Article

Cite This: ACS Appl. Polym. Mater. 2019, 1, 2590−2596 pubs.acs.org/acsapm

All-Aqueous Direct Deposition of Fragrance-Loaded Nanoparticles

onto Fabric Surfaces by Electrospraying
Long Ye,† Zixie Li,† Rui Niu,† Zhuxian Zhou,‡ Youqing Shen,‡ and Liming Jiang*,†
†
Key Laboratory of Macromolecular Synthesis and Functionalization of Ministry of Education, Department of Polymer Science and
Engineering, Zhejiang University, Hangzhou 310027, China
‡
Key Laboratory of Biomass Chemical Engineering of Ministry of Education and Center for Bionanoengineering, College of
Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, China
*
S Supporting Information
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

ABSTRACT: Encapsulation of bioactive aroma compounds

into nanostructured matrixes has emerged as an attractive
Downloaded via LINKOPING UNIV on October 22, 2019 at 19:25:11 (UTC).

means to prolong the longevity of perfumery products.

Existing technologies applied for fragrance micro/nano-
encapsulation primarily rely on wet chemical processes,
which suffer from some drawbacks such as the tedious
preparation involving emulsion formulations and possible
contamination of residual additives. Herein, we proposed an
all-aqueous electrospraying method to prepare composite
nanoparticles made up of fragrance/2-hydroxypropyl-β-cyclo-
dextrin complexes and regenerated silk fibroin with a greater
than 90% aroma-encapsulation efficiency within the matrixes.
Compared to fragrance/CD inclusion complexes, the as-
prepared silk nanocomposites are capable of more effectively preserving the volatile cargo and exhibited an ideal zero-order
release kinetics with slow release rate upon the treatment of alcohol. Furthermore, a great benefit of this approach is that it
allows the direct deposition of fragrance-carrying nanoparticles on the silk fabrics during the electrospraying fabrication.
KEYWORDS: fragrance, silk fibroin, nanoencapsulation, electrospray, sustained release, fabric

■ INTRODUCTION
Fragrances and flavors are widely applied in cosmetics, textiles,
small size and large surface area make nanoparticles strongly
permeable and thus possible to embed in the matrixes of
leather, papermaking, food, and pharmaceutical industries.1 interest without the need for binders.11 To date, fragrance-
However, perfumery products usually suffer from low shelf life loaded nanoscale capsules or particles have been mainly
and aroma deterioration because most olfactory ingredients obtained by nanoprecipitation,12 ionic gelification,13 mini-
have high volatility and chemically labile functional groups emulsion polymerization,14,16 interfacial polymerization,17 a
under normal storage conditions.2,3 Therefore, it has always sol−gel process,18 layer-by-layer self-assembly,19 coacerva-
been an interesting topic to seek an effective encapsulation tion,20 and so on. These traditional methods normally involve
system for fragrances and to further develop prolonged cumbersome emulsification steps, and in most cases, the
fragrant articles, such as flavor-releasing garments with well- residual organic solvents and nondegradable additives, such as
being or healing effects.4−6 Microencapsulation of fragrances surfactants or synthetic polymers in the final products, seemed
into suitable material matrixes remains the most widely used to be unavoidable, with potentially negative impacts on human
method to improve its chemical stability or control the release health. As a result, it is highly desirable to explore effective
of volatile components.7−10 Nevertheless, one inevitable strategies to alleviate these problems and allow direct aromatic
shortcoming of microcapsules is their tendency to agglomerate, finishing of fabrics.
and they cannot be firmly embedded in fibrous substrates due Electrospray, as a variant of electrospinning, is a well-studied
to the large particle size (1−1000 μm in diameter), which approach to the manufacture of polymeric particles with sizes
limits their applications in finishing textiles.7,8 ranging from several tens of nanometers to ∼100 μm.21 Given
In recent years, quite a few efforts have been dedicated to its simplicity and versatility, electrospray has gained popularity
the incorporation or encapsulation of aroma molecules in in fabricating nanostructures that may have potential for a
various polymeric and inorganic nanostructured carriers to variety of biomedical applications, especially in the field of drug
obtain controlled or prolonged fragrance-release systems.11−18
In contrast to more frequently applied micron-sized particles, Received: May 16, 2019
nanoparticles may offer dramatically improved colloidal Accepted: August 13, 2019
stability and better dispersion in media. Additionally, the Published: August 13, 2019

© 2019 American Chemical Society 2590 DOI: 10.1021/acsapm.9b00457

ACS Appl. Polym. Mater. 2019, 1, 2590−2596
ACS Applied Polymer Materials Article

delivery.22−25 Nevertheless, the use of electrospray to spectrometer (Bruker, Germany). Acquisition parameters: TD = 256
efficiently encapsulate volatile substances such as odorous (for F1) and 2048 (for F2); DS = 16; NS = 10. The morphology of
molecules or flavors remains a great challenge, considering that electrosprayed samples was examined by a S-4800 field-emission
such a liquid-atomization technique through electrical force scanning electron microscope (Hitachi, Japan) after sputtering with
gold at an accelerating voltage of 3 kV. The particle size was analyzed
easily causes the odorants to volatilize with the solvent during using SEM images by the ImageJ software (version 1.51j8; National
electrospraying.21,26 In this context, Pan and Koo employed a Institutes of Health, USA) and expressed as mean ± standard
coaxial electrospray technology to incorporate peppermint oil deviation based on a minimum of 100 random measurements. The
in core−shell structured microcapsules.27 They achieved a high surface charge property of the SF nanoparticles in 90% aqueous
encapsulation efficiency of approximately 85% when an ethanol solution was determined on a zeta potentiometer (Zetasizer
alginate−pectin complex with a mass ratio of 8:2 worked as Nano ZS3600, Malvern Instruments, U.K.). Each sample was
the shell material. More recently, Koocheki’s group prepared measured three times. Gas chromatography (GC) measurements
Alyssum homolocarpum seed gum nanocapsules through an were carried out on a 7890A gas chromatograph (Agilent
emulsion electrospraying process for loading D-limonene with Technologies, USA) equipped with a DB-608 capillary column (30
m × 320 μm × 0.5 μm) and flame ionization detector.
∼90% encapsulation efficiency, which involved an initial step Preparation of the Regenerated Silk Fibroin. Regenerated silk
of the emulsification of the perfume in the gum solution.28 fibroin (SF) was prepared according to previously reported methods
Herein, we propose a strategy for the construction of with some modifications.35 Briefly, Bombyx mori cocoons were boiled
nanoscale fragrance-delivery systems from the perspective of in aqueous sodium carbonate solution (0.02 M) for 30 min and then
green chemistry and facile aromatic finishing. In brief, we rinsed thoroughly with deionized (DI) water. This process was
sought to fabricate composite nanoparticles by electrospraying repeated three times to completely remove the glue-like sericin and
an aqueous solution of regenerated silk fibroin (SF) containing other impurities. The degummed silk was dissolved in an aqueous
fragrance/2-hydroxypropyl-β-cyclodextrin (HP-β-CD) inclu- solution of LiBr (9.3 M) at 60 °C, and the resulting mixture was
sion complexes and directly deposit them on the surface of dialyzed against DI water for 3 days using a dialysis membrane
(molecular weight cutoff = 8−14 kDa; Yuanye Bio-Technology,
silk fabrics. As a complexing agent, HP-β-CD is able to capture Shanghai, China) and then lyophilized to obtain regenerated silk
hydrophobic guest molecules of suitable sizes into its fibroin as a white sponge-like solid.
hydrophobic cavity to form water-soluble inclusion com- Preparation of Fragrance/HP-β-CD Inclusion Complexes. To
plexes29,30 that not only caters to the electrospray under an aqueous solution of HP-β-CD (10 mg/mL) was added 5 equiv of
aqueous conditions but also can prevent premature fragrance rose oxide or D-limonene, and the resulting mixture was stirred at
loss during the atomization of charged droplets. Choosing a room temperature for 2 days to achieve the complexation equilibrium.
regenerated SF of natural source as the substrate material is After removal of the organic phase, the aqueous layer was lyophilized
due to its good water-solubility, good biocompatibility, and to yield corresponding inclusion complexes as a white powder.
excellent mechanical properties,31 as well as good spinn- Phase-Solubility Diagram. A phase-solubility diagram of the
fragrance/HP-β-CD inclusion complex system was drawn according
ability.24,32 It is also noteworthy that the initially formed SF to the method proposed by Higuchi and Connors.36 Specifically, the
particles will dissolve in aqueous media but become water- fragrance rose oxide or D-limonene (5 equiv) was separately added to
insoluble once the conformation of fibroin molecules trans- the solution of HP-β-CD (25 mL) with various concentrations (i.e., 1,
forms from α-helix (silk I) to antiparallel β-sheet (silk II), 3, 5, 7, and 9 mmol/L); then, the resulting mixture was stirred at 25
induced by external stimuli such as shear or polar solvents, °C complexation equilibrium. After centrifugation, 5.0 mL of the
because β-sheet chains have a pronounced tendency for aqueous layer was extracted with ethyl acetate (7 mL × 3). The
crystallization.32,33 It is envisioned that the formation of combined extract was subjected to quantification of the fragrance
crystalline domains should be favorable for suppressing the content by gas chromatography analysis (GC), and then, the fragrance
permeation of entrapped components in matrixes.34 Thus, in concentration was plotted as a function of the HP-β-CD
concentration. The determination of fragrance concentration was
addition to inherent host−guest interactions, the silk matrix carried out in triplicate, and the average of three measurements was
would have potential to further enhance the diffusion barrier of taken. GC operation parameters are shown below.
the encapsulated cargo.

■
For the AL-type phase solubility diagram, the apparent stability
constant (Ks) can be calculated by the following equation36
EXPERIMENTAL SECTION
Materials and Methods. 2-Hydroxypropyl-β-cyclodextrin (HP- k
Ks =
β-CD, degree of substitution = 5; 97%) was purchased from Aladdin S0(1 − k)
(Shanghai, China). Rose oxide was kindly offered by Shanghai
Research Institute of Fragrance & Flavor Industry (Shanghai, China). where k is the slope of the phase solubility diagram and S0 is the
D-Limonene (95%) was supplied from J&K Scientific (Beijing, intrinsic solubility of the guest molecule. Because in most cases S0 is
China). Silk scarves were acquired from Wensli Co. Ltd. (Hangzhou, very small or cannot be measured accurately, it is often replaced by
China). Bombyx mori cocoons were procured in June 2017 from the intercept of the phase solubility diagram by extrapolating the
Tongxian Huicong Silk Textile Co. Ltd. (Tongxiang, China). Other curve to [host] = 0.
chemicals (analytical grade) were purchased from Sinopharm Electrospraying Procedure. Spraying solutions were prepared
Chemical Reagent Co. Ltd. (Shanghai, China) and used as received. by dissolving the regenerated SF in DI water (3−6 wt %) at room
Infrared spectra were recorded on a TENSOR II FT-IR temperature under gentle stirring followed by mixing with a
spectrometer (Bruker, Germany) at 2 cm−1 resolution by accumu- preformed fragrance/CD inclusion complex RoseIC or LimIC in
lation of 32 scans at the wavenumber range from 4000 to 400 cm−1. different mass ratios of SF and IC. The electrospray setup consisted of
1
H NMR spectra were recorded on a Bruker AVANCE III 400 an injection pump (Pump 11 Elite, Harvard Apparatus, USA), a
spectrometer (Bruker, Germany). The samples were dissolved in D2O stainless-steel nozzle containing an 18-gauge needle, and a high-
for analysis (∼70 mg/mL). The chemical shifts are presented in parts voltage generator (DW-P303-1ACF0, Tianjin Dongwen High Voltage
per million (ppm) with the residual water peak (4.79 ppm) as the Power Supply Co. Ltd., China). The spraying solution was loaded
internal standard. Acquisition parameters: DS = 2; NS = 16. Two- into a 10 mL glass syringe (GASTIGHT #1010, Hamilton, USA) and
dimensional rotating frame nuclear Overhauser effect spectroscopies placed onto the pump. The pump then fed the liquid through the
(2D ROESY) were performed on a Bruker AVANCE III 500 polytetrafluoroethylene (PTFE) tube into the needle where a jet was

2591 DOI: 10.1021/acsapm.9b00457

ACS Appl. Polym. Mater. 2019, 1, 2590−2596
ACS Applied Polymer Materials Article

Figure 1. (A) Partial IR spectra of RoseIC, rose oxide, and dry HP-β-CD. (B) 1H NMR spectrum of RoseIC in D2O. (C) Partial 2D ROESY
spectrum of RoseIC in D2O. (D) Phase-solubility diagram of the rose oxide/HP-β-CD system in water at 25 °C. The error bars represent the
standard deviation of three independent measurements.

formed at the needle tip by manipulating the processing parameters to determine the LC and EE by GC analysis under the same
(i.e., the flow rate Q, applied voltage U, and the distance L from the conditions as described above.
needle tip to the collector). All of the electrospray experiments were Washing Durability Test of Nanoparticle-Deposited Silk
carried out at room temperature under ambient air conditions Fabric. A piece of silk scarf (3 cm × 3 cm) was put on the grounded
(relative humidity 35−50%). A grounded copper plate covered with a collector, and the electrospray was conducted under the established
piece of aluminum foil or silk scarf was used to collect the particles optimum conditions (i.e., SF conc. = 4 wt %, RoseIC/SF (w/w) =
generated from the liquid jet. During the spraying process, a mixture 3:4; Q = 1 μL/min, U = 16 kV, L = 16 cm; r.t., relative humidity
of EtOH/H2O (9:1, v/v) was sprayed onto the collected samples at 50%). After completion of the electrospray, the nanoparticle-
an interval of ∼10 min to solidify the SF particles. To examine the deposited fabrics were soaked in an aqueous solution of ethanol
dispersibility of sprayed SF particles in alcoholic media and their zeta (90 vol %) for ∼15 s to induce the formation of water-insoluble
potential, a Petri dish filled with ethanol/water (9:1, v/v) was used to particles. After drying, 10 pieces of treated fabrics were soaked in 5%
collect the developing particles. The fragrance loading capacity (LC) aqueous solutions of a neutral liquid detergent (Blue Moon,
and encapsulation efficiency (EE) were calculated by the following Guangzhou, China) and then ultrasonically washed for 5 min, 10
equations on the basis of GC measurements (see the next section for min, 15 min, ..., 50 min, respectively. Washing for 5 min was
details). considered a cycle. The washed scarf samples were then rinsed for 5
min in water. After vacuum drying, the silk fabrics were observed by a
weight of loaded fragrance scanning electron microscope (SEM). Washing durability was
LC = × 100%
weight of matrix evaluated by the retention rate of nanoparticles deposited on the
surface of fabrics, where the retention rate was defined as the particle
weight of loaded fragrance number in a square of 5 μm × 5 μm divided by the initial particle
EE = × 100% number in the same area before washing.

■
weight of fragrance in feeding
Fragrance Release Study. Release of fragrance from the RESULTS AND DISCUSSION
inclusion complexes and sprayed SF nanoparticles were studied
using gas chromatography. Ten mg of the sample was placed in a 20 We first prepared the inclusion complex of rose oxide with HP-
mL headspace vial and sealed with a PTFE/silicone rubber septum. At β-CD by dispersing the two raw materials in water with
given time intervals, 250 μL of fragrance vapor was withdrawn from sufficient stirring at ambient temperature for 2 days until the
the headspace of the vial and injected into the GC system for analysis. complexation equilibrium was established. After removal of the
Meanwhile, 250 μL of dry high-pure air was supplied to the vial after organic layer, the aqueous phase was lyophilized to gain the
each sampling to avoid negative pressure in the vial. The GC desired inclusion complex as a white powder. For comparison,
parameters were set as follows for rose oxide analysis: inlet we also synthesized a D-limonene/HP-β-CD complex using the
temperature, 250 °C; injection mode, splitless; column temperature, same method. Both complexes are hereinafter referred to as
hold for 3 min at 50 °C and then heat to 200 °C at a rate of 5 °C/ RoseIC and LimIC, respectively.
min; detector temperature, 250 °C; for limonene analysis: inlet
temperature, 250 °C; injection mode, splitless; column temperature, To validate the formation of the CD complexes, we
hold for 1 min at 65 °C and then heat to 100 °C at a rate of 2 °C/ performed FT-IR and 1H NMR analysis. As shown in Figure
min, hold for 1 min at 100 °C; detector temperature, 250 °C. The S1, IR spectra of RoseIC and HP-β-CD are very close, and the
sprayed samples before and after fragrance release were dispersed in characteristic absorptions of CD skeleton, including the CO
DI water and then extracted with ethyl acetate. The extract was used stretching mode of secondary alcohols at 1033 and 1083 cm−1,
2592 DOI: 10.1021/acsapm.9b00457
ACS Appl. Polym. Mater. 2019, 1, 2590−2596
ACS Applied Polymer Materials Article

Figure 2. SEM micrographs of (a) RoseIC@SF and (b) LimIC@SF nanoparticles generated by the electrospray process under optimized
conditions (SF conc. = 4 wt %, IC/SF = 3:4 (w/w); 1 μL/min of flow rate, 16 kV of voltage, and tip-to-collector distance of 16 cm; r.t., RH 50%).
Insets: SEM images of the corresponding alcohol-treated samples. The scale bar in the images is 2 μm.

Figure 3. Release profiles of rose oxide (A) and limonene (B) at 25 °C from their respective CD inclusion complexes and the corresponding SF
nanoparticles before and after treatment with alcohol. The fragrance release test was carried out in triplicate, and an average of three measurements
was taken.

as well as the asymmetric stretching vibration of COC hydrogen 5-H, but neither of the two possible orientations
glycosidic linkages between monosaccharidic units at 1156 adopted by guest molecules in the CD cavities was
cm−1, were almost unchanged before and after complexation.37 overwhelmingly dominant.
In the RoseIC spectrum, most absorption from the rose oxide As seen in Figure 1D, the rose oxide/HP-β-CD complex-
merged into those of the host molecules. However, the typical ation system exhibited an AL -type of phase-solubility
adsorption peaks of rose oxide at 1679 (CC stretching), behavior.36 That is, the rose oxide content in the aqueous
1255 (CO stretching), and 847 cm−1 (CH wagging) phase increased linearly in proportion to the CD concen-
could be identified. Meanwhile, the peak corresponding to the tration, indicating a 1:1 stoichiometry of the host−guest
scissoring vibration of methyl groups slightly shifted from 1376 interactions, which is quite consistent with the host/
to 1384 cm−1 (Figure 1A).38 These observations indicated that guest molar ratio of RoseIC determined by 1H NMR.
the guest molecules are embedded in the CD cavities.39 According to the phase-solubility diagram, the apparent
Furthermore, the dedicated proton signals assigned to rose stability constant (Ks) was estimated to be 3156 L/mol for
oxide and to HP-β-CD are clearly discernible in the 1H NMR the complex at 25 °C (see the Experimental Section for
spectrum (Figure 1B), suggesting that the complex is details).36 In contrast to what was observed for RoseIC, the
molecularly soluble in D2O. On the basis of 1H NMR analysis, inclusion complex LimIC has a much lower apparent stability
the molar ratio of guest to host components was determined to constant (Ks = 221 L/mol) and the molar ratio of limonene to
be 0.94:1 for the complex (see section S1.1 and Figure S2 in CD is as low as 0.24:1, although they showed the same AL-type
the Supporting Information for details). phase-solubility diagram (see section S1.2 and Figure S3 in the
Figure 1C shows the 2D ROESY spectrum of RoseIC, where Supporting Information). This difference is in concert with the
cross-peaks ascribed to dipolar interactions between the lower water solubility (13.8 mg/L) and higher saturated vapor
interior proton signals of the CD cavity (e, viz., the 5-H pressure (1.541 mmHg) of limonene compared to rose oxide
protons in the D-glucose unit) and the methyl signals (m and (63.97 mg/L, 0.551 mmHg) at 25 °C.19 Generally, CD−
o) from rose oxide are clearly observed. The appearance of fragrance complexes with Ks in the range 100−5000 L/mol are
these peaks further proves that the inclusion complex was of great value from the view of practical applications,
successfully obtained through host−guest interaction.40 More- as documented in the literature.41
over, the signal intensity of [e, m] and [e, o] is roughly the These CD inclusion complexes (ICs) dissolved very well in
same, which means that the terminal methyl groups (both m water with the regenerated SF under ambient conditions, and
and o) of rose oxide were located in close proximity to the the resulting solution allowed directly for electrospray
2593 DOI: 10.1021/acsapm.9b00457
ACS Appl. Polym. Mater. 2019, 1, 2590−2596
ACS Applied Polymer Materials Article

Figure 4. SEM micrographs of RoseIC@tSF-deposited silk fabrics before washing (A) and after 10 times of washing (B); the scale bar is 2 μm. (C)
The change in retention of nanoparticles deposited on the silk samples with washing times. The error bars represent the standard deviation of three
independent measurements.

fabrication. We noted that an appropriate combination of the the entrapped spices. After that, the fragrance was released
composition of spraying solution and the processing param- steadily at a relatively slow rate of kr = 0.85%/d, and about
eters is crucial for the formation of a stable cone-jet and, in 12.7% of rose oxide escaped from the complex within 11 days.
turn, of uniform nanoscale particles on the collector. Overall, In contrast, the accumulated release curve for the nanoparticle
SF concentration played a key role in having stable spraying RoseIC@SF was steady over the observation period, following
conditions (Figures S4 and S5). Following optimization zero-order kinetics with a much lower release rate (kr = 0.24%/
experiments, a 4 wt % SF solution with an IC/SF mass ratio d) compared to that of RoseIC. The total fraction of aroma
of 3:4 was found to produce fiber-free spherical particles with a released from the silk nanoparticles was less than 3% in the
smooth surface morphology. Figure 2 shows the respective same time range, only being approximately one-fourth of that
SEM images for as-prepared nanoparticles RoseIC@SF and for the complex.
LimIC@SF obtained under the same processing conditions. After treatment with alcohol, the nanoparticle RoseIC@tSF
Both samples contain discrete particles with no overlapping as released aroma more slowly than its pristine state (Figure 3A).
a result of mutual Coulombic repulsion during the electrospray In this case, the kr value and the total amount of fragrance
atomization.26 released over an 11-day period were down to 0.10%/d
On the basis of the analysis of SEM images, the average and 1.4%, respectively. This decrease in the release rate should
diameter of RoseIC@SF and LimIC@SF particles collected on stem from the ethanol-triggered conformational transition of
aluminum foil was estimated to be 301.2 ± 51.8 and 363.2 ± fibroin from helix−coil to β-sheet,32,33 as evidenced by IR
103.1 nm, respectively. Upon exposure to an aqueous ethanol spectroscopy (Figure S7). The β-sheet tends to form a
solution, the size of the two particles shrunk to 247.9 ± 65.8 crystalline structure and thus a denser molecular network,
and 298.6 ± 96.0 nm (Figure 2, insets). These alcohol-treated thereby elongating the diffusion path of odorous molecules in
silk nanoparticles (denoted as RoseIC@tSF and LimIC@tSF) the matrixes. This is also responsible for the above-mentioned
were found to resist dissolution and displayed a negative zeta shrinkage of particle sizes. Additionally, the lower fragrance-
potential (around −20 mV, Figure S6), which would help to loading capacity and consequent lack of sufficient driving force
keep them stable in aqueous suspension. The loading capacity toward the cargo are likely another factor for slow release.
of rose oxide and limonene was 3.90 and 0.89 wt % with As is also the case for the rose oxide-containing counterparts,
respect to the matrix material, which respectively corresponded the release of aroma from limonene-loaded systems showed
to 93.7 and 91.3% encapsulation efficiency. The preservation of similar features. By fitting the curves in Figure 3B, the release
limonene in the SF nanoparticles was comparable to that of rates (kr) were determined as 2.63, 0.86, and 0.12%/d for
capsules reported by Koocheki et al. using an emulsion LimIC and its SF nanoparticles before and after treatment with
electrospraying process, but the latter has a higher loading alcohol, respectively. A closer inspection of Figure 3A and B
capacity (∼9.21%).28 reveals that, after coating with SF by electrospray, the 11-day
Subsequently, we investigated the fragrance-release profiles accumulated release percentage of limonene from LimIC@tSF
of the composite nanoparticles at room temperature using the can be decreased by about 15 times compared to that of LimIC
headspace gas chromatography measurements;42 Figure 3 (2.5% vs 37.8%), whereas the total amount of rose oxide
depicts the results. As a control experiment, the release of rose released was about 8 times lower than that of its CD complex
oxide from its CD complex (RoseIC) was a two-step process RoseIC (1.4% vs 12.7%). This observation suggests that this
(Figure 3A). In the initial 12 h, the complex liberated ∼3% of CD-assisted encapsulation strategy is particularly attractive for
2594 DOI: 10.1021/acsapm.9b00457
ACS Appl. Polym. Mater. 2019, 1, 2590−2596
ACS Applied Polymer Materials Article

the loading and controlled release of highly volatile limonene/HP-β-CD inclusion complex (LimIC), opti-
fragrances.43−46 With regard to facile and green preparation mization of process parameters for electrospray, and
and to controlled release of aroma molecules, the sprayed SF characterization of fibroin nanoparticles and silk fabrics
nanoparticles outperformed the previously reported fragrant (PDF)
nanocapsules.10,47 More importantly, the kinetic characteristics

■
of the zero-order release observed for the present aroma-
delivery systems are highly desirable, because they allow AUTHOR INFORMATION
constant release of entrapped olfactory molecules and hence
Corresponding Author
keep the smell at a certain level.48,49
Finally, we explored the feasibility of using the electrospray *E-mail: [email protected].
technique to directly adhere nanoparticles to the substrate ORCID
surface, which would have great advantages in various Zhuxian Zhou: 0000-0002-7104-9915
applications such as fabric finishing. To this end, a piece of Youqing Shen: 0000-0003-1837-7976
silk scarf (3 cm × 3 cm) was put on the grounded collector and Liming Jiang: 0000-0002-1511-8605
the electrospray was carried out under the established
optimum conditions. After the completion of electrospray, Notes
the silk fabric samples were first subjected to a transient The authors declare no competing financial interest.
soakage in 90 vol % aqueous ethanol solution to solidify the
deposited nanoparticles and then examination of their washing
durability by observing variation in the particle number in a
■ ACKNOWLEDGMENTS
This work is financially supported by the National Key
certain region (5 μm × 5 μm) of SEM images. Research and Development Program Nanotechnology Specific
RoseIC@tSF nanoparticles directly deposited on the silk Project from the Ministry of Science and Technology of China
scarf have an average diameter of 241.6 ± 73 nm comparable (No. 2016YFA0200301).
to particles collected on the aluminum foil (247.9 ± 65.8 nm),
as shown in Figure 4A and Figure S8. It was observed that, at
the end of the 10th washing cycle, the particle size slightly
increased to 269.6 ± 74.5 nm due to the swelling effect of the
■ REFERENCES
(1) Surburg, H.; Panten, J. Common fragrance and flavor materials:
SF substrate, but the spherical morphology remained intact preparation, properties and uses, 5th ed.; Wiley-VCH: Weinheim,
(Figure 4B). Importantly, the particle retention percentage was Germany, 2006.
still more than 80% after 10 runs of washing with water, (2) Ohloff, G.; Pickenhagen, W.; Kraft, P. Scent and chemistry: the
molecular world of odors; Wiley-VCH: Weinheim, Germany, 2012.
although every washing cycle indeed led to the removal (3) Herrmann, A. The chemistry and biology of volatiles; John Wiley &
of adhered particles (Figure 4C). Undoubtedly, strong Sons: Chichester, U.K., 2010.
interactions such as hydrogen bonds and chain entanglements (4) Herrmann, A. Controlled release of volatiles under mild reaction
forming between the nanoparticle and silk substrate are conditions: from nature to everyday products. Angew. Chem., Int. Ed.
primarily responsible for the excellent washing resistance. 2007, 46, 5836−5863.
Moreover, the embedment of nanoparticles in clefts of fiber (5) Madene, A. Flavour encapsulation and controlled release − a
surfaces may contribute to their attachment on the fabrics. review. Int. J. Food Sci. Technol. 2006, 41, 1−21.

■
(6) He, L.; Hu, J. Preparation and application of flavor and fragrance
CONCLUSIONS capsules. Polym. Chem. 2018, 9, 4926−4946.
(7) Rodrigues, S. N.; Rodrigues, A. E. Scentfashion®: micro-
In summary, we established an efficient approach to produce encapsulated perfumes for textile application. Chem. Eng. J. 2009, 149,
fragrance-loaded nanoparticles on the basis of the host−guest 463−472.
chemistry and electrospray technique, which allows for more (8) Rodrigues, S. N.; Fernandes, I. P.; Martins, I. M.; Mata, V. G.;
than 90% encapsulation efficiency of fragrances in matrixes and Barreiro, F.; Rodrigues, A. E. Microencapsulation of limonene for
direct deposition of nanoparticles on the silk fabric. The textile application. Ind. Eng. Chem. Res. 2008, 47, 4142−4147.
composite nanoparticles integrate the intrinsic benefits of CDs (9) Elesini, U. S.; Urbas, R. Melamine formaldehyde microcapsules
with inclusion complexation ability and silk fibroin matrixes with fragrance core material: preparation, properties, and end use.
Text. Res. J. 2017, 87, 2435−2448.
with excellent biocompatibility and barrier effect. In view of its
(10) Ichiura, H. Direct preparation of gelatin microcapsules on paper
advantages in simple and green preparation procedures as well surface using simple coacervation technique. J. Appl. Polym. Sci. 2013,
as the resulting composite nanoparticles featuring a low rate 129, 2139−2144.
and constant aroma-release profile, i.e., an ideal zero-order (11) Hu, J.; Xiao, Z. B. Synthesis and characterization of
release kinetics, the dual barrier strategy proposed in the polybutylcyanoacrylate-encapsulated rose fragrance nanocapsule.
present study may have great potential for applications in Flavour Fragrance J. 2011, 26, 162−173.
perfume related industries and, in principle, can also be used in (12) Qiu, C.; Sun, Q. J. Preparation and characterization of essential
the fabrication of controlled or prolonged-release systems of oil-loaded starch nanoparticles formed by short glucan chains. Food
other bioactive substances such as hydrophobic drugs. Chem. 2017, 221, 1426−1433.

■
(13) Hu, J. Preparation and properties of cinnamon-thyme-ginger
composite essential oil nanocapsules. Ind. Crops Prod. 2018, 122, 85−
ASSOCIATED CONTENT 92.
*
S Supporting Information (14) Theisinger, S.; Landfester, K. Encapsulation of a fragrance via
The Supporting Information is available free of charge on the miniemulsion polymerization for temperature-controlled release.
ACS Publications website at DOI: 10.1021/acsapm.9b00457. Macromol. Chem. Phys. 2009, 210, 411−420.
(15) Liu, C.; Wang, Y. H. Core-shell nanocapsules containing
Additional information on the characterization of rose essential oil for textile application. J. Appl. Polym. Sci. 2018, 135,
oxide/HP-β-CD inclusion complex (RoseIC) and D- 45695.

2595 DOI: 10.1021/acsapm.9b00457

ACS Appl. Polym. Mater. 2019, 1, 2590−2596
ACS Applied Polymer Materials Article

(16) Hofmeister, I.; Landfester, K.; Taden, A. pH-Sensitive (38) Stuart, B. Infrared spectroscopy: fundamentals and applications;
nanocapsules with barrier properties: fragrance encapsulation and Wiley: Chichester, U.K., 2004.
controlled release. Macromolecules 2014, 47, 5768−5773. (39) Kfoury, M.; Fourmentin, S. Investigation of monoterpenes
(17) Ye, K.; Lu, X. H. Use of caprylic/capric triglyceride in the complexation with hydroxypropyl-β-cyclodextrin. J. Inclusion Phenom.
encapsulation of dementholized peppermint fragrance leading to Macrocyclic Chem. 2014, 80, 51−60.
smaller and better distributed nanocapsules. RSC Adv. 2016, 6, (40) Schneider, H. J. NMR studies of cyclodextrins and cyclodextrin
84119−84126. complexes. Chem. Rev. 1998, 98, 1755−1785.
(18) Cao, Z. H.; Qi, D. M. Synthesis of fragrance/silica nanocapsules (41) Marques, H. M. C. A review on cyclodextrin encapsulation of
through a sol-gel process in miniemulsions and their application as essential oils and volatiles. Flavour Fragrance J. 2010, 25, 313−326.
aromatic finishing agents. Colloid Polym. Sci. 2015, 293, 1129−1139. (42) Xiao, Z. B.; Zhu, G. Y. Preparation and sustained-releasing
(19) Sadovoy, A. V.; Lomova, M. V.; Antipina, M. N.; Braun, N. A.; characterization of aromatic wallpaper. Prog. Org. Coat. 2017, 104,
Sukhorukov, G. B.; Kiryukhin, M. V. Layer-by-layer assembled 50−57.
multilayer shells for encapsulation and release of fragrance. ACS (43) Kayaci, F.; Uyar, T. Solid inclusion complexes of vanillin with
Appl. Mater. Interfaces 2013, 5, 8948−8954. cyclodextrins: their formation, characterization, and high-temperature
(20) Xiao, Z. B.; Zhu, G. Y. Preparation, characterization and stability. J. Agric. Food Chem. 2011, 59, 11772−11778.
rheological behavior of chitosan nanocapsule emulsion encapsulated (44) Uyar, T.; Hacaloglu, J.; Besenbacher, F. Electrospun
tuberose fragrance. Pol. J. Chem. Technol. 2016, 18, 1−8. polystyrene fibers containing high temperature stable volatile
(21) Jaworek, A. Electrospray application to powder production and fragrance/flavor facilitated by cyclodextrin inclusion complexes.
React. Funct. Polym. 2009, 69, 145−150.
surface coating. J. Aerosol Sci. 2018, 125, 57−92.
(45) Uyar, T.; Nur, Y.; Hacaloglu, J.; Besenbacher, F. Electro-
(22) Lee, Y. H.; Mei, M.; Bai, M. Y.; Zhao, S.; Chen, D. R. Release
spinning of functional poly(methyl methacrylate) nanofibers contain-
profile characteristics of biodegradable-polymer-coated drug particles
ing cyclodextrin-menthol inclusion complexes. Nanotechnology 2009,
fabricated by dual-capillary electrospray. J. Controlled Release 2010,
20, 125703.
145, 58−65. ̇
(46) Celebioglu, A.; Kayaci-Senirmak, F.; Ipek, S.; Durgun, E.; Uyar,
(23) Hao, S. L.; Wang, B. C. Rapid preparation of pH-sensitive T. Polymer-free nanofibers from vanillin/cyclodextrin inclusion
polymeric nanoparticle with high loading capacity using electrospray complexes: high thermal stability, enhanced solubility and antioxidant
for oral drug delivery. Mater. Sci. Eng., C 2013, 33, 4562−4567. property. Food Funct. 2016, 7, 3141−3153.
(24) Cao, Y.; Ran, H. T. Drug release from core-shell PVA/silk (47) Wen, Z.; You, X. K. Liposomal incorporation of rose essential
fibroin nanoparticles fabricated by one-step electrospraying. Sci. Rep. oil by a supercritical process. Flavour Fragrance J. 2011, 26, 27−33.
2017, 7, 11913. (48) Birajdar, M. S.; Lee, J. Sonication-triggered zero-order release
(25) Qu, J.; Li, M. Z. Silk fibroin nanoparticles prepared by by uncorking core−shell nanofibers. Chem. Eng. J. 2016, 288, 1−8.
electrospray as controlled release carriers of cisplatin. Mater. Sci. Eng., (49) Celia, C.; Grattoni, A. Sustained zero-order release of intact
C 2014, 44, 166−174. ultra-stable drug-loaded liposomes from an implantable nanochannel
(26) Gañań -Calvo, A. M.; Dávila, J.; Barreto, A. Current and droplet delivery system. Adv. Healthcare Mater. 2014, 3, 230−238.
size in the electrospraying of liquids. Scaling laws. J. Aerosol Sci. 1997,
28, 249−275.
(27) Koo, S. Y.; Pan, C. H. Microencapsulation of peppermint oil in
an alginate-pectin matrix using a coaxial electrospray system. Int. J.
Food Sci. Technol. 2014, 49, 733−739.
(28) Khoshakhlagh, K.; Koocheki, A. Development and character-
ization of electrosprayed Alyssum homolocarpum seed gum nano-
particles for encapsulation of D-limonene. J. Colloid Interface Sci. 2017,
490, 562−575.
(29) Szejtli, J. Introduction and general overview of cyclodextrin
chemistry. Chem. Rev. 1998, 98, 1743−1754.
(30) Szente, L.; Szejtli, J. Highly soluble cyclodextrin derivatives:
chemistry, properties, and trends in development. Adv. Drug Delivery
Rev. 1999, 36, 17−28.
(31) Altman, G. H.; Kaplan, D. L. Silk-based biomaterials.
Biomaterials 2003, 24, 401−416.
(32) Chen, C.; Cao, C. B. Preparation of non-woven mats from all-
aqueous silk fibroin solution with electrospinning method. Polymer
2006, 47, 6322−6327.
(33) Rössle, M.; Riekel, C. Structural evolution of regenerated silk
fibroin under shear: Combined wide- and small-angle X-ray scattering
experiments using synchrotron radiation. Biopolymers 2004, 74, 316−
327.
(34) Wang, X. Q.; Kaplan, D. L. Silk coatings on PLGA and alginate
microspheres for protein delivery. Biomaterials 2007, 28, 4161−4169.
(35) Kim, U. J.; Kaplan, D. L. Three-dimensional aqueous-derived
biomaterial scaffolds from silk fibroin. Biomaterials 2005, 26, 2775−
2785.
(36) Higuchi, T.; Connors, K. A. Phase-solubility techniques. In
Advances in analytical chemistry and instrumentation; Reilley, C. N.,
Ed.; Interscience Publishers-John Wiley & Sons: New York, 1965;
Vol. 4, pp 117−121.
(37) Kayaci, F.; Uyar, T. Solid inclusion complexes of vanillin with
cyclodextrins: their formation, characterization, and high-temperature
stability. J. Agric. Food Chem. 2011, 59, 11772−11778.

2596 DOI: 10.1021/acsapm.9b00457

ACS Appl. Polym. Mater. 2019, 1, 2590−2596