were used
were used
solutions.
All
All chemical
chemical
without
All chemical
without anycompounds
any
compounds were
were
further purification.
compounds
further purification. purchased
were purchased
purchased
Sigma-Aldrich
from
from Sigma-Aldrich (St. Louis,
(St. Louis, MO, MO, USA) USA) andandwerewereusedused without
without any anyfurther
furtherpurification.
purification.
from Sigma-Aldrich
Sigma-Aldrich (St. (St. Louis,
Louis, MO,MO, USA) USA) and and were
were used
used without
without any any further
further purification.
purification.
Table 1. Chemical formulas, molecular structures, and optical properties of the dyes used for doping
Table 1. Chemical formulas, molecular structures, and optical properties of the dyes used for doping
Table
the 1.
Table
Table
Table
1.1.Chemical
Chemical
1. Chemical
polymer formulas,
formulas,molecular
formulas, structures,
molecular
formulas, molecular
solutions.
Chemical
and optical
structures,
molecular structures,
structures, and
properties
and optical
and optical
of the
properties
optical properties
properties of
dyes
of the
the dyes
used
of the
dyes used
for doping
dyes
used for
used for doping
for doping
doping
thethe polymer
polymer solutions.
solutions.
the
the polymer
polymer solutions.
solutions.
the polymer solutions. Molecular Absorption Emission
Dye Chemical formula Molecular
Molecular Absorption
Absorption Emission
Emission
Dye
Dye Chemical
Chemical formula
formula Molecular
structure Absorption
wavelengths Emission
wavelengths
Dye Chemical formula Molecular
structure
Molecular Absorption
wavelengths
Absorption Emission
wavelengths
Emission
Dye
Dye Chemical
Chemicalformula
Formula structure
structure wavelengths
wavelengths wavelengths
wavelengths
structure
Structure wavelengths
Wavelengths wavelengths
Wavelengths
Coumarin 7 C20H19N3O2 437 and 455 nm 485 and 505 nm
Coumarin
Coumarin 77 7 CC C20H19N3O2
20H19N3O2 437437
andand
455455
nm nm 485485
andand
505505
nm nm
Coumarin
Coumarin 20H19N3O2 437 and 455 nm 485 and 505 nm
Coumarin7 7 C
C2020HH1919
NN3O
3O2 2 437437
andand
455455
nmnm 485485
andand
505505
nmnm

Coumarin 6 C20H18N2O2S 448 and 465 nm 495 and 515 nm

Coumarin
Coumarin 6 6 66 CC C20H18N2O2S
20H18N2O2S 448448
andand
465465
nm nm 495495
andand
515515
nm nm
Coumarin
Coumarin
Coumarin 6 C20
C H
20
20 HH NN
1818 2O
18N2O 22OS S
2S2
448
448 and
and
448 and 465
465 nm
465 nm
nm 495 and
495495 515
andand nm
515515
nmnm

430, 457, and 487 515, 550, and 575

Fluorescein C20H12O5 430,430, 457,
457, andand 487 515,
487 515, 550,
550, andand
575575
Fluorescein
Fluorescein
Fluorescein CCCC H
H2012H 12O5
O125 O5 430, 430,
457, 457, and
nm
andnm 487
487 nm 515,
515,550,
550,and
nmand575
575 nm
Fluorescein 20 430, 457, and 487 515, 550,nmand 575
Fluorescein C20H
2020
H12 O
12O5
5
nm
nm nmnm
nm nm

Rhodamine 6G C28H31N2O3Cl 534 nm 560 nm

Rhodamine
Rhodamine 6G6G CC282831H
CC
28H
H 31N
N31 N2OO3Cl
2O32Cl 3
Cl 534
534534
nmnm
nm 560
560 560
nm nm
nm
Rhodamine
Rhodamine 6G
6G 28H31N2O3Cl
C28H31N2O3Cl 534
534 nm
nm 560
560 nm
nm

Sulforhodamine B CCC2727H
H29N22NaO77SS22 550
550 550 nm
nm nm 580
580nm
nm
Sulforhodamine 27H29
Sulforhodamine
SulforhodamineB B CC 29N2NaO7S2
27H29N2NaO7S2 550 nm 580
580 nm nm
Sulforhodamine B
B 27H29N2NaO7S2
C27H29N2NaO7S2 550 nm
550 nm 580 nm
580 nm
Polymers 2018, 10, 737 4 of 18

Table 1. Cont.
Polymers 2018, 10, x FOR PEER REVIEW 4 of 17
Polymers 2018, 10, x FOR PEER REVIEW Molecular Absorption 4 of 17
Emission
Dye Chemical Formula
Structure Wavelengths Wavelengths

Sulforhodamine
Sulforhodamine
Sulforhodamine 101
101101 CC
C31 H HH
31
3129
29ClN
ClN 22OS
2O62SO
29 ClN
6S2
6 2 nm 575 nm
575nm
575 590 nm590 nm
590 nm

During the
During
Duringthe thefibers’
fibers’
fibers’production
production
production through
through
throughthe electrospinning
the process,
theelectrospinning
electrospinning the fluid
process,
process, was
the
the pumped
fluid
fluid was at a
waspumped
pumpedat ataa
rate of 0.5 mL/h through a syringe with an automatic pump (New Era Pump System). The syringe
rate
rateofof0.5
0.5mL/h
mL/h through
through aa syringe
syringe withwith an anautomatic
automaticpumppump(New (NewEra EraPumpPumpSystem).
System).The Thesyringe
syringe
needle was positively charged using a high-voltage supply (DC power supply: 30 kV Spellman SL300,
needle
needlewaswaspositively
positivelycharged
chargedusing
usingaahigh-voltage
high-voltagesupplysupply(DC
(DCpower
powersupply:
supply:30 30 kV
kV Spellman
Spellman SL300,
SL300,
New York, NY, USA). The resulting electric field caused solution jets to be pulled from the end of the
New
New York,
York, NY,
NY, USA).
USA). The
The resulting
resulting electric
electric field
field caused
caused solution
solution jets
jetsto
to be
be
droplet formed on the needle tip (the droplet formed a Taylor cone under the influence of the electric pulled
pulled from
from the
the end
end of
ofthe
the
droplet
droplet
field) formed
formed
reaching, ason
on the
theneedle
fibers, needle tip
tip(the
the grounded (the droplet
droplet
metal formed
formed
collector aaTaylorof cone
Taylor
consisting acone
copperunder
under the
frame.theinfluence
influenceof ofthe
theelectric
electric
field) reaching,
field)The
reaching, as
electrodesasfibers,
fibers,
were the
thegrounded
grounded
positioned metal
metalcollector
at distances consisting
collector15
between consisting
and 20 cm. ofofThe
aacopper
copper frame.
frame.of 20 kV
high voltage
The
Theelectrodes
produced electrodes were
were
the electrically positionedjet ofat
positioned
charged at
thedistances
polymerbetween
distances solution, 15
between 15and 20
20cm.
anddried
which cm.andThe
The high
high voltage
solidified into a of
voltage of 20
20kV
kV
polymer
produced
producedthefiber along the
theelectrically trajectory
electrically charged towards
charged jet of the
jetthe collector.
ofpolymer Using high
solution,
the polymer voltages
which which
solution, resulted
dried and in the
solidified
dried drawing
into a polymer
and solidified into a
of very
fiber
polymer fine
along fibers
the
fiber (submicrometric
trajectory
along towards
the trajectory orthe
even nanoscale)
collector.
towards from high
Using
the collector.a liquid (polymer
voltages
Using solution
resulted
high voltages inorthe
melt)
resulted with
drawing
in of very
the drawing
highfibers
aspect(submicrometric
fine
of very fineratios
fibers and with theor fiber
(submicrometric evendiameter
or even inversely
nanoscale) fromproportional
nanoscale) a from to the applied
liquida (polymer
liquid voltage.
solution
(polymer or The set-with high
melt)
solution or melt) with
up used to produce the dye-doped polymer fibers is illustrated in Figure 1.
aspect ratiosratios
high aspect and with
and the
withfiber diameter
the fiber inversely
diameter proportional
inversely to the
proportional toapplied voltage.
the applied TheThe
voltage. set-up
set-
up used
used to produce
to produce the dye-doped
the dye-doped polymer
polymer fibers
fibers is illustrated
is illustrated in Figure
in Figure 1. 1.

Figure 1. Schematic illustration of the experimental setup used for electrospinning of the dye-doped
polymer solutions.

Imaging of the solutions and fiber mats collected on copper frames was done at a 365 nm
Figure1.1.Schematic
Schematicillustration
illustrationof ofthe
theexperimental
experimentalsetupsetupused
usedfor
forelectrospinning
electrospinning ofthe
thedye-doped
dye-doped
Figure
wavelength using a UVIlite lamp LF106L (Cambridge, UK) (6 W, filter 50 × 150 mm, 700of µW/cm 2).
polymer
polymer solutions.
solutions.
The characterization of the dye-doped polymer submicronic fibers from the point of view of
structure and morphology was performed using scanning electron microscopy (SEM) (ZEISS EVO 50
XVP). Imaging
For SEMof
Imaging of the
the solutions
imaging, solutions
small pieces andoffiber
and fiber mats
the mats
mats collected
were placed on
collected onsticky
on copper
coppercarbonframes was
discs.was
frames done
Because
done at aa 365
of at
the 365 nm
nm
wavelength using
method used,using
wavelength a UVIlite
the density of the
a UVIlite lamp LF106L
fibersLF106L
lamp observed (Cambridge, UK) (6
in the lower-magnification
(Cambridge, W,
UK) (6 W, filterfilter 50
images × 150 mm,
50 × differed
150 mm, from700
700one µW/cm
µW/cm2 ).
2).

sampleTheto characterization
another. Prior to of
the the dye-doped
imaging using the polymer
scanning submicronic
electron fibers
microscope,
The characterization of the dye-doped polymer submicronic fibers from the point of view of
from
the the
samplespoint
were of view of
sputtered
structure with
and amorphology
thin layer of gold
was using an ANATECH
performed using Hummerelectron
scanning VI DC sputtering
microscopy system.
(SEM) (ZEISS EVO 50
structure and morphology was performed using scanning electron microscopy (SEM) (ZEISS EVO
XVP).In For
orderSEMto evaluate
imaging, the optical
small properties
pieces of the of the were
mats electrospun
placed nanofibers,
on sticky the absorption
carbon discs. and
Because of the
50 XVP). For SEM
transmission
imaging, measurements
spectroscopy
small pieces ofwere the mats
made
were placed
using a
on sticky carbon
UV-vis-NIR CARY
discs.
5000
Because of
method used, the density of the fibers observed in the lower-magnification images differed from one
the method used, the density
spectrophotometer, of the fibers observed inevaluated
the lower-magnification images differed from
sample to another.and the photoluminescence
Prior to the imaging using (PL) was
the scanning using a FLS920 EDINBURGH
electron microscope, the samples were
one sample to another. Prior to the imaging using the scanning electron
INSTRUMENTS spectrofluorimeter (equipped with a 450 W Xe lamp and double monochromators microscope, the samples were
sputtered with a thin layer of gold using an ANATECH Hummer VI DC sputtering system.
sputtered with a thin
in both excitation and layer of gold
emission). Theusing an ANATECH
chromaticity measurementsHummer wereVI DC using
made sputtering system.
a Minolta CS-
2000In
In order to evaluate theMinolta,
optical properties of the electrospun nanofibers, the absorption and
order to evaluate
spectroradiometer (Konica the opticalTokyo,properties
Japan). of the electrospun nanofibers, the absorption
transmission spectroscopy measurements were made using a UV-vis-NIR CARY 5000
and transmission spectroscopy measurements were made using a UV-vis-NIR CARY 5000
spectrophotometer, and the photoluminescence (PL) was evaluated using a FLS920 EDINBURGH
INSTRUMENTS spectrofluorimeter (equipped with a 450 W Xe lamp and double monochromators
in both excitation and emission). The chromaticity measurements were made using a Minolta CS-
2000 spectroradiometer (Konica Minolta, Tokyo, Japan).
Polymers 2018, 10, 737 5 of 18

spectrophotometer, and the photoluminescence (PL) was evaluated using a FLS920 EDINBURGH
INSTRUMENTS spectrofluorimeter (equipped with a 450 W Xe lamp and double monochromators in
both excitation and emission). The chromaticity measurements were made using a Minolta CS-2000
spectroradiometer
Polymers 2018, 10, x FOR(Konica Minolta, Tokyo, Japan).
PEER REVIEW 5 of 17

3. Results
3. Results and
and Discussion
Discussion

3.1. Single-Dye-Doped
3.1. Single-Dye-Doped Polymer
Polymer Fibers
Fibers
Submicronic fiber
Submicronic fiber mats
mats were
were produced
produced using
using copper
copper frames
frames asas collectors
collectors during
during the
the
electrospinning process. Images of the single-dye-doped polymer solutions used for the
electrospinning process. Images of the single-dye-doped polymer solutions used for the electrospinning
method and their
electrospinning corresponding
method self-supportingself-supporting
and their corresponding electrospun fiber mats under
electrospun either
fiber matsvisible
under or UV
either
light are
visible orpresented in Figure
UV light are 2. in Figure 2.
presented

C7 C6 F Rh 6G SRh B SRh 101

Figure 2. Images of the polymer solutions and the corresponding electrospun submicronic fiber mats
Figure 2. Images of the polymer solutions and the corresponding electrospun submicronic fiber mats
collected on copper frames in visible light (upper) and UV light (lower).
collected on copper frames in visible light (upper) and UV light (lower).

There are many parameters that have to be controlled during the electrospinning process. One
There
has to are many
control parameters
the ambient that have to
parameters be controlledhumidity,
(temperature, during the air
electrospinning process.
currents, etc.), One has
the solution
to control the ambient parameters (temperature, humidity, air currents, etc.), the solution
parameters such as the polymer concentration (MW and solvent), and also the set-up parameters (the parameters
such as the
collector polymerthat
geometry concentration (MW andfiber
results in different solvent), and alsothe
alignments, thedistance
set-up parameters (the collector
between electrodes, the
geometry that results in different fiber alignments, the distance between electrodes,
applied voltage, the flow rate, and the needle diameter). By varying these parameters, the tailoring the applied
voltage,
of the flow
the fibers’ rate, and the
morphological needle (diameter,
properties diameter). texture,
By varying these parameters,
and pattern) the tailoring of the
becomes possible.
fibers’
Themorphological
PMMA matrix properties
was chosen(diameter,
as the texture, and pattern)
carrier polymer becomes
because possible.
the hydrophobic properties of
PMMA would ensure the fibers’ integrity from both morphological and optical points of view.
Besides its favorable optical properties, our experiments have shown that PMMA also offers the
mechanical strength necessary for the collection of suspended fibers with submicronic diameters and
lengths on the centimeter scale (sample size was 3 cm × 3 cm).
Lower- and higher-magnification SEM images of the single-dye-doped polymer fibers produced
Polymers 2018, 10, 737 6 of 18

The PMMA matrix was chosen as the carrier polymer because the hydrophobic properties
of PMMA would ensure the fibers’ integrity from both morphological and optical points of view.
Besides its favorable optical properties, our experiments have shown that PMMA also offers the
mechanical strength necessary for the collection of suspended fibers with submicronic diameters and
lengths on the centimeter scale (sample size was 3 cm × 3 cm).
Lower- and higher-magnification SEM images of the single-dye-doped polymer fibers produced
by electrospinning are presented in Figure 3 for all the dyes that were used. The lower-magnification
SEM images obtained at 1000× illustrate the random placement of the nanofibers and the uniformity
of the diameters’ distributions, which are difficult to observe in the higher-magnification SEM images.

Figure 3. Cont.
Polymers 2018, 10, 737 7 of 18

Polymers 2018, 10, x FOR PEER REVIEW 7 of 17

(e) (e’)

(f) (f’)
Figure 3. Scanning electron microscopy (SEM) images at two different magnifications (1000× and
Figure 3. Scanning electron
10,000×) of the microscopy
electrospun (SEM)
polymer fibers images
doped at two
with (a,a’) different
coumarin magnifications
7, (b,b’) (1000× and
coumarin 6, (c,c’)
10,000×) of the electrospun polymer fibers doped with (a,a’) coumarin 7, (b,b’)
fluorescein, (d,d’) rhodamine 6G, (e,e’) sulforhodamine B, and (f,f’) sulforhodamine 101. coumarin 6, (c,c’)
fluorescein, (d,d’) rhodamine 6G, (e,e’) sulforhodamine B, and (f,f’) sulforhodamine 101.
The fibers’ diameters ranged between 300 nm and 1 µm.
The thicknesses of the electrospun mats are very important parameters, particularly for the
The fibers’ diameters
intensities ranged
of absorption andbetween 300 nm
luminescence. and 1 itµm.
However, is difficult to precisely measure such
thicknesses because
The thicknesses of theof electrospun
the fact that themats
electrospun mats are
are very fluffy (aired),
important containing lots
parameters, of empty
particularly for the
space, and because their thicknesses cannot be assimilated with the thicknesses of a certain number
intensities of absorption and luminescence. However, it is difficult to precisely measure such
of overlapped fibers.
thicknesses because
Because of theway
of the factanthat the electrospun
electrospun mats are
fiber mat is formed fluffy
in the (aired),
optically containing
transparent regime lots
(i.e., of empty
space, andatbecause
low fiber densities), it is difficult to define a meaningful geometrical thickness, as up to 90–95% ofnumber of
their thicknesses cannot be assimilated with the thicknesses of a certain
the mat can be empty space. This is further complicated by the flexibility of the fibers, which makes
overlapped fibers.
the mats compressible in an uncertain way.
Because of the way an electrospun fiber mat is formed in the optically transparent regime (i.e., at
However, given the optical nature of the application at hand, a relevant characteristic is the
low fiber densities), it is difficult
optical transmission of thetofiber
define
matsa inmeaningful geometrical
the visible range. This is thickness,
directly linked as up to 90–95%
to the true of the
mat can begeometrical
empty space. This
thickness butisis further
far easier complicated
to measure. As itby the flexibility
depends on the fiberof the fibers,
density, which makes the
this “thickness”
can be controlled
mats compressible by varying way.
in an uncertain the collection time. All the samples were produced using the same
collection time, which means that they should have had approximately the same transmission values
However, given the optical nature of the application at hand, a relevant characteristic is the optical
and fiber densities.
transmission of the fiber
In order mats in the
to demonstrate thesimilarity
visible of range. Thisregarding
the samples is directly linked tothicknesses,
the measured the true we geometrical
thickness evaluated
but is fartheeasier to measure. As it depends on the fiber density, this
transmission spectra in the interval 600–800 nm in which the transmittance could be “thickness” can be
compared, because in this wavelength interval, there were no absorption bands
controlled by varying the collection time. All the samples were produced using the same collection of the dyes.
Information regarding the optical transmission values of the samples are presented in the
time, which means that they should have had approximately the same transmission values and
Supplementary Materials, Figure S1.
fiber densities.Previous studies have shown that the presence of different dyes in polymer solutions leads to
In order to demonstrate
changes the similarity
in the morphologies of thenanofibers
of the electrospun samplesasregarding
a result of the measured
the different sizesthicknesses,
of dye we
evaluated molecules [45]. In order
the transmission to avoidin
spectra fabricating fibers with
the interval different
600–800 nmmorphologies,
in which the the transmittance
concentration of could be
compared, because in this wavelength interval, there were no absorption bands of the dyes.
Information regarding the optical transmission values of the samples are presented in the
Supplementary Materials, Figure S1.
Previous studies have shown that the presence of different dyes in polymer solutions leads to
changes in the morphologies of the electrospun nanofibers as a result of the different sizes of dye
molecules [45]. In order to avoid fabricating fibers with different morphologies, the concentration of the
polymer in the solution was increased compared to prior investigations [44,45]. Thus, for a 12.5 wt %
concentration of PMMA in DMF, uniform submicronic fibers were obtained by electrospinning for
Polymers 2018, 10, x FOR PEER REVIEW 8 of 17
Polymers 2018, 10, x FOR PEER REVIEW 8 of 17
the polymer
Polymers in737
2018, 10, the solution was increased compared to prior investigations [44,45]. Thus, for a8 12.5 of 18
the%polymer
wt in the solution
concentration of PMMA was increased
in DMF, compared
uniform to prior
submicronic investigations
fibers were obtained[44,45]. Thus, for a 12.5
by electrospinning
wt %
for allconcentration
single-dye-dopedof PMMA in DMF,
polymer uniform
solutions. It submicronic fibers were
could be observed thatobtained by electrospinning
all the fibers had smooth
all single-dye-doped
for all single-dye-doped
surfaces polymer solutions.
(e.g., surfaces of polymer
Rh 6G-doped It could
solutions.
fibersItare be observed
could that
be observed
presented all
in Figure the
that fibers
4).all
Rhthe had smooth
6Gfibers had surfaces
was chosen smooth
as an
(e.g., surfaces
surfaces because
example of Rh
(e.g., surfaces6G-doped fibers
of Rh 6G-doped
its molecule are presented
fiberssize
has an average in
are when Figure
presented 4). Rh
in Figure
compared 6G
with4).was chosen
theRhother
6G was as an example
dyeschosen
used inasthis
an
because
exampleits
study. molecule
because has an average
its molecule has ansize whensize
average compared with the other
when compared withdyes used in
the other thisused
dyes study.
in this
study.

Figure 4. Scanning electron microscopy (SEM) image presenting the surface uniformity for rhodamine
Figure 4. Scanning electron microscopy (SEM) image presenting the surface uniformity for rhodamine
Figure
6G (Rh 4. Scanning polymer
6G)-doped electron microscopy
fibers. (SEM) image presenting the surface uniformity for rhodamine
6G (Rh 6G)-doped polymer fibers.
6G (Rh 6G)-doped polymer fibers.
However, for the C6-doped polymer fibers, we observed the rare occurrence of a beads-on-string
However,
However,
morphology for
for the
(Figure C6-doped
the5),
C6-doped polymer
polymer
likely formed at fibers,
fibers, we observed
we observed
the beginning theelectrospinning
the
of the rare occurrence
rare occurrence ofof aa beads-on-string
beads-on-string
process during the
morphology
morphology
period (Figure
when (Figure 5), likely
5), likely
a stabilization formed
formed
of the at the
at the
process beginning
beginning
takes of the
of the
place. The electrospinning
electrospinning
appearance process
of such process during
during
a specific the
the
polymer
period
fiber when
when aa stabilization
periodmorphology stabilization of
of the
the process
process takes
for the electrospinning takes
of theplace.
place. The appearance
The appearance
C6-dye-doped of such
of
solution such a
a specific polymer
specificwith
is consistent polymer
the
fiber
fiber morphology
morphology
previous for
forthethe
studies [45]. electrospinning of the
electrospinning of C6-dye-doped solution
the C6-dye-doped is consistent
solution with the with
is consistent previous
the
studies [45].
previous studies [45].

(a) (b)
(a) (b)
Figure 5. Beads-on-string morphology observed for coumarin 6 (C6) sample: 1000× (a), and 10,000×
Figure 5. Beads-on-string morphology observed for coumarin 6 (C6) sample: 1000× (a), and 10,000×
(b).
Figure 5. Beads-on-string morphology observed for coumarin 6 (C6) sample: 1000× (a), and
(b).
10,000× (b).
The appearance of beads on fibers is strongly related to the viscosity and surface tension (among
otherThe appearance
parameters) of beads
[60,61]. In theonC6-doped
fibers is strongly
PMMArelated
fibers, to
thethe viscosity and
appearance surface
of beads was tension
likely (among
related
other The appearance of beads on C6-doped
fibers is strongly related to the viscosity and surface tension (among
to theparameters) [60,61].
intrinsic properties InoftheC6, leading PMMA to the fibers,
highestthe appearance
probability of the
for beads was
occurrencelikelyofrelated
such
other
to theparameters)
intrinsic [60,61]. In oftheC6,
C6-doped PMMA
to thefibers, the probability
appearance of beads was likely related to
morphology. It isproperties
well known that leading
C6 fluorescence highest
in solvents dependsfor the occurrence
critically of such
on concentration
the intrinsic properties
morphology. It is well of C6, leading
known that to fluorescence
the highest probability fordepends
the occurrence of suchconcentration
morphology.
and on the pattern of substitution forC6the amine group in[62].
solvents
Relatively critically
large shifts inon both absorption
It is well known
and fluorescence that
on the patternwere C6 fluorescence
of substitution in
foronlysolvents
the amine depends
groupbut critically
[62].also on
Relativelyconcentration
large [63].
shiftsC6 and
in is on
both the pattern
absorption
and reported not in solutions in polymers known for its
of substitution for the amine group [62]. Relatively large shifts in both absorption and fluorescence
high degree of sensitivity to its local environment, which may result in alterations toforthe
and fluorescence were reported not only in solutions but also in polymers [63]. C6 is known its
were reported
high degree of not only in solutions but also in polymers [63]. C6 is known for its high degree of
morphological andsensitivity
optical host’sto properties,
its local environment, which[64,65].
including viscosity may Thus,
result the
in presence
alterations of C6tomay
the
sensitivity to its local environment, which may result in alterations to the morphological
morphological and optical host’s properties, including viscosity [64,65]. Thus, the presence of C6 may and optical
Polymers 2018, 10,
Polymers 73710, x FOR PEER REVIEW
2018, 9 of 189 of 17

have affected the viscosity and the surface tension of the polymer solution more so than for the other
host’sdyes,
properties,
leadingincluding viscosity
to the rare [64,65].
appearance Thus, the
of beads presence
during of C6 may haveprocess.
the electrospinning affected the viscosity
and the surface tension of the polymer solution more so than for the other
The optical absorbance and PL spectra of the single-dye-doped fiber mats dyes, leading
weretomeasured
the rare and
appearance
plotted,ofand
beads
theduring
results the
are electrospinning process.
presented in Figure 6a,b.
The optical absorbance and PL spectra of the single-dye-doped fiber mats were measured and
plotted, and the results are presented in Figure 6a,b.

C7 C6 F
Rh 6G SRh B SRh 101
1.0
Absorbance (a.u.)

0.5

0.0
400 500 600
Wavelength (nm)
(a)

1.4x107
C7 exc=420 nm
7
1.2x10
Emission intensity (a.u.)

C6 exc=440 nm
F exc=490 nm
1.0x107
Rh 6G exc=510 nm
6
8.0x10 SRh B exc=550 nm
SRh 101 exc=550 nm
6.0x106

4.0x106

2.0x106

0.0

450 500 550 600 650

Wavelength (nm)
(b)
Figure 6. Absorption (a), and photoemission (b) spectra of single-dye-doped polymer fibers.
Figure 6. Absorption (a), and photoemission (b) spectra of single-dye-doped polymer fibers.

As expected, the optical absorptions of the single-dye-doped fiber mats covered the spectral
domain 400–600 nm with increasing intensities from the blue region towards the red region, while
the emissions covered the spectral domain 450–650 nm with higher intensities in the blue-green
Polymers 2018, 10, 737 10 of 18

As expected, the optical absorptions of the single-dye-doped fiber mats covered the spectral
domain 400–600 nm with increasing intensities from the blue region towards the red region, while the
emissions covered the spectral domain 450–650 nm with higher intensities in the blue-green region
and significantly
Polymers 2018, 10, lower intensities
x FOR PEER REVIEW of the emission in the orange-red region of the visible 10 ofspectra.
17
The decreasing of the PL intensities was in total agreement with studies from the literature related
to theregion and significantly
efficiencies of the dyeslower whenintensities
dissolved of in
the emissionsolvents
different in the orange-red
[66–68]. Thereregionisof the visible
a strong relation
spectra. The decreasing of the PL intensities was in total agreement with studies from the literature
between PL and the molecular structure of dyes, indicating different efficiencies. This further leads
related to the efficiencies of the dyes when dissolved in different solvents [66–68]. There is a strong
to different PL intensities, although the dyes had the same concentration (10−3 M) in the solution of
relation between PL and the molecular structure of dyes, indicating different efficiencies. This further
PMMA (12.5 wt % in DMF).
leads to different PL intensities, although the dyes had the same concentration (10−3 M) in the solution
Depending
of PMMA (12.5 onwtthe% in conditions
DMF). and solvent, fluorescein may dimerize. A dimer–monomer
equilibrium appeared,
Depending onthus
the leading
conditionsto the
andappearance of different
solvent, fluorescein maypeaks in the A
dimerize. absorption spectra [69].
dimer–monomer
Moreover, different
equilibrium forms (cationic,
appeared, thus leading neutral,
to the anionic,
appearance andofdianionic) of theinfluorescein’s
different peaks the absorption molecule
spectra may
[69]. in
be found Moreover, different
a dye-doped forms (cationic,
solution neutral, anionic,
[70]. Therefore, we mayand dianionic)
observe moreofpeaks
the fluorescein’s molecule and
in both absorption
may spectra
emission be foundof inaa F-doped
dye-dopedpolymer
solution [70].
fiberTherefore, we may observe
mat. Absorption more peaksalso
peaks appeared in both absorption of
at wavelengths
and emission spectra of a F-doped
less than 350 nm, in the UV region of the spectrum. polymer fiber mat. Absorption peaks appeared also at
wavelengths of less than 350 nm, in the UV region of the spectrum.
The 420 nm excitation with C7-doped fibers revealed the overlapping of two peaks appearing at
The 420 nm excitation with C7-doped fibers revealed the overlapping of two peaks appearing at
485 and 505 nm, whereas for C6-doped fibers, two peaks at 495 and 515 nm appeared under 440 nm
485 and 505 nm, whereas for C6-doped fibers, two peaks at 495 and 515 nm appeared under 440 nm
excitation. The appearance of the shoulder in PL may have been due to the protonated form of the dye,
excitation. The appearance of the shoulder in PL may have been due to the protonated form of the
whichdye,
waswhich
previously reportedreported
was previously for coumarins [66]. The
for coumarins 490The
[66]. nm490
excitation with F-doped
nm excitation fibersfibers
with F-doped revealed
a broad PL spectrum formed by an overlapping of peaks between 515
revealed a broad PL spectrum formed by an overlapping of peaks between 515 and 575 nm. and 575 nm. The Rh 6G-doped
fibersThe
exhibited a peakfibers
Rh 6G-doped at 560 nm under
exhibited a peak510atnm560excitation,
nm under 510 while
nm under 550 while
excitation, nm excitation,
under 550 the
nm SRh
excitation,
B-doped fibers the SRh B-doped
presented fibersatpresented
a PL peak 580 nm and a PLthepeakSRhat 101-doped
580 nm and fibers
the SRh 101-doped
presented anfibers
emission
peak presented
at 590 nm.an emission peak at 590 nm.
Next,Next, the emissive
the emissive properties
properties ofofthe
theoverlapping
overlapping single-dye-doped
single-dye-doped fibers’ layers
fibers’ werewere
layers evaluated.
evaluated.
By varying the thickness of the layers, we were able to tune the emission spectra of the overlapped
By varying the thickness of the layers, we were able to tune the emission spectra of the overlapped
fiber mats and thus able to enhance the blue and red contributions to the spectra or to obtain a
fiber mats and thus able to enhance the blue and red contributions to the spectra or to obtain a balanced
balanced combination of the peaks. The downside of such an approach is that there are a limited
combination
number of of layers
the peaks.
that canThebedownside
used and of such
that too an
manyapproach is that there
layers overlap, furtherareresulting
a limitedin number
the
of layers
obstruction of light and the screening of the first layers’ emissions. PL excited at 420 nm for different of
that can be used and that too many layers overlap, further resulting in the obstruction
light overlapping
and the screening of the first
combinations layers’
of three emissions. PLfiber
single-dye-doped excited at 420
mats, C6, nm for different
Rh 6G, and SRh overlapping
101, are
combinations
presentedof in three
Figuresingle-dye-doped
7. fiber mats, C6, Rh 6G, and SRh 101, are presented in Figure 7.

1.4x106 overlapped mats 1

overlapped mats 2
Emission intensity (a.u.)

1.2x106 overlapped mats 3

1.0x106

8.0x105

6.0x105

4.0x105

2.0x105

0.0
450 500 550 600 650
Wavelength (nm)
Figure
Figure 7. Photoluminescence (PL)
7. Photoluminescence (PL) spectra
spectraofofoverlapping matsmats
overlapping of coumarin 6, rhodamine
of coumarin 6G, and 6G,
6, rhodamine
sulforhodamine 101
and sulforhodamine 101doped
dopedfibers with
fibers different
with thicknesses.
different thicknesses.

The volumes of the dye-doped solutions electrospun for the different overlapping fiber mats
were varied, leading to a variation in the thicknesses of the layers, until a balanced PL spectrum was
Polymers 2018, 10, 737 11 of 18

The volumes of the dye-doped solutions electrospun for the different overlapping fiber mats
were varied, leading to a variation in the thicknesses of the layers, until a balanced PL spectrum was
achieved. Thus, the balance in sample 2 was achieved by overlapping C6, Rh 6G, and SRh 101 mats in
a 1/5/10 ratio, while sample 1 was formed by overlapping C6, Rh 6G, and SRh 101 submicronic fibers
in a 10/5/5 ratio and sample 3 was formed by overlapping C6, Rh 6G, and SRh 101 submicronic fibers
in an equal 10/10/10 ratio.

3.2. Dye-Doped Polymer Fibers Obtained from Mixed Solutions

Copying the complexity of white light requires a more versatile approach; therefore, we used
mixed single-dye-doped polymer solutions in different percentages in order to be able to tune the
emissions of the electrospun fiber mats.
Table 2 presents the whole range of mixed solutions used for testing the emissive properties of the
polymer fiber mats. Nine mixtures were prepared using single-dye-doped polymer solutions. Mixtures
a, b, and c were prepared without the F solution, and a pronounced gap appeared in the PL spectra
in the range 520–540 nm (observed in Figure 7 for overlapping mats). Therefore, although having a
complicated overlapping of peaks in the PL spectrum due to the presence of various aggregates, as
previously explained, fluorescein was found to be a good solution for leveling the spectrum in the
yellow region. Thus, six additional mixtures containing six different dye-doped polymer solutions in
different ratios (including fluorescein) were prepared. The spectra of mixtures d, e, and f were only
slightly different from the spectrum of mixture 3. Therefore, only three mixtures were chosen to be
further analyzed by optical and morphological measurements, namely, mixtures 1, 2, and 3, which
illustrate the possibility of balancing the intensities between red and blue emissions.

Table 2. Composition of dye-doped polymer solution mixtures.

Percentage of Single-Dye Solution

Solution
C7 C6 FL Rh 6G SRh B SRh 101
Mix a 20 20 - 20 20 20
Mix b 16.66 33.33 - 33.33 8.33 8.33
Mix c 12.5 25 - 25 12.5 25
Mix 3 10 20 20 20 10 20
Mix d 12.5 22.5 22.5 22.5 10 10
Mix e 17 22.5 22.5 22.5 7.5 7.5
Mix f 5 25 25 25 5 5
Mix 2 15 30 30 10 7.5 7.5
Mix 1 12.5 25 40 7.5 7.5 7.5

PL spectra of the fiber mats produced by the electrospinning of different combinations of

single-dye-doped polymer solutions (mixtures 1, 2, and 3) are presented in Figure 8a. The spectra
illustrate the possibility to balance the luminescence between blue and red emissions, depending
on the ratios of the different dye-doped solutions. Commission Internationale de L’Eclairage (CIE)
coordinates of the fibers obtained by electrospinning of different mixtures are presented in Figure 8b.
The CIE measurements depicted the fine-tuning of the intensities of colors emitted by the fiber
mats composing the white light. Thus, the emissions of the submicronic fibers obtained from the
C7/C6/F/Rh6G/SRhB/SRh101 mixtures had the CIE coordinates of (0.27, 0.29) for the composition
10/20/20/20/10/20 (mixture 3), (0.38, 0.44) for the composition 15/30/30/10/7.5/7.5 (mixture 2),
and (0.44, 0.44) for the composition 12.5/25/40/7.5/7.5/7.5 (mixture 1).
The excitation wavelength for all the fibers obtained by the electrospinning of mixed solutions
was 420 nm, corresponding to the excitation wavelength of C7, the dye with the smallest values for
both the excitation and the emission wavelengths. The electrospinning of the mixture formed by
C7/C6/F/Rh6G/SRhB/SRh101 in a ratio of 15/30/30/10/7.5/7.5 (mixture 2; presented in Figure 8a)
Polymers 2018, 10, 737 12 of 18

resulted in a submicronic fiber mat that exhibited white-light emission. The UV image of the
white-light-emitting fiber mat (mixture 2) compared with the green-emitting and red-emitting fiber
mats is presented in Figure 9.
Polymers 2018, 10, x FOR PEER REVIEW 12 of 17

6.0x105
Emission intensity (a.u.)

4.0x105

2.0x105
mix 1
mix 2
mix 3
0.0
450 500 550 600 650
Wavelength (nm)
(a)
CIE 1931
520

0.8 540

560
0.6
500 580
y

O O
0.4 600
2 3
620
O

0.2
1
480

0.0 460
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
x
(b)
Figure 8. (a) Photoluminescence (PL) spectra of submicronic fibers produced by electrospinning from
(a) Photoluminescence
Figure 8. different mixtures of dye-doped(PL) spectra
polymer of submicronic
solutions, and (b) theirfibers produced
corresponding by electrospinning
coordinates on
from different mixtures
Commission of dye-doped
Internationale polymer
de L’Eclairage solutions,
(CIE) and (b)
1931 color space their corresponding
chromaticity diagram. coordinates on
Commission Internationale de L’Eclairage (CIE) 1931 color space chromaticity diagram.
It could be observed both for the overlapping fiber mats and for the fiber mats obtained by
electrospinning mixtures of single-dye-doped polymer solutions that for equal amounts of different
It could
dyes,betheobserved both tofor
red contribution thethe overlapping
spectra had a higherfiber mats
intensity. and
The for the
increased fiber of
intensity mats obtained by
the red
contribution
electrospinning appeared
mixtures as a result of the fact
of single-dye-doped that the solutions
polymer red component
thatwas excited amounts
for equal by both the
of different
wavelength of excitation and by the light emitted by the green-yellow components of the mixtures.
dyes, the red contribution to the spectra had a higher intensity. The increased intensity of the red
contribution appeared as a result of the fact that the red component was excited by both the wavelength
of excitation and by the light emitted by the green-yellow components of the mixtures.
Polymers 2018, 10, 737 13 of 18
Polymers 2018, 10, x FOR PEER REVIEW 13 of 17

Polymers 2018, 10, x FOR PEER REVIEW 13 of 17

Figure 9. Blue-green (coumarin 7 (C7))-, white-light (mixture 2)-, and orange-red (sulforhodamine 101
Figure 9. Blue-green (coumarin 7 (C7))-, white-light (mixture 2)-, and orange-red (sulforhodamine 101
(SRh 101))-emitting flexible and thin fiber mats under UV light excitation (365 nm).
(SRh Figure
101))-emitting flexible
9. Blue-green and thin
(coumarin fiberwhite-light
7 (C7))-, mats under UV light
(mixture excitation
2)-, and (365(sulforhodamine
orange-red nm). 101
(SRh 101))-emitting flexible and thin fiber mats under UV light excitation (365 nm).
Morphology studies have showed that electrospinning mixtures of dye-doped polymer
Morphology
solutions studies
in different have showed
combinations that also
results electrospinning mixtures ofwith
dye-doped polymer solutions
Morphology studies have showed that in submicronic
electrospinning fibers
mixtures ofsmooth surfaces,
dye-doped polymeruniform
in different
dimensional combinations
solutions in distribution, results also
and diameters
different combinations in submicronic
comparable
results also fibers with
to those
in submicronic smooth
fibersofwith surfaces, uniform
single-dye-doped dimensional
electrospun
smooth surfaces, uniform
distribution,
dimensional
polymer andThe
fibers. diameters
distribution,
diameters comparable
and of diameters
the fibers to comparable
those
obtainedof single-dye-doped
byto electrospinning electrospun
those of single-dye-doped
mixtures of polymer
electrospun
solutions fibers.
also
The diameters
rangedpolymer
between of the
fibers.
300Thefibers
nmdiametersobtained
and 1 µm. ofThe by electrospinning
the fibers obtainedofby
SEM images the mixtures of
electrospinning solutions
submicronic fibers mixtures also ranged
areofpresented
solutions in between
also
Figure
300
10. nm andbetween
ranged 1 µm. The 300 SEM
nm and images
1 µm.of Thethe submicronic
SEM images of thefibers are presented
submicronic fibers arein presented
Figure 10.in Figure
10. dye-doped polymer fibers produced by electrospinning presented similar optical properties
The
The dye-doped polymer fibers produced by electrospinning presented similar optical properties
over The dye-doped polymer fibers produced by electrospinning presented similar optical properties
over aa long
long period
period of of time.
time. TheThe PL PL ofof the
the electrospun
electrospun fibersfibers waswas very
very stable.
stable. The
The fibers
fibers showed
showed
over
identical a
PL long period
signals afterof time.
storage The PL
under of the
normal electrospun
atmospheric fibers was very
conditions. stable.
Surface The fibers
enrichment showed
of the dye
identical PL signals
identical PL signalsafter
afterstorage
storageunder
under normal atmosphericconditions.
normal atmospheric conditions. Surface
Surface enrichment
enrichment of theof the
is commonly
dye is commonly observed in
observed dye-doped polymeric
inindye-doped systems [71]. The fibers may have presented a possible
dye is commonly observed dye-doped polymeric systems[71].
polymeric systems [71].
TheThe fibers
fibers maymayhavehave presented
presented a a
segregation
possible of the
segregation dyes on
of of their
thethedyes surfaces during their formation, but this was difficult to be confirmed
possible segregation dyeson ontheir
theirsurfaces duringtheir
surfaces during theirformation,
formation, butbutthisthis
waswas difficult
difficult to be to be
experimentally
confirmed
confirmed because of the
experimentally
experimentally fact that
because
because the
ofofthe solidification
the fact
fact that of fibers takes
thesolidification
that the solidification of of place
fibers
fibers over
takes
takes a very
place overshort
place over
a veryperiod
a very
of time.
shortshort
periodperiod of time.
of time.

(a) (a’)

(a) (a’)

(b) (b’)

Figure 10. Cont.

(b) (b’)
Polymers 2018, 10, 737 14 of 18
Polymers 2018, 10, x FOR PEER REVIEW 14 of 17

(c) (c’)
Figure 10. Scanning electron microscopy (SEM) images of submicronic fibers obtained by
Figure 10. Scanning electron microscopy (SEM) images of submicronic fibers obtained by
electrospinning of mixtures of single-dye-doped polymer fibers: (a,a’) mix 1; (b,b’) mix 2; (c,c’) mix 3.
electrospinning of mixtures of single-dye-doped polymer fibers: (a,a’) mix 1; (b,b’) mix 2; (c,c’) mix 3.
4. Conclusions
4. Conclusions
We present a simple method to fabricate flexible, white-light-emitting nanofibers using the
electrospinning
We present a simplemethodsmethod
of dye-doped polymers.
to fabricate Different
flexible, mixtures of single-dye-doped
white-light-emitting polymer
nanofibers using the
electrospinning methods of dye-doped polymers. Different mixtures of single-dye-dopedstudy
solutions were used in order to tune the emissions of electrospun nanofibers. The present polymer
shows
solutions thatused
were electrospun
in ordernanofibers
to tune the obtained
emissionsfromofmixtures
electrospunof single-dye-doped
nanofibers. Thesolutions present
present study shows
white-light emissions and may have potential applications as new light sources or sensory materials
that electrospun nanofibers obtained from mixtures of single-dye-doped solutions present white-light
for smart textiles. White-light-emitting electrospun submicronic fibers were successfully prepared
emissions and may have potential applications as new light sources or sensory materials for smart
through the electrospinning of mixtures of single-dye-doped PMMA solutions in DMF using a single
textiles. White-light-emitting
capillary electrospun
spinneret. The emission submicronic
intensities of colorsfibers were successfully
composing prepared
the white light changedthrough
as the the
electrospinning of mixtures of single-dye-doped PMMA solutions in DMF using
composition of the mixtures changed, increasing either the blue-green component or the orange-red a single capillary
spinneret.
component of PL. The white-light-emitting submicronic fibers obtained from the of
The emission intensities of colors composing the white light changed as the composition
the mixtures changed, increasing
C7/C6/F/Rh6G/SRhB/SRh101 eitherwith
mixture the blue-green
compositioncomponent or thehad
15/30/30/10/7.5/7.5 orange-red component
CIE coordinates of of
(0.38,
PL. The 0.44). Our results show
white-light-emitting that white-light-emitting
submicronic fibers obtained fibers
fromcan
thebeC7/C6/F/Rh6G/SRhB/SRh101
produced through the use of
multicomponent
mixture with compositionsingle-dye-doped PMMA mixtures.
15/30/30/10/7.5/7.5 had CIE coordinates of (0.38, 0.44). Our results show
that white-light-emitting
Supplementary Materials: fibers
The can be produced
following through
are available the
online at use of multicomponent
www.mdpi.com/link, Figure S1:single-dye-doped
Transmission
PMMA spectra for the single-dye-doped polymer fiber mats produced by electrospinning.
mixtures.
Author Contributions: M.E. carried out electrospun fibers’ morphology and optical characterization
Supplementary Materials:
measurements. The following
A.E. fabricated are available
the dye-doped online at http://www.mdpi.com/2073-4360/10/7/737/s1,
self-supporting PMMA mats and optimized the conditions to
Figureobtain
S1: Transmission
homogeneousspectra for the
electrospun single-dye-doped
fibers. polymer
M.E. and I.E. proposed andfiber matsthe
planned produced by electrospinning.
research and cooperated with
Authorthe Contributions:
analysis of results. All
M.E.the carried
authors collaborated with the fibers’
out electrospun writing of the reported work.
morphology and optical characterization
measurements. A.E. fabricated the dye-doped self-supporting PMMA
Funding: This research was funded by IFA-CEA Project number C5-08/2018.
mats and optimized the conditions to
obtain homogeneous electrospun fibers. M.E. and I.E. proposed and planned the research and cooperated with
the analysis of results. All
Acknowledgments: Thethe authors
authors collaborated
acknowledge thewith the writing
financial of the reported
support provided work.of Romania-France
in the frame
IFA-CEA collaboration from Project No. C5-08/2016. The authors thank Silviu Polosan for help and assistance
Funding: This research was funded by IFA-CEA Project number C5-08/2018.
with the chromaticity measurements.
Acknowledgments: The authors acknowledge the financial support provided in the frame of Romania-France
Conflicts
IFA-CEA of Interest:
collaboration The authors
from Project declare no conflict of
No. C5-08/2016. interest.
The authors thank Silviu Polosan for help and assistance
with the chromaticity measurements.
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Conflicts of Interest: The authors declare no conflict of interest.
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