Dual-mode
Anti-counterfeiting
With the development of information technology and economy, the demand
for anti-counterfeiting technology is becoming increasingly urgent in
many fields such as food, medicine, clothing, and communication. The
most common single color anti-counterfeiting is limited due to its
single mode practical application. Herein we present a multimode
anti-counterfeiting film based on Y-TCPP/DBCZ PVA composite gel film
(Figure 6a). Considering the risk of MOF being damaged by direct
exposure to alkali, writing with PVA dispersion of DBCZ and MOF is more
suitable than applying MOF and DBCZ onto PVA films. We prepared
multifunctional gel 1 (a dispersion of 1 mg MOF, 100 mg PVA, and 4 mL
water), gel 2 (a dispersion of 0.2 mg DBCZ, 100 mg PVA, and 4 mL water),
and gel 3 (a dispersion of 1 mg MOF, 0.2 mg DBCZ, 100 mg PVA, and 4 mL
water) as ink for writing. Afterwards, use multifunctional gel 1, 2, and
3 to write the numbers ”1”, ”3”, and ”6” on the substance, respectively.
Due to insufficient sample size to construct continuous strokes,
additional multifunctional gel is added to the corresponding stroke.
After drying and cross-linking, the composite gel film is immersed in a
Tris solution with pH=13. After the fluorescence turns red, excess
alkaline solution is wiped off and dried. The dried film exhibits
obvious red ”1”, blue ”3”, and rose red ”6” under excitation of 365 nm
light. After turning off ultraviolet light, a yellow-green ”3” and a
faintly visible ”6” can be seen. After soaking the film in an artificial
sweat solution at pH=4.7 for 20 minutes and drying, the light red ”1”,
blue ”3”, and light purple ”6” were displayed under excitation of 365 nm
light. After turning off ultraviolet light, the yellow-green ”3” remains
unchanged from before sweat treatment, and the weaker lightness ”6” is
clearly visible (Figure 6b). These experimental results prove the
application prospect of Y-TCPP/DBCZ PVA mixed gel in dual-mode
anti-counterfeiting materials, and show the application value of organic
afterglow materials with adjustable solid emission in
anti-counterfeiting.
Conclusions
Based on the advantage of Y-TCPP MOF for OH- specific
response, a two-color stimulus response gel was constructed in
combination with DBCZ PVA system, and a sweat pH sensing and
anti-counterfeiting mode that is economical, applicable, easy to prepare
and operate was found. A MOF with specific response to OH- was
synthesized and combined with the DBCZ PVA system to construct a
stimulus responsive thin film material with fluorescence red blue color
changing with pH, which has good repeatability. The phosphorescence of
the mixed system exhibits a significant decrease in emission intensity
and luminescence lifetime at pH=13. The above spectroscopy results are
visible to the naked eye. A sweat pH sensor was constructed and
exhibited different luminescence changes under different conditions. The
effect of different pH sweat on luminescence may be used for health
testing. A fluorescent phosphorescent composite anti-counterfeiting
material has been constructed, which can achieve dual-mode
anti-counterfeiting performance. Under alkaline and sweat conditions, it
exhibits different fluorescence and phosphorescence properties visible
to the naked eye.
Experimental
Materials
Yttrium nitrate hexahydrate
(Y(NO3)3·6H2O, 99.9%),
7H-dibenzo[c, g]carbazole (DBCZ, 98%), polyvinyl alcohol 1799 (PVA,
1799 type, alcoholysis degree 98-99%), lactate (90%) were purchased
from Aladdin Co., Ltd. Tetra-(4-carboxyphenyl) porphyrin (TCPP, 95%)
was purchased from Leyan Co., Ltd. Glutaraldehyde (25% aqueous
solution), hydrochloric acid (36%-38% HCl aqueous solution), urea
(99.0%), glucose (AR), tris-(hydroxymethyl)aminomethane (Tris, 99.5%),
sodium hydroxide (NaOH, 99%) sodium chloride (NaCl, 99.5%) were
purchased from Sinopharm Chemical Reagent Co., Ltd. Artificial sweat
were purchased from Shenzhen Zhongwei equipment co., LTD. All other
solvents and reagents were of analytical grade and used as received.
Milli-Q water (18.2MΩ·cm) was used in all cases.
Instruments
Use GeminiSEM 500 to record the scanning electron microscope (SEM) image
and the X-ray energy dispersion spectrum (EDS) image. The steady-state
fluorescence and phosphorescence measurements were obtained on the
Hitachi F-4600 fluorescence spectrophotometer at room temperature. X-ray
photoelectron spectroscopy (XPS) was performed on ESCALAB 250Xi X-ray
photoelectron spectrometer. X-ray diffraction (XRD) was performed on the
Rigaku SmartLab 9kW. Use SHIMADZU UV-2700 PC spectrophotometer to
measure UV-vis absorption spectrum. Fourier transform infrared
spectroscopy (FT-IR) was measured by using BRUKER TENSOR II.
Preparation of Y-TCPP MOF
The synthesis method is taken from the previous
report.[27] TCPP (21.0 mg, 0.0266 mmol) was
completely dissolved in DMF (45.0 mL) in a 100 mL round bottom flask.
Y(NO3)3·6H2O (15.0 mg,
0.0392 mmol) was dissolved in 3 mL ultra-pure water. Then
Y(NO3)3 solution was added into TCPP
solution and stirred evenly. The mixture was stirred and heated to 60 °C
for 2 h, further heated to 100 °C for 2 h. After cooling, the reacted
liquid was centrifuged at 10000 rpm for 25 min, collected the
precipitation, and washed twice with ethanol to obtain brown solid. The
brown product attached to the bottle wall could be dispersed by soaking
in anhydrous ethanol. Finally, Y-TCPP was stored in ethanol and need to
be shaken to uniform dispersion before use. The concentration of the
dispersion solution is obtained by measuring a quantitative liquid in a
bottle and weighing the solid after drying in a vacuum oven at 60 °C for
30 hours.
Preparation of Y-TCPP/DBCZ PVA mixed gel
100 mg of PVA was added into a glass bottle containing 4 mL of
ultra-pure water, and heated at 90 °C until it is completely dissolved.
After cooling, 1 mg of centrifuged Y-TCPP MOF was added and the mixed
solution was ultrasoniced until well-distributed. 1 mg of DBCZ was
dissolved in 0.1 mL of ethanol and ultrasoniced until it is fully
dissolved. 20 μL DBCZ solution was added to PVA solution and stirred for
0.5 h. The dispersion solution is light brown and unobvious turbidity
was observed. 0.1 mL of sample was dropped onto a glass sheet and dried
in air at 40 °C for 1 hour to form the gel film.
Preparation of water-resistant mixed gel
0.15 mL of 25% glutaraldehyde, 0.25 mL of concentrated hydrochloric
acid and 2.6 mL of acetone was stirring evenly as the cross-linking
solution. The gel film was completely immersed in a 5 mL beaker
containing 3 mL cross-linking solution for 5 min, then take it out and
blow off the excess liquid with nitrogen, placed in a ventilated
environment for 1 h. The gel film is stable and can not be eroded by
water.
Supporting Information
The supporting information for this article is available on the WWW
under https://doi.org/10.1002/cjoc.2023xxxxx.
Acknowledgement
This study was supported by the Basic Research Fund for the Central
Universities (WK3450000006).
References
- Sakharov, D. A.; Shkurnikov, M. U.; Vagin, M. Yu.; Yashina, E. I.;
Karyakin, A. A.; Tonevitsky, A. G. Relationship between Lactate
Concentrations in Active Muscle Sweat and Whole Blood. Bull.
Exp. Biol. Med. 2010 , 150, 83–85.
- Patterson, M. J.; Galloway, S. D. R.; Nimmo, M. A. Variations in
Regional Sweat Composition in Normal Human Males. Acta Physiol.
Scand. 2002 , 174, 41–46.
- Ardalan, S.; Hosseinifard, M.; Vosough, M.; Golmohammadi, H. Towards
Smart Personalized Perspiration Analysis: An IoT-Integrated
Cellulose-Based Microfluidic Wearable Patch for Smartphone
Fluorimetric Multi-Sensing of Sweat Biomarkers. Biosens.
Bioelectron. 2020 , 168, 112450.
- Son, J.; Bae, G. Y.; Lee, S.; Lee, G.; Kim, S. W.; Kim, D.; Chung, S.;
Cho, K. Cactus-Spine-Inspired Sweat-Collecting Patch for Fast and
Continuous Monitoring of Sweat. Adv. Mater. 2021 , 33,
40, 2102740.
- Yang, X.; Yi, J.; Wang, T.; Feng, Y.; Wang, J.; Yu, J.; Zhang, F.;
Jiang, Z.; Lv, Z.; Li, H.; Huang, T.; Si, D.; Wang, X.; Cao, R.; Chen,
X. Wet-Adhesive On-Skin Sensors Based on Metal–Organic Frameworks for
Wireless Monitoring of Metabolites in Sweat. Adv. Mater.2022 , 34, 44, 2201768.
- Lee, J.; Pyo, M.; Lee, S.; Kim, J.; Ra, M.; Kim, W.-Y.; Park, B. J.;
Lee, C. W.; Kim, J.-M. Hydrochromic Conjugated Polymers for Human
Sweat Pore Mapping. Nat. Commun. 2014 , 5, 3736.
- Yang, D. S.; Ghaffari, R.; Rogers, J. A. Sweat as a Diagnostic
Biofluid, Science 2023 , 379, 6634, 760–761.
- Gao, W.; Ota, H.; Kiriya, D.; Takei K.; Javey, A. Flexible Electronics
toward Wearable Sensing. Acc. Chem. Res. 2019 , 52, 3,
523–533.
- Lv, M.; Zhou, W.; Tavakoli, H.; Bautista, C.; Xia, J.; Wang, Z.; Li,
X. Aptamer-Functionalized Metal-Organic Frameworks (MOFs) for
Biosensing. Biosens. Bioelectron. 2021 , 176, 112947.
- Cai, Y.; Zhu, H.; Zhou, W.; Qiu, Z.; Chen, C.; Qileng, A.; Li, K.;
Liu, Y. Capsulation of AuNCs with AIE Effect into Metal-Organic
Framework for the Marriage of a Fluorescence and Colorimetric
Biosensor to Detect Organophosphorus Pesticides. Anal. Chem.2021 , 93, 19, 7275–7282.
- Zhang, H.-W.; Zhu, Q.-Q.; Yuan, R.; He, H. Crystal Engineering of
MOF@COF Core-Shell Composites for Ultra-Sensitively Electrochemical
Detection. Sensor. Actuat. B-Chem. 2021 , 329, 129144.
- Biswas, S.; Lan, Q.; Xie, Y.; Sun, X.; Wang, Y. Label-Free
Electrochemical Immunosensor for Ultrasensitive Detection of
Carbohydrate Antigen 125 Based on Antibody-Immobilized Biocompatible
MOF-808/CNT. ACS Appl. Mater. Interfaces 2021 , 13, 2,
3295–3302.
- Zhao, L.; Song, X.; Ren, X.; Wang, H.; Fan, D.; Wu, D.; Wei, Q.
Ultrasensitive Near-Infrared Electrochemiluminescence Biosensor
Derived from Eu-MOF with Antenna Effect and High Efficiency Catalysis
of Specific CoS2 Hollow Triple Shelled Nanoboxes for Procalcitonin.Sensor. Actuat. B-Chem. 2021 , 191, 113409.
- Shu, Y.; Su, T.; Lu, Q.; Shang, Z.; Xu, Q.; Hu, X. Highly Stretchable
Wearable Electrochemical Sensor Based on Ni-Co MOF Nanosheet-Decorated
Ag/rGO/PU Fiber for Continuous Sweat Glucose Detection. Anal.
Chem. 2021 , 93, 48, 16222–16230.
- Adeel, M.; Asif, K.; Rahman, Md. M.; Daniele, S.; Canzonieri, V.;
Rizzolio, F. Glucose Detection Devices and Methods Based on
Metal–Organic Frameworks and Related Materials. Adv. Funct.
Mater. 2021 , 31, 52, 2106023.
- Kang, J.-Y.; Koo, W.-T.; Jang, J.-S.; Kim, D.-H.; Jeong, Y. J.; Kim,
R.; Ahn, J.; Choi, S.-J.; Kim, I.-D. 2D Layer Assembly of Pt-ZnO
Nanoparticles on Reduced Graphene Oxide for Flexible
NO2 Sensors. Sensor. Actuat. B-Chem.2021 , 331, 129371.
- Xiao, J.; Fan, C.; Xu, T.; Su, L.; Zhang, X. An Electrochemical
Wearable Sensor for Levodopa Quantification in Sweat Based on a
Metal-Organic Framework/Graphene Oxide Composite with Integrated
Enzymes. Sensor. Actuat. B-Chem. 2022 , 359, 131586.
- Li, Y.; Wang, R.; Wang, G.-E.; Feng, S.; Shi, W.; Cheng, Y.; Shi, L.;
Fu, K.; Sun, J. Mutually Noninterfering Flexible Pressure–Temperature
Dual-Modal Sensors Based on Conductive Metal–Organic Framework for
Electronic Skin. ACS Nano 2022 , 16, 1, 473–484.
- Zhou, W.-L.; Lin, W.; Chen, Y.; Liu, Y. Supramolecular Assembly
Confined Purely Organic Room Temperature Phosphorescence and Its
Biological Imaging. Chem. Sci. 2022 , 13, 7976-7989.
- Zeng, Y.; Nguyen, V. P.; Li, Y.; Kang, D. H.; Paulus, Y. M.; Kim, J.
Chorioretinal Hypoxia Detection Using Lipid-Polymer Hybrid Organic
Room-Temperature Phosphorescent Nanoparticles. ACS Appl. Mater.
Interfaces 2022 , 14, 16, 18182–18193.
- Zhang, Y.; Chen, X.; Xu, J.; Zhang, Q.; Gao, L.; Wang, Z.; Qu, L.;
Wang, K.; Li, Y.; Cai, Z.; Zhao, Y.; Yang, C. Cross-Linked
Polyphosphazene Nanospheres Boosting Long-Lived Organic
Room-Temperature Phosphorescence. J. Am. Chem. Soc.2022 , 144, 13, 6107–6117.
- Song, Z.; Shang, Y.; Lou, Q.; Zhu, J.; Hu, J.; Xu, W.; Li, C.; Chen,
X.; Liu, K.; Shan, C.-X.; Bai, X. A Molecular Engineering Strategy for
Achieving Blue Phosphorescent Carbon Dots with Outstanding Efficiency
Above 50%. Adv. Mater. 2023 , 35, 6, 2207970.
- Yu, X.; Liu, K.; Wang, B.; Zhang, H.; Qi, Y.; Yu, J. Time-Dependent
Polychrome Stereoscopic Luminescence Triggered by Resonance Energy
Transfer Between Carbon Dots-In-Zeolite Composites and Fluorescence
Quantum Dots. Adv. Mater. 2023 , 35, 6, 2208735.
- Liu, H.; Ye, W.; Mu, Y.; Ma, H.; Lv, A.; Han, S.; Shi, H.; Li, J.; An,
Z.; Wang, G.; Huang, W. Highly Efficient Blue Phosphorescence from
Pillar-Layer MOFs by Ligand Functionalization. Adv. Mater.2022 , 34, 5, 2107612.
- Zhou, B.; Yan, D. Hydrogen-Bonded Two-Component Ionic Crystals Showing
Enhanced Long-Lived Room-Temperature Phosphorescence via TADF-Assisted
Förster Resonance Energy Transfer. Adv. Funct. Mater.2019 , 29, 4, 1807599.
- Lin, F.; Wang, H.; Cao, Y.; Yu, R.; Liang, G.; Huang, H.; Mu, Y.;
Yang, Z.; Chi, Z. Stepwise Energy Transfer: Near-Infrared Persistent
Luminescence from Doped Polymeric Systems. Adv. Mater.2022 , 34, 15, 2108333.
- Wang, X.; Chu, C.; Wu, Y.; Deng, Y.; Zhou, J.; Yang, M.; Zhang, S.;
Huo, D.; Hou, C. Synthesis of Yttrium(III)-Based Rare-Earth
Metal-Organic Framework Nanoplates and Its Applications for Sensing of
Fluoride Ions and pH. Sensor Actuat. B-Chem. 2020 ,
321, 128455.
- Zhang, Y.; Su, Y.; Wu, H.; Wang, Z.; Wang, C.; Zheng, Y.; Zheng, X.;
Gao, L.; Zhou, Q.; Yang, Y.; Chen, X.; Yang, C.; Zhao, Y. Large-Area,
Flexible, Transparent, and Long-Lived Polymer-Based Phosphorescence
Films, J. Am. Chem. Soc. 2021 , 143, 34, 13675–13685.
- Mukherjee, S.; Thilagar, P. Recent Advances in Purely Organic
Phosphorescent Materials. Chem. Commun. 2015 , 51,
10988–11003.