RESEARCH ARTICLE

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Synthesis of Nanosized 𝜸-Cyclodextrin Metal-Organic

Frameworks as Carriers of Limonene for Fresh-Cut Fruit
Preservation Based on Polycaprolactone Nanofibers
Zeyu Qin, Qinbo Jiang, Yucheng Zou, Meiyu Chen, Jiawen Li, Yang Li, and Hui Zhang*

and biochemical changes, and foodborne

To address the issue of bacterial growth on fresh-cut fruits, this paper ailments.[3] To control the growth of mi-
reports the synthesis of nanosized 𝜸-cyclodextrin metal-organic frameworks croorganisms, techniques such as the ad-
(CD-MOFs) using an ultrasound-assisted method and their application dition of antibacterial food additives, ir-
as carriers of limonene for antibacterial active packaging. The effects of the radiation with ultraviolet rays, ultrasonic
processing technology, high-pressure pro-
processing parameters on the morphology and crystallinity of the CD-MOFs
cessing, and active antibacterial packaging
are investigated, and the results prove that the addition of methanol is the key are employed.[2] Among these, active an-
to producing nanosized CD-MOFs. The limonene loading content of the nano- tibacterial packaging can inhibit microor-
sized CD-MOFs can reach approximately 170 mg g−1 . The sustained-release ganisms by releasing antibacterial agents
behaviors of limonene in the CD-MOFs are evaluated. Molecular docking sim- such as natural antibacterial agents and
nanomaterials.[4] Recently, plant essential
ulations reveal the distribution and binding sites of limonene in the CD-MOFs.
oils (EOs) have been widely used in packag-
CD-MOFs are deposited on the surfaces of polycaprolactone (PCL) nanofibers ing owing to their strong antibacterial effect
via an immersion method, and limonene-loaded CD-MOF@PCL nanofibers are and “natural” characterization. However,
prepared. The morphology, crystallinity, thermal stability, mechanical proper- EOs have some limitations, such as volatil-
ties, and antibacterial activity of the nanofibers are also studied. The nanofiber ity, heat sensitivity, poor water solubility,
film effectively inhibits bacterial growth and prolongs the shelf life of fresh-cut and susceptibility to oxidation. Therefore,
encapsulation technology has been adopted
apples. This study provides a novel strategy for developing antibacterial
to overcome these drawbacks. In recent
active packaging materials based on CD-MOFs and PCL nanofibers. years, several useful technologies have been
used to enhance sustained drug release and
retention in active packaging, including par-
ticle encapsulation, nanoemulsions, Pick
1. Introduction ering emulsions, and electrospinning.[5] Cyclodextrin (CD) trap-
ping is a typical particle encapsulation method. Although many
Fruits are nutritionally important foods rich in bioactive scholars have demonstrated that EO/CD inclusions improve an-
compounds, including vitamins, minerals, antioxidants, and tibacterial activities and reduce the release rate of EOs, the load-
phytochemicals.[1] A fresh-cut product, as defined by the United ing capacity of CD inclusions is relatively low, generally approxi-
Fresh Produce Association, is a type of fruit or vegetable that has mately 10%, which limits their application.[6,7]
been processed by trimming, peeling, and/or cutting and then Metal-organic frameworks (MOFs) are porous polymeric ma-
packaged or bagged as a ready-to-use product that provides con- terials that offer versatile platforms for the delivery of drugs and
sumers with convenience, flavor, and high nutrition while pre- bioactive compounds. MOFs consist of organic bridging ligands
serving its freshness.[2] Consequently, fresh-cut fruits are popular (dicarboxylic acid, tricarboxylic acid, tetracarboxylic acid, and im-
among consumers. However, without a protective covering, the idazolate) that coordinate with metal ions (secondary building
cut surface of the fruit is constantly exposed to the environment, units), such as alkaline metals (Ca or Mg) or Fe, Mn, Al, Zr, and
and fresh-cut fruits are much more prone to microbial contami- Ti, to form open crystalline frameworks with stable porosity.[8]
nation, which leads to a loss of nutritional content, physiological In contrast to conventional porous materials, MOFs exhibit a
larger surface area, which confers remarkable cargo-loading ca-
pacity and suitability for efficient encapsulation.[9] For exam-
Z. Qin, Q. Jiang, Y. Zou, M. Chen, J. Li, Y. Li, H. Zhang
College of Biosystems Engineering and Food Science ple, Lawson et al. demonstrated that the MOF 74 family could
Zhejiang University load curcumin at a high content, ranging from 30% to 50%.[10]
Hangzhou310058, China Chen et al. introduced insulin into crystalline mesoporous MOF
E-mail: [email protected] NU-1000 and achieved a high loading of approximately 40 wt%
within 30 min.[11] However, most MOFs are composed of metals
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/smll.202400399
(Co, Ni, Cr, and Gd) and nonfood-grade organic linkers that are
toxic and unsuitable for food packaging applications. Therefore,
DOI: 10.1002/smll.202400399

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Scheme 1. Schematic of the preparation of L@𝛾-CD-MOF@PCL nanofibers and their application in the preservation of fresh-cut apples.

𝛾-CD MOFs prepared by using 𝛾-CD and Group IA (K/Rb/Cs) infrared spectroscopy (ATR-FTIR), X-ray diffraction (XRD), dif-
metal salts are preferable. They have body-centered cubic ex- ferential scanning calorimetry (DSC), and thermal gravimetric
tended structures with large spherical pores 17 Å in diameter and analysis (TGA). The limonene loading and release behavior of the
apertures 7.8 Å across. A 𝛾-CD-MOF crystal consists of a porous, L@CD-MOF@PCL nanofibers were evaluated. Furthermore, the
body-centered cubic array of (𝛾-CD)6 cubic units, which are con- antibacterial activities of the nanofibers and their application in
nected by coordination of the secondary face hydroxyl groups on the preservation of apples were investigated (Scheme 1).
alternating D-glucopyranosyl residues to one of the alkali metal
cations. Owing to their high cargo loading capacity and safety, 2. Results and Discussion
𝛾-CD-MOFs have been applied in the food and pharmaceutical
industries.[12] For instance, Li et al. developed 𝛾-CD-MOF-K to 2.1. Morphology and Crystalline Property of CD-MOF
adsorb ethylene gas in storage packaging and delay red kiwi fruit
ripening.[13] Lu et al. prepared a cross-linked 𝛾-CD-MOF as a car- CD-MOFs were prepared using a hydrothermal method with the
rier of iodine for the treatment of periodontitis. Thus, using 𝛾- assistance of ultrasound, where the polyethylene glycol (PEG)
CD-MOF to encapsulate EO is feasible.[14] amount, methanol volume, ultrasonic time, and temperature af-
Currently, active packaging based on nanofibers is gaining fected the morphology of the nanosized CD-MOFs. Figure 1A il-
popularity because nanofibers exhibit high specific surface areas, lustrates the synthesis of regular cubic CD-MOFs when 64 mg of
high porosity, and flexible designs for functionalization, which PEG was added with a reaction temperature of 50 °C, ultrasoni-
are desirable characteristics for active food packaging.[15] There- cation time of 5 min, and methanol content of 8 mL. Moreover,
fore, we attempted to load antibacterial 𝛾-CD-MOFs onto the as the amount of PEG increased, the CD-MOFs ceased to adhere
surfaces of nanofibers. Although nanofibers loaded with MOFs to each other and the edges became distinct. These results con-
have been used in drug delivery, gas and heavy-metal ion ad- firm that PEG could facilitate crystallization and regulate the size
sorption, energy storage, and biosensing, the potential of these and uniformity of CD-MOFs, which is consistent with previous
nanostructures for use in antibacterial packaging remains to research.[20] Figure 1B demonstrates that the volume of methanol
be explored.[16–19] Moreover, research on 𝛾-CD-MOF loading on influenced the size of the CD-MOFs significantly, with a reac-
nanofibers is scarce, because 𝛾-CD-MOFs prepared via traditional tion temperature of 50 °C, PEG amount of 64 mg, and ultrason-
methods (vapor diffusion and solvothermal methods) are mi- ication time of 5 min, reducing this size from 1180 to 144 nm
croscale, making loading these 𝛾-CD-MOFs onto nanofibers dif- when the volume increased from 0 to 8 mL. This change occurred
ficult. Hence, in this study, we first investigated the conditions because the large volume of methanol caused oversaturation,
for preparing nanosized 𝛾-CD-MOFs and the effects of param- which increased the number of nucleation sites.[21] Figure 1C re-
eters of the fabrication process on the morphology and struc- veals that the size of the CD-MOFs first decreased and then in-
ture of nanosized 𝛾-CD-MOFs. We then used limonene, the ma- creased as the ultrasonication time varied from 5 to 20 min, with a
jor component of citrus EO, as the model molecule to investi- 50 °C reaction temperature, PEG content of 64 mg, and methanol
gate the interaction between 𝛾-CD-MOF and limonene. The ef- amount of 8 mL. Ultrasonic wave generates acoustic cavitation,
fects of the loading conditions on the limonene loading content which affects nucleation and crystal growth rates.[22] A similar
were also studied. Finally, we deposited nanosized 𝛾-CD-MOFs trend was observed in the fabrication of TMU-21 ({[Zn2 (oba)2 (4-
on the surfaces of polycaprolactone (PCL) nanofibers and encap- bpmn)]·(DMF)1.5 }n ), where the size of TMU-21 decreased as the
sulated limonene (L) in CD-MOF@PCL. The L@CD-MOF@PCL ultrasonication time increased from 30 to 60 min, but plate-
nanofibers were characterized using attenuated total reflectance like structures with micro dimensions were formed when the

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Figure 1. Effects of processing parameters such as the amount of PEG (A1, 0 mg; A2, 32 mg; A3, 64 mg; A4, 128 mg), volume of methanol (B1, 0 mL;
B2, 2 mL; B3, 4 mL; B4, 8 mL), ultrasonication time (C1, 0 min; C2, 5 min; C3, 10 min; C4, 20 min), and temperature (D1, 30 °C; D2, 40 °C; D3, 50 °C;
D4, 60 °C) on the morphology of CD-MOFs.

reaction time reached 90 min.[23] The effect of the ultrasonication cluding cellulose,[28] starch,[29] and CD-MOF.[30] We found that
time on the size of MOF has not been clarified. Qiu et al. reported the amount of PEG and the volume of methanol had stronger
that the size of Zn3 (BTC)2 ·12H2 O increased as the reaction time effects on the RC than the ultrasonication time and tempera-
increased from 10 (50–100 nm) to 30 min (100–200 nm).[24] In ture. As shown in Figure 2, except for the samples whose PEG
contrast, some researchers have found that a longer ultrasoni- addition amounts were 0 and 32 mg, the other samples exhib-
cation time resulted in smaller MOFs. The width of a TMU-4 ited diffraction peaks at approximately 3.9°, 6.9°, 7.9°, 8.7°, 9.9°,
([[Zn2 (oba)2 (4-bpdb)]·2DMF]n ) plate decreased from 173 nm in 11.9°, 13.4°, 16.9°, 19.2°, 20.5°, and 22.9°, which are character-
30 min to 123 nm in 90 min.[25] Figure 1D indicates that when istic diffraction peaks of 𝛾-CD-MOF and observed in the sim-
the PEG amount was 64 mg, ultrasonication time was 5 min, ulated XRD results for CD-MOFs.[31] Comparing the XRD pat-
and methanol volume was 8 mL, 𝛾-CD-MOF tended to agglom- terns of the as-synthesized and simulated samples indicated that
erate under low temperatures (30 °C and 40 °C). A high reac- the as-synthesized sample was not a pure phase. Instead, it con-
tion temperature leads to larger CD-MOFs because high tem- tained both crystalline and amorphous regions. Thus, the RC
peratures result in vigorous molecular motion and rapid crystal was used to evaluate the purity of sample, as shown in Table 1.
growth.[26] When the PEG addition amount was 0 and 32 mg, two broad
Figure 2 and Table 1 illustrate the effects of the PEG amount, peaks appeared at 16.9° and 22.7°, indicating amorphous struc-
methanol volume, ultrasonication time, and temperature on the tures. According to Table 1, increasing in the amount of PEG
crystalline properties of the nanosized CD-MOFs. The relative improved the RC because surfactants such as PEG, PVP, and
crystallinity (RC) is defined as the mass fraction of the crystalline PVSA can decrease the nucleation rate and increase the degree
regions in a material and indicates the degree of long-range order of crystallinity.[32–34] However, the increase in methanol volume
in a crystalline material. This characteristic was originally used decreases the RC because methanol can induce supersaturation.
to calculate the RC of polymer-PET because polymers contain Supersaturation governs the kinetics and morphology of crys-
both crystalline and amorphous regions.[27] Many researchers tal growth. Higher supersaturation not only leads to a higher
have employed this method to calculate the RC of materials, in- nucleation rate but also increases the likelihood of producing

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Figure 2. Effects of the amount of A) PEG, B) volume of methanol, C) ultrasonication time, and D) temperature on the XRD pattern of CD-MOF.

irregular crystal shapes and low crystallinity. Lower supersatura- in a significant increase in RC, probably because the increase in
tion not only results in a lower crystallization rate but also fa- temperature improved the crystallization rate. Mulyati et al. also
vors the formation of regular crystal shapes and single-crystal found that when the reaction time was the same, the higher the
forms.[21,35] The RC increased as the ultrasonication time in- reaction temperature, the higher the RC of MOF-5.[37] However,
creased from 0 to 5 min, but a continuous increase in time did Khoshhal et al. found that the RC was 100%, 95.97%, and 61.25%
not result in a significant difference in the RC. This phenomenon for Cu-BTC synthesized at 80, 110, and 140 °C, because Cu2 O was
proved that ultrasound could shorten the crystallization time, produced at high temperatures.[38]
the products reached their maximum crystallinity very quickly.[22]
Gordon et al. observed the same phenomenon, in which neither
the power nor the time of the ultrasound had a significant in- 2.2. N2 Adsorption–Desorption Measurements and Loading
fluence on the crystallinity.[36] Temperature can affect nucleation Capacity of CD-MOFs
and crystal growth by altering the solubility and supersaturation
of a sample, consequently increasing or decreasing the relative To examine the effect of the size of CD-MOF on the Brunauer-
crystallinity. In our study, the increase in temperature resulted Emmett-Teller (BET) surface area and pore size of 𝛾-CD-MOF,

Table 1. Effect of parameters on the RC of various CD-MOFs

PEG 0 mg 32 mg 64 mg 128 mg

RC (%) 16.68 ± 1.67c) 42.43 ± 2.39b) 45.67 ± 3.12a),b) 46.24 ± 2.45a)

Methanol (mL) 0 2 4 8
RC (%) 64.13 ± 3.51a) 52.81 ± 1.93b) 45.43 ± 3.76c) 46.12 ± 2.20c)
Time (min) 0 5 10 20
RC (%) 40.12 ± 2.03b) 43.76 ± 3.56a),b) 45.12 ± 2.47a) 44.29 ± 1.34a)
Temperature (°C) 30 40 50 60
RC (%) 35.71 ± 1.73c) 42.91 ± 1.98b) 45.21 ± 3.09a) 43.52 ± 2.12a),b)
a–d)
The values are given as the mean ± SD, and the entries in the same column that differ significantly (p < 0.05).

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Figure 3. A) N2 adsorption analytical curve and B) size distribution of various CD-MOFs.

we synthesized various nanosized 𝛾-CD-MOFs by varying the increased from 30 to 40 °C, the loading content increased from
volume of methanol (1, 2, 4, and 8 mL), which were labeled as 134.8 to 172.7 mg g−1 . A further increase in temperature did not
CD-MOF-1, CD-MOF-2, CD-MOF-4, and CD-MOF-8. Figure 3A significantly increase the loading content because a higher tem-
shows that the isotherms of all 𝛾-CD-MOFs displayed a type I perature resulted in limonene evaporation. Similarly, the load-
shape, indicating the presence of micropores.[39] Figure 3B re- ing capacity increased rapidly when the reaction time was ex-
veals that the pore diameters of all 𝛾-CD-MOFs ranged from 1 to tended from 1 to 9 h. These results agree with those of previ-
2 nm. As shown in Table 2, the BET specific area increased from ous studies.[42,43] Therefore, the optimal loading conditions were
110.90 to 469.41 m2 g−1 , and the average pore diameter decreased a molar ratio of 1:8, reaction temperature of 40 °C, and reac-
from 1.9 to 1.74 nm. These results, along with the SEM results, tion time of 9 h, and the maximum loading content was ap-
suggest that a smaller CD-MOF size resulted in a larger BET sur- proximately 170 mg g−1 . Subsequent samples were prepared
face area and smaller average pore size. The adsorption capacity under the optimal loading conditions. Adsorption/desorption
is proportional to the specific surface area;[40] therefore, smaller tests were performed over six cycles to assess the stability and
CD-MOFs could load more limonene. In addition, according to reusability of CD-MOF. As shown in Figure 4D, the reusability
previously published papers, the BET surface area differs sub- of nanosized CD-MOF (CD-MOF-8) was higher than that of CD-
stantially from laboratory to laboratory, varying from 495 to 1220 MOF (CD-MOF-1). However, compared with other MOFs such
m2 g-1 . This variation can be attributed to two factors. First, the as HKUST[44,45] and ZIF,[46,47] the reusability of the nanosized
solvent and organic linker retention differ. Second, the degree of CD-MOFs was poor, because high-valence metal ions and ligands
channel collapse differs during solvent evacuation.[41] can form more rigid structures than potassium ion and CD.[48,49]
Hence, part of the structure of the CD-MOF collapsed when ex-
posed to external stimuli, which led to a decrease in the loading
2.3. Effects of Parameters on Limonene Loading Content of capacity.
Nanosized 𝜸-CD-MOF

The effects of the molar ratio (𝛾-CD unit: L), temperature, and 2.4. Characterization of L@CD-MOF
time on the limonene loading content of nanosized 𝛾-CD-MOF
(CD-MOF-8) were evaluated. As depicted in Figure 4, the load- The effect of limonene loading on the morphology of the CD-
ing content increased to 173.3 mg g−1 as the molar ratio (𝛾- MOFs was evaluated. Figure 5 shows that the edges of the block-
CD: limonene) decreased from 1:2 to 1:8. The loading content shaped CD-MOF-1 become blurred after encapsulation, but CD-
plateaued as the molar ratio increased. When the temperature MOF-4 and CD-MOF-8 remained intact after limonene was
loaded onto the CD-MOFs. Reducing materials to the nanoscale
Table 2. BET surface areas and average pore diameters of various CD- can increase their mechanical strength.[50] For example, the hard-
MOFs ness of nanosized ZIF-8 is higher than that of microscale ZIF-
8.[51] Mechanical stability influences MOF collapse. Some MOFs
BET surface area [m2 g−1 ] Average pore diameter [nm] can collapse under various external stimuli.[41,52,53] Hence, the
edges of CD-MOF-1 became blurred because stirring and heat-
CD-MOF-1 110.90 ± 20.14d) 1.90 ± 0.34a)
ing led to the collapse of CD-MOF-1 during limonene loading.
CD-MOF-2 157.72 ± 26.25c) 1.75 ± 0.19b)
The Fourier-transform infrared (FTIR) spectra of the samples
CD-MOF-4 274.60 ± 30.92b) 1.74 ± 0.13c)
are shown in Figure 6A. The peaks of 𝛾-CD at 1151, 1077, and
CD-MOF-8 469.41 ± 52.80a) 1.74 ± 0.12c) 1019 cm−1 can be attributed to C─C stretching, C─O stretch-
a–d)
The values are given as the mean ± SD, and the entries in the same column that ing vibrations, and stretching vibration of the C─O─C glyco-
differ significantly (p < 0.05). sidic bridge. The peaks at 1643 and 2929 cm−1 are due to ─OH

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Figure 4. Effects of A) molar ratio, B) temperature, and C) reaction time on the limonene loading content of nanosized 𝛾-CD-MOF. D) Change in
limonene content after recycle adsorption/desorption.

bending and C─H stretching vibration, respectively. A broad of solvent (approximately 14%) occurred from 25 °C to 170 °C;
peak located at 3300 cm−1 is related to the O─H stretching the degradation of the CD-MOF crystal structure (approximately
vibration.[54] The characteristic peaks of limonene are observed 42%) occurred from 200 °C to 330 °C; and the complete decom-
at 2962, 2923, 2874, and 2855 cm−1 corresponding to C-H stretch- position of CD-MOF (13%) occurred from 350 °C to 400 °C. The
ing vibration, and the specific absorption band at 1645 cm−1 re- weight loss curves of the L@CD-MOFs are similar to those of
flects the stretching vibration of C═C. The C─H deformation vi- the CD-MOFs, except that the initial weight loss of the L@CD-
bration peaks are seen at 989 and 890 cm-1 .[55] L@CD-MOF ex- MOF is larger than that of the CD-MOF because of the presence
hibited the CH3 stretching peak at 2923 cm-1 and bending peak of limonene. As illustrated in the DTG curves, the temperature
at 1376 cm-1 of limonene, confirming that limonene was loaded corresponding to the maximum weight loss rate (Tmax ) of the
onto the CD-MOFs. Moreover, two peaks existed in the range CD-MOFs and L@CD-MOFs was more than 270 °C. The ther-
from 1600 to 1700 cm-1 in L@CD-MOF, whereas CD-MOF, 𝛾- mal analysis results prove that 𝛾-CD-MOFs were thermally sta-
CD, and limonene only displayed one peak in this region, in- ble, which could protect limonene from the impacts of changes
dicating the presence of limonene in L@CD-MOF. The nuclear in the environment. Chen et al. also prepared thermally stable 𝛾-
magnetic resonance (NMR) spectra further prove that limonene CD-MOFs for encapsulating curcumin, which delayed curcumin
was encapsulated in the CD-MOFs because L@CD-MOF-8 ex- decomposition.[56] Hu et al. demonstrated the thermal stability
hibited both characteristic peaks of limonene and CD-MOF-8, as of 𝛼-CD-MOFs, 𝛽-CD-MOFs, and 𝛾-CD-MOFs, with their main
shown in Figure 6B. weight loss occurring in the temperature ranges of 230–316 °C,
Figure 6C shows that the characteristic peaks of CD-MOFs 253–353 °C, and 215–322 °C, respectively.[31]
were present in L@CD-MOF, and the RC of L@CD-MOF was
lower than that of the original CD-MOF. Moreover, L@CD-MOF-
8 exhibited a higher RC than L@CD-MOF-1, which suggested 2.5. Molecular Docking
that the process of loading limonene was more destructive to
the structure of CD-MOF-1, which is consistent with the SEM The molecular docking results revealed the optimal binding
results in Figure 5. As shown in Figure 6D, the weight loss of sites for limonene when loaded into CD-MOFs. As shown in
𝛾-CD occurred at 25–130 °C and 283–360 °C, corresponding to Figure 7, using a CD hexamer as the model for the CD-MOFs,
the loss of solvent (methanol and water) and decomposition of limonene molecules tended to enter the cavities of individual CD
𝛾-CD, respectively.[31] The main weight loss of CD-MOF-1 and monomers at low limonene concentrations. As the number of
CD-MOF-8 can be divided into three stages: The weight loss limonene molecules increased, the cavities of CD were gradually

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Figure 5. SEM results for various CD-MOFs. A) CD-MOF-1, B) CD-MOF-2, C) CD-MOF-4, D) CD-MOF-8, E) L@CD-MOF-1, F) L@CD-MOF-2, G)

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L@CD-MOF-4, and H) L@CD-MOF-8.
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Figure 6. A) FTIR spectra of 𝛾-CD, L@CD, CD-MOFs, L@CD-MOFs, and L. B) NMR spectra of limonene, L@CD-MOF-8, and CD-MOF-8. C) XRD
patterns and D) TGA results of 𝛾-CD, CD-MOFs, and L@CD-MOFs.

filled with limonene molecules, with each cavity accommodating 2.6. Releasing Curves of Limonene
two limonene molecules. When some of the CD cavities were oc-
cupied, the limonene molecules entered the larger internal cav- Figure 8 illustrates the effect of the size of the CD-MOF on the
ities of the CD-MOFs, which accounted for the significantly im- limonene loading content and the releasing behaviors of various
proved loading capacity of the CD-MOFs. Several scholars have CD-MOFs at room temperature (approximately 20 °C) and un-
drawn similar conclusions. For instance, Shen et al. found that der room humidity (40% RH). As the volume of methanol in-
when the hydrophobic cavities of all 𝛾-CDs were occupied, caf- creased from 1 to 8 mL, the limonene loading content increased
feic acid tended to enter the large hydrophilic cavities of CD- from 112.4 to 178.9 mg g−1 , suggesting that CD-MOF with a
MOFs.[30] Han et al. observed three typical domains for sulfur smaller size had a higher adsorption capacity. This result is con-
hexafluoride: one in the middle of 𝛾-CD pairs; another being the sistent with the BET surface area results. Moreover, in the first
cavity of single 𝛾-CD; and the third being the hydrophilic cavity of 9 d, the limonene content decreased sharply and the decrease
𝛾-CD-MOF.[57] in CD-MOF size led to an increase in the released amount of

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Figure 7. Molecule docking simulations of limonene distributed in CD-MOF. The molar ratios of limonene molecules to 𝛾-CD unit were A) 1:6, B) 1:1,
and C) 2:1.

limonene (39.3, 49.1, 92.5, and 102.8 mg g−1 for L@CD-MOF- 2.8. Characterization of PCL Nanofibers with Deposited
1, L@CD-MOF-2, L@CD-MOF-4, and L@CD-MOF-8, respec- CD-MOFs
tively). However, after 9 d, the limonene content in all CD-MOFs
decreased slowly, and the remaining content reached approxi- As shown in Figure 10A, each sample exhibited a peak at
mately 40 mg on day 21. Figure 8B proves that L@CD-MOF-8 1734 cm-1 , which is the characteristic peak of PCL correspond-
had the highest release ratio (approximately 80%) and a lifetime ing to the C═O stretching vibration. Further, when CD-MOFs
of 21 d. These results prove that the nanosized CD-MOFs not only were deposited on the nanofibers, a broad peak at approximately
possess a higher loading capacity but also release limonene more 3400 cm-1 appeared, indicating the O─H stretching vibration of
slowly.[40] the CD-MOF.[60] Moreover, as the immersion time increased, the
intensity of O-H stretching vibration increased, suggesting that
the CD-MOF loading content increased.
2.7. Morphology of PCL Nanofibers with Deposited CD-MOFs In Figure 10B, at low scattering angles, a higher background
is observed because of the scattering of radiation in the air.
The PCL nanofibers coated with CD-MOF layers are shown Figure 10B illustrates the differences in the XRD patterns of
in Figure 9. As the immersion time increased, the loading PCL and MOF@PCL. PCL exhibited characteristic peaks at 21.4°
amount of CD-MOFs increased, and the interspace between and 23.5°, indicating its crystalline nature.[61] In addition to
the nanofibers was filled with CD-MOFs. In addition, accord- the characteristic peaks of PCL, L@CD-MOF@PCL-30 exhib-
ing to Figure 9B,C, the CD-MOFs in MOF@PCL-60 were larger ited weak peaks at 5.16° and 7.4°. In contrast, MOF@PCL-60,
than those in L@MOF@PCL-60, indicating that encapsulating L@MOF@PCL60, and MOF@PCL90 displayed peaks at 3.9°,
limonene damaged the crystallinity of the CD-MOFs. This phe- 5.7°, 6.9°, 11.9°, 13.4°, and 16.7°, which are characteristic of CD-
nomenon was because the structures formed by potassium ions MOF, indicating the deposition of CD-MOF on the nanofibers. In
and CDs were not as rigid as those formed by other hypervalent addition, the intensity of the peak at 5.7° in the XRD pattern of
ions and ligands.[48,49] Hence, part of the CD-MOF structure col- MOF@PCL-60 was greater than that of L@MOF@PCL60, prov-
lapsed during the loading process, leading to decreases in size ing the crystallinity of the MOF in L@MOF@PCL-60 decreased
and crystallinity. A similar phenomenon has been observed in after the loading of limonene, which was consistent with SEM re-
the XRD patterns of other CD-MOFs loaded with drugs.[58,59] sults. The intensity of the sharp peak at 21.4° in the XRD pattern

Figure 8. A) Changes of limonene content in L@CD-MOF-1, L@CD-MOF-2, L@CD-MOF-4, and L@CD-MOF-8. B) Release ratio of limonene from
L@CD-MOF-1, L@CD-MOF-2, L@CD-MOF-4, and L@CD-MOF-8.

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Figure 9. SEM images of A) MOF@PCL-30, B) MOF@PCL-60, C) L@MOF@PCL-60, and D) MOF@PCL-90.

of MOF@PCL-90 decreased, confirming that excessive immer- Figure 11A shows that all samples were typical brittle materials
sion damaged the crystalline structure of PCL. because the elongation at break of all samples was less than 5%,
Figure 10C illustrates the thermal stabilities of various sam- and the stress–strain curves of all samples displayed only brittle
ples. An endothermic peak existed at 53.3 °C corresponding to regions.[63] Figure 11B–D demonstrates that as the immersion
the melting point (Tm ) of PCL in each DSC curve. The deposi- time increased from 30 to 90 min, the elastic modulus decreased
tion of the CD-MOF on the nanofibers caused peak splitting. As from 129.16 to 53.85 MPa, tensile strength decreased from 1.17
shown in Figure 10C, one main weight-loss stage occurred for to 0.39 MPa, and elongation at break decreased from 3.55% to
each sample. The weight loss stage of PCL ranged from 350 °C 1.15%. The mechanical properties were determined by the inter-
to 450 °C, which was related to the degradation of PCL. For action between the polymer molecules, and a long immersion
MOF@PCL and L@MOF@PCL, the stage ranged from 300 °C time caused chain disentanglement of PCL, leading to a decrease
to 400 °C, which was related to the degradation of CD-MOF in mechanical performance.[64]
and PCL. According to the DTG curves in Figure 10D, the Tmax
values of PCL, MOF@PCL-30, MOF@PCL-60, L@MOF@PCL,
and MOF@PCL-90 were 412 °C, 374 °C, 361 °C, 349 °C, and 2.10. Loading Content and Releasing Behavior of Limonene in
356 °C, respectively, indicating that a longer immersion time Different Nanofibers
and limonene encapsulation process could decrease the ther-
mal stability. Some researchers have reported that, when ZIF- According to Figure 12A, the limonene content of
8 was deposited on polylactic acid nanofibers, the thermal sta- L@MOF@PCL-60 (92.51 mg g−1 ) was significantly higher
bility of the nanofibers is impaired as the incubation time was than that of L@MOF@PCL-30 (55.44 mg/g), because a longer
extended.[62] immersion time resulted in more CD-MOFs on the nanofibers.
Moreover, the rate of decline in the limonene content during
the early stage was higher than that during the later stages.
2.9. Mechanical Properties of PCL Nanofibers with Deposited For the L@MOF@PCL-60 nanofibers, the amount of limonene
CD-MOFs significantly decreased by 30.14 mg g−1 in the first three days,
but from day 3 to day 24, it decreased by 38.13 mg g−1 . According
The elastic modulus, tensile strength, and elongation at break to Figure 12B, release ratio of all nanofibers plateaued out on
of the films are indicators of their mechanical properties. day 24.

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Figure 10. A) FTIR spectra, B) XRD patterns, C) DSC curves, D) TGA and DTG curves of the PCL, the MOF@PCL-30, the MOF@PCL-60, the
L@MOF@PCL-60, and the MOF@PCL-90 nanofibers.

Figure 11. A) Stress–strain curve and B) elastic modulus, C) tensile strength, and D) elongation at break of the PCL, MOF@PCL-30, MOF@PCL-60,
L@MOF@PCL-60, and MOF@PCL-90 nanofibers.

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Figure 12. A) Variations in limonene content and B) release profile of L@MOF@PCL-30, L@MOF@PCL-60, and L@MOF@PCL-90 nanofibers during
30 d of storage.

2.11. Antibacterial Effects of Different Nanofibers tion rate of nanofiber film on bacterial growth on fresh-cut ap-
ples. As shown in Figure 13B, on day 7, the inhibition rates of
The inhibition zones were used to evaluate the antibacte- L@MOF@PCL-60 and L@MOF@PCL-90 reached 38.73% and
rial activity of L@MOF@PCL. As shown in Figure 13A, 50.01%, respectively, indicating that these two nanofiber films
PCL and L@MOF@PCL-30 exhibited no inhibitory activity. could inhibit bacterial growth. The effects of the L@MOF@PCL-
L@MOF@PCL-60 and L@MOF@PCL-90 displayed stronger in- 60 nanofibers on the total soluble solids (TSS) and titratable
hibitory effects against S. aureus than E. coli because E. coli is acidity (TA) of fresh-cut apples are shown in Figure 13C,D.
a gram-negative bacterium that has a thick layer on the out- Compared with the apples in the PCL group, the TSS of ap-
side and cell wall. To further evaluate the antibacterial activity ples in the L@MOF@PCL-60 group decreased more slowly than
of L@MOF@PCL during application, we measured its inhibi- that in the PCL group, because fewer bacteria in apples of the

Figure 13. A) Inhibition zones of the PCL, L@MOF@PCL-30, L@MOF@PCL-60, and L@MOF@PCL-90 nanofibers against S. aureus (the top culture
dish) and E. coli (the bottom culture dish). B) Inhibition rate of L@MOF@PCL-30, L@MOF@PCL-60, and L@MOF@PCL-90 nanofiber films on day 7.
Effects of the PCL and L@MOF@PCL-60 nanofibers on the C) TSS and D) TA of apples.

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L@MOF@PCL-60 group consumed less respiration substrate and collector was 15 cm. MOF@PCL nanofibers were fabricated using an
such as soluble saccharides. The TA of the apples in the PCL immersion method. First, the PCL nanofibers were immersed in a 7 mg
group decreased during the first three days and then increased. mL−1 KOH solution for 30 min and then dried in a vacuum oven. Next, the
dried nanofibers were immersed in 20 mg mL−1 𝛾-CD mixed solution (wa-
However, the TA of the apples in the L@MOF@PCL-60 group de-
ter:ethanol = 5:3) at 40 °C for 10 min, and the methanol solution of PEG
creased in the first four days and then increased. In addition, after (8 mg mL−1 ) was added to the 𝛾-CD mixed solution. The volumes of the
three days, the TA of the apples in the PCL group was higher than two solutions were equal. After the PCL nanofibers were immersed in the
that of the apples in the L@MOF@PCL-60 group. This feature solution for 30, 60, or 90 min, they were removed and washed thrice with
can be attributed to two factors. During storage, organic acids ethanol. The collected nanofibers were dried in a vacuum oven. Accord-
can be consumed by fruit respiration, which causes a decrease ing to the immersion time, the nanofibers were denoted as MOF@PCL-
30, MOF@PCL-60, and MOF@PCL-90. The preparation conditions for
in TA in the earlier stage. In contrast, bacteria produce organic
L@MOF@PCL-60 were the same as those used for the preparation of
acids that increase TA.[65–67] L@CD-MOF.
Characterization: The morphologies of CD-MOF, L@CD, MOF@PCL,
and L@MOF@PCL were analyzed using a field-emission scanning elec-
3. Conclusion tron microscope (GeminiSEM 300, Zeiss, Germany), and the average CD-
MOF size and nanofiber diameter were determined using the ImageJ soft-
This paper demonstrated that nanosized 𝛾-CD-MOFs could be
ware. The crystallinity of 𝛾-CD, CD-MOF, PCL, L@CD-MOF, MOF@PCL
synthesized using an ultrasound-assisted method, and the sizes nanofibers, and L@MOF@PCL nanofibers was investigated via powder
and crystallinities of the nanosized 𝛾-CD-MOFs could be adjusted X-ray diffraction (PXRD, PA Nalytical B.V., the Netherland) measurement.
by changing the processing parameters. The 𝛾-CD-MOFs could A diffraction range of 2𝜃 from 3° to 60° was selected. The relative crys-
act as efficient carriers of limonene and achieve a high loading tallinity (RC) of each sample was calculated using the JADE 4.0 software,
content (17.6%) and stable release. The molecular docking simu- by applying the following equation:
lations revealed that limonene molecules tended to enter the cav-
ities of CD monomers and the internal cavities of 𝛾-CD-MOFs. IC
RC = (1)
The 𝛾-CD-MOFs could be deposited on the surfaces of PCL IC + IA
nanofibers via the immersion method, forming a porous and
where IC is the integrated area between the crystalline reflections and
uniform layer. The L@MOF@PCL nanofibers exhibited good an-
amorphous halo, and IA is the integrated area between the amorphous
tibacterial activity against E. coli and S. aureus and improved the halo and baseline.
preservation quality of fresh-cut apples. This study provides a FTIR spectra at 400 to 3600 cm-1 of CD-MOF, L@CD, L@CD-MOF,
novel strategy for developing antibacterial active packaging ma- and L@MOF@PCL were collected on an FTIR spectrometer (Nicolet 170-
terials based on 𝛾-CD-MOFs and PCL nanofibers. SX apparatus, Thermo Nicolet Ltd., USA) with an attenuated total reflec-
tion unit. NMR spectra were recorded on a Bruker 400 MHz spectrom-
eter using deuterated dimethyl sulfoxide as the solvent. N2 adsorption–
desorption isotherms were measured at 77 K using a porosimeter (ASAP
4. Experimental Section 2460 3.01, Micromeritics, USA), which was used to analyze the BET surface
area and pore structures of the samples. TGA was performed using a TGA
Preparation of Nanosized (Nano)-CD-MOFs: Nano-CD-MOFs were
Q500 instrument (TA Instruments, Newcastle, USA). DSC was performed
synthesized using a hydrothermal method with the assistance of ultra-
using a DSC-1 instrument (Metter-Toledo Corp., Switzerland). The heating
sound. 𝛾-CD (162 mg) and potassium hydroxide (KOH, 56 mg) were dis-
rate for thermal analysis was 10 °C min−1 . The mechanical properties of
solved in a mixture of methanol (3 mL) and water (5 mL). The mixed so-
the PCL and L@MOF@PCL nanofibers were measured using a mechani-
lution was placed in a water bath at a certain temperature and subjected
cal testing instrument (Instron 5944, USA). Films with a thickness of 189
to ultrasound (28 kHz, 100 W) for a certain period to ensure the complete
± 10 μm were cut into 5 mm × 20 mm pieces. The clamp speed was set
dissolution of 𝛾-CD and KOH. A certain amount of PEG (Mw ≈ 20000)
to 1 mm min−1 .
was then dissolved in a certain volume of methanol; after complete disso-
Determination of Limonene Loading Content: The limonene loading
lution, the solution was added to the previous solution, and the ultrasonic
content was evaluated according to a method employed in a previous
treatment was continued for some time. Finally, the solution was left to
study.[6] L@CD-MOF and L@MOF@PCL nanofibers were added to 10 mL
stand for 60 min at room temperature and the CD-MOFs were collected
of 75% ethanol (1 mg mL−1 ) and sonicated for 15 min. The mixture was
by discarding the supernatant and washing three times with methanol via
then centrifuged at 4000 × g for 5 min, and the absorbance of the super-
centrifugation. The collected CD-MOF was dried under a vacuum at 50 °C,
natant was measured at 231 nm using a Microplate Reader (Infinite M200
and the effects of processing parameters such as the temperature, ultra-
PRO, Tecan Co., Ltd., Switzerland). The concentration of limonene was cal-
sonic treatment time, PEG amount, and methanol volume on the mor-
culated based on the standard limonene concentration–absorbance cali-
phology and crystalline structure of CD-MOFs were investigated.
bration curve. The regression equation is as follows:
Preparation of L@CD-MOF and L@CD Inclusion: L@CD-MOF and
L@CD inclusions were prepared using an impregnation method. A certain ( )
amount of nano-CD-MOF or 𝛾-CD was suspended in limonene ethanol Y = 0.0041X + 0.0328 r 2 = 0.9994 (2)
solution (43.2 mg mL−1 ) for 9 h with a magnetic stirrer at 40 °C. The in-
clusions were collected via centrifugation and washed three times with where X (μg mL−1 ) is the limonene loading content and Y is the ab-
ethanol, and then the inclusions were dried under a vacuum at 40 °C. The sorbance of limonene at 231 nm.
effects of the molar ratio (𝛾-CD monomer unit: L), temperature, and time Reusability Experiments: The CD-MOFs were regenerated according to
on the loading content were investigated. the following procedure. L@CD-MOF was immersed in methanol and
Preparation of PCL, MOF@PCL, and L@MOF@PCL Nanofibers: The stirred for 4 h. The mixture was then centrifuged at 4000 × g for 5 min, and
PCL nanofibers were produced via electrospinning. A 20 wt% PCL (Mw the CD-MOFs were collected by discarding the supernatant. The collected
≈ 80 000) solution was prepared by dissolving a certain amount of PCL CD-MOFs were dried under a vacuum at 50 °C for more than 12 h until
and a small amount of chitosan in hexafluoroisopropanol, which was then limonene was undetectable. The regenerated CD-MOF was used for the
spun into a nanofiber mat. A positive voltage of 20 kV and flow rate of next adsorption cycle. Recyclable adsorption experiments were conducted
0.5 mL h−1 were set. The distance between the tip of the syringe needle over six adsorption–desorption cycles.

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Limonene Release: To measure the release rate of limonene, a certain Data Availability Statement
amount of L@CD-MOF or L@MOF@PCL was kept for some time in the
open air in the laboratory under room temperature (20 °C) and humidity The data that support the findings of this study are available from the
(40% RH). The limonene content in the samples was evaluated every 3 d. corresponding author upon reasonable request.
The calculation method was the same as that described in Section 2.6.
Molecule Docking: Molecular docking was performed to identify L cav-
ity sites. The structural model was retrieved from the Cambridge Crystal-
lographic Data Center (CSD Ref code: LAJLAL, CCDC number 773709). Keywords
The structural model of limonene was obtained from PUBMED (Pub-
antibacterial active packaging, fresh-cut fruits, limonene, polycaprolactone
Chem CID 22311). Energy minimization was performed by the Scien-
nanofibers, 𝛾-cyclodextrin metal-organic frameworks
tific Compass Company (Hangzhou, China). Molecular docking was con-
ducted using the AutoDockTools-1.5.7 software. In the docking model,
the extended aperiodic CD-MOF structure, which omitted K+ and OH− , Received: January 17, 2024
was constructed as the receptor. The CD-MOF model consisted of six Revised: March 31, 2024
molecules, including six hydrophobic cavities and one hydrophilic cavity. Published online:
The search area was limited to a 70 × 70 × 70 Å cube box centered on the
typical CD-MOF structure. The grid space of 0.645 Å was used to cover the
entire CD-MOF structure, and the local potential of atoms was calculated
via the Gasteiger-Marsili method. The remaining docking parameters were
set to the default values. [1] A. B. Perumal, L. Huang, R. B. Nambiar, Y. He, X. Li, P. S. Sellamuthu,
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This study was funded by the National Natural Science Foundation of
China (grant no. 32272463). The authors thank teacher Chaogang Xing [20] T. Rajkumar, D. Kukkar, K.-H. Kim, J. R. Sohn, A. Deep, J. Ind. Eng.
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