Rapid Detection of Micro Nanoplastics Via Integration of Luminescent Metal Phenolic Networks Labeling and Quantitative Fluorescence Imaging in A Portable Device

1 Rapid Detection of Micro/Nanoplastics Via
2 Integration of Luminescent Metal Phenolic

3 Networks Labeling and Quantitative Fluorescence
4 Imaging in A Portable Device
5
6 Haoxin Yea, Xinzhe Zhengb, Haoming Yanga, Matthew D. Kowalc, Teresa M. Seifriedc, Gurvendra
7 Pal Singha, Krishna Aayusha, Guang Gaod, Edward Grantc, David Kittsa, Rickey Y. Yadaa, Tianxi
8 Yanga*
9 a Food, Nutrition and Health, Faculty of Land and Food Systems, The University of British
10 Columbia, Vancouver V6T1Z4, Canada
11 b Department of Computer Science, Faculty of Engineering, The University of Hong Kong, Hong
12 Kong 999077, China
13 c Department of Chemistry, Faculty of Science, The University of British Columbia, Vancouver
14 V6T1Z4, Canada
15 d Life Sciences Institute, The University of British Columbia, Vancouver V6T1Z2, Canada
16
17 *Corresponding author: Tianxi Yang (tianxi.yang@ubc.ca)
18
19
20
21
22
23
24 KEYWORD: micro-and nano-plastics; luminescent metal–phenolic networks; fluorescence
25 imaging; on-site detection ; wireless portable device
https://doi.org/10.26434/chemrxiv-2023-jnbm1 ORCID: https://orcid.org/0000-0003-4197-9262 Content not peer-reviewed by ChemRxiv. License: CC BY-NC-ND 4.0
26 ABSTRACT
27 The fact that there is an accumulation of micro-and nano-plastics (MNPs) in ecosystems which
28 poses tremendous environmental risks for terrestrial and aquatic organisms is undeniable. Thus,
29 designing improved rapid, field-deployable, and sensitive analytical devices that can assess the
30 potential risks of MNPs pollution is critical. Since current techniques for MNPs detection have
31 limited effectiveness, we sought to design a wireless portable device that will allow rapid, sensitive,
32 and on-site detection of MNPs. Coupling this capacity with remote data processing via machine
33 learning algorithms in a mobile device APP will further enable quantitative fluorescence imaging
34 of MNPs. To achieve this goal, we utilized a developed supramolecular labeling strategy,
35 employing luminescent metal-phenolic networks (L-MPNs) composed of zirconium ions, tannic
36 acid, and rhodamine B, to label a wide range of MNP sizes (i.e.,10 μm, 1 μm, 500 nm, and 50 nm).
37 Results showed that our device can quantify MNPs and detect particle quantities as low as 330
38 micro-plastic particles and 3.08×106 nano-plastic particles in less than 20 min; while also
39 successfully facilitating quantitative analysis of real-world MNPs samples. The determination of
40 diverse types of MNPs released from commercial plastic cups revealed that the quantity of released
41 plastic particles reached ranges of hundred-million after exposure to boiling water and subsequent
42 30 min cooling. The device was shown to be user-friendly and operative on a mobile APP by
43 untrained personnel to conduct data processing remotely and effectively. The analytical platform
44 integrating quantitative fluorescence imaging, customized data processing, decision tree model
45 and low-cost analysis ($0.015 per assay) has great potential for high-throughput screening of
46 various types of MNPs in agri-food and environmental systems.
47
48 1. INTRODUCTION
49 Use of conventional plastics are abundant for many facets of contemporary life, including but
50 not limited to applications for construction, textiles, medical devices and food packaging
51 materials.1–3 However, the extensive use of plastics has led to substantial contamination of
52 terrestrial and marine ecosystems that is worrisome to the public and government regulators alike.
53 Currently, approximately 20%–42% of the total global plastics formerly used now reside in the
54 land and 53 million metric tons of plastic trash is estimated to enter aquatic ecosystems per year
55 by 2030.4,5 Even more shocking is the fact that large visible plastic residues in the agri-food and
56 environmental systems can interact with various substances that result in degradation to micro-
57 plastics (MPs, particle size from 1 μm to 5 mm) and nanoplastics (NPs, particle size less than 1
58 μm) as a result mechanical sheer stress, exposure to heat and ultraviolet (UV) photooxidation or
59 microbial degradation.6–8 These plastic fragments transport easily from one substrate to another
60 through the food chains and water circulation causing adverse changes to the environmental
61 systems. It has been reported that micro-and nano-plastics (MNPs) pose a huge threat to the health
62 of living organisms, with nanoplastics in particular exhibiting toxic outcomes in humans.
63 Underlying health risks to such contamination include inducing oxidative stress and inflammation
64 and increasing risk of onset of death from cardiovascular and respiratory diseases, lung cancer.
65 More acute effects related to MNPs exposure include potentially affecting growth, development
66 and reproduction of organisms by disturbing the normal metabolism.9–11
67 Reliable detection of MNPs is critical for risk assessment analyses. Present day methods for
68 detection and quantify MNPs are suboptimal. Although imaging techniques, such as Transmission
69 Electron Microscopy (TEM), Confocal Laser Scanning Microscopy (CLSM), and Atomic Force
70 Microscopy (AFM) offer satisfactory visualization capabilitiy for MNPs, these techniques are
71 lacking for quantitative analysis.12–15 Alternative approaches, such as Particle Tracking Analysis
72 (PTA), Inductively Coupled Plasma–Mass Spectrometry (ICP-MS), and Gas Chromatography–
73 Mass Spectrometry (GC-MS) are effective to determine MNPs concentrations; nonetheless, these
74 methods also have limitations that include high cost of laboratory materials, time-consuming
75 operations, and trained personnel to perform the analyses.16–18 Additionally, the quantification of
76 MNPs in diverse real-world plastic samples, including those derived from river water, soil or
77 released from commercial plastic packaging, presents considerable challenges. As such, there is
78 strong motivation to develop a rapid, reliable and convenient analytical approach to quantify
79 MNPs.
80 The rapidly advancing field of developing fluorescence-enabled portable microscopy presents

81 a rapid and on-site imaging approach for specific analyte detection due to remarkable sensitivity
3
82 and portability. The technique has used for imaging various fluorescently labeled substances, such
83 as chloride, heavy metal ions, RNA, viruses and bacteria,19–24 thus serving as a point-of-care
84 diagnostic or an environmental inspection tool. Researchers have reported that fluorescence
85 staining of micro-plastics is a promising method for fast recognition of plastic particles. For
86 instance, Leonard et al.25 developed a smartphone that was based on detecting micro-plastics
87 utilizing Nile Red staining. However, this approach requires a 24-hour waiting period to mitigate
88 unwanted background signal interference and also lacks the capability to identify nano-plastics
89 specificaly. Moreover, Nile Red pH instability poses a further challenge to ensure assay accuracy,
90 especially when analyzing environmental samples having diverse pH levels.26 Traditional
91 fluorescent labeling methods for plastic particles, such as combined swelling-diffusion and
92 covalent coupling techniques are also very complex, and have inherent cumbersome pre-treatment
93 work for labeling particles.27,28
94 In order to achieve rapid and accurate MNPs detection using a fluorescence-enabled method,
95 a robust labeling method is needed. Metal phenolic networks (MPNs) are a class of naturally
96 derived low-toxic and stimulus-responsive metal–organic networks constructed from metal ions
97 and phenolic ligands.29–31 MPNs capture a variety of particle types (e.g., organic, inorganic, and
98 biological entities) through the coordination between metal ions and phenolic ligands and have
99 been used for various imaging techniques, such as near-infrared region (NIR) II
100 fluorescence/photoacoustic imaging and magnetic resonance imaging.32–34 Recently, MPNs have
101 been integrated with organic dyes through π interactions that create various luminescent metal
102 phenolic networks (L-MPNs) by a rapid and versatile coating process (< 5 min).35 The outcome
103 has demonstrated outstanding effectiveness in labeling diverse particles by producing ultra-thin
104 coatings with tailored luminescence and exhibited stable fluorescence properties in various
105 conditions (e.g., different pH environments, serum or cell cytosol matrices).35 Therefore, the
106 utilization of L-MPNs as a labeling strategy provides great potential to enable fast and precise
107 fluorescence detection of MNPs.
108 The use of portable devices for fluorescence detection of MNPs is important consideration for
109 convenient and on-site deployable detection. However, portable devices previously designed often
110 necessitated specific smartphone models for integration, thus limitating factors such scalability,
111 portability, and compatibility with other mobile pad or laptop devices. In sum, it is crucial to
112 develop an analytical system that achieves both on-site and remote detection of plastic particles,
113 considering the potential presence of plastic particles in inaccessible areas where access is
114 restricted for specialists or inspectors. Finally, it is equally important to create a user-friendly
115 device that allows effective operation by untrained personnel and supports local or remote data
116 processing for fast fluorescence imaging analysis.
117 This work describes our design of a wireless portable device that enables rapid, sensitive and
118 on-site/remote detection of MNPs. We employed L-MPNs for labeling and concentrating MNPs,
119 followed by detection and customized image processing via machine learning algorithms applied
120 for in a mobile device that supports quantitative fluorescence imaging analysis. This device
121 described herein, offers a quick MNPs detection (< 20 min) with compatible data transmission
122 with various mobile devices, such as smartphones, pads, and laptops through WIFI connection.
123 The result is wireless communication and remote data processing up to a distance of 10 meters
124 from mobile devices to the portable device. The user-friendly design of the device allows for
125 untrained personnel to process data effectively (Scheme 1).
126 In this study, we selected tannic acid (TA), Zr4+, and rhodamine B (RhB) as model reagents
127 to prepare L-MPNs. We utilized polystyrene (PS) particles of various sizes (10 μm, 1 μm, 500 nm,
128 and 50 nm) to represent a wide range of plastic particle sizes found in known environmental
129 situations. Our goal was to demonstrate high-performance of our assay, particularly in overcoming
130 the challenges in visualizing plastic particles smaller than 10 μm, using traditional optical
131 microscopy along with known difficulties related to nano-plastic detecstion. The TA/Zr4+ molar
132 ratio was optimized for L-MPNs and the formation of MNPs labeled by L-MPNs (L-
133 MPNs@MNPs) was validated by confocal fluorescence imaging. To demonstrate the feasibility
134 of our device peforming well with on-site detection of real-world samples, we used it to evaluate
135 MNPs released from six different commercial plastic cups composed of PS, polypropylene (PP),
136 polylactic acid (PLA), and polyethylene terephthalate (PET).
137 Our device to quantify plastic particle detection has distinct advantages that include the
138 following features: (1) the deployment of a highly-efficient labeling strategy utilizing L-MPNs to
139 enable accurate detection of micro-and nano-plastics; (2) the development of a multi-compatible
140 portable device with wireless communication capabilities, allowing on-site and remote detection;
141 (3) the provision of both rapid, and sensitive detection via quantitative fluorescence imaging in a
142 portable device; (4) the requirement for minimal sample pretreatment, low sample volume (1 μL),
143 cost-effective device fabrication and low-cost sample analysis (approximately $0.015/sample); (5)
144 User-friendly data processing without the need for trained personnel.
145
146 Scheme 1. Key attributes of the portable device for micro-and nano-plastics detection. The
147 microscope functions as a rapid, on-site detection apparatus for MNPs, with a detection time of
148 less than 20 min. It offers compatibility with various mobile devices (e.g., smartphones, pads and
149 laptops), enabling remote connections up to a distance of ~10 m. A smartphone is presented as an
150 example of a mobile device that can remotely process data acquired from the microscope
151 efficiently, allowing for quantitively fluorescence imaging of MNPs. Data processing is user-
152 friendly and can be executed by untrained personnel. Images in the scheme are created by
153 Midjourney.
154 2. RESULTS AND DISCUSSION
155 2.1. Labeling Mechanism of Micro-and Nano-Plastics with L-MPNs
156 To accurately detect MNPs, we tested a mechanism of labeling MNPs with L-MPNs. The L-
157 MPNs labeling strategy could be applied to plastic particles using a simple self-assembly process
158 (Figure 1a).36 PS particles with sizes of 10 μm (8.78 × 105 mL-1) and 50 nm (1.37 × 1013 mL-1) were
159 selected as being representatives of microparticles and nanoparticles, respectively. TA (0.34 μM),
160 Zr4+ (0.20 mM) and RhB (0.01 mM) were selected as model reagents at these concentrations to
161 form L-MPNs because TA/Zr4+ based MPNs exhibits high stability under various pH and thermal
162 conditions, minimally affecting the fluorescence of RhB.37,38 In this study, we separated and
163 concentrated our analysis target (L-MPNs@MNPs) by centrifugation and evaluated the
164 concentrated precipitates in various reagent conditions by optical images. As shown in Figure S1a,
165 in the control group, micro-plastics dispersed in distilled water solution precipitated, likey due to
166 high molecular mass, while nano-plastics precipitates were negligable under the same recovery
167 conditions (e.g., centrifugation speed = 7500 rpm for 10 min). Others have reported that
168 ultracentrifugation at 20,000 rpm enabled direct separation of nano-plastics (600 – 1000 nm), but
169 this required a longer process time (e.g., 2 h).39 Moreover, the use of ultracentrifugation may
170 present feasibility challenges when dealing with nano-plastics with smaller particle sizes and
171 points to a difficulty in separating nano-plastics for detection. Interestingly, the addition of Zr4+
172 can promote the formation of nano-plastics precipitates (Figure S1a), possibly due to an
173 electrostatic interaction between the negatively charged polystyrene surface (Figure 1b) and the
174 positively charged Zr4+. This would facilitate separation of nano-plastics using L-MPNs labeling
175 approaches following centrifugation. We further examined the binding ability of RhB to MNPs
176 using optical images and a traditional fluorescence spectroscopy to eliminate interference of non-
177 specific signals that would adversely affect our Limit of Detection (LOD) of MNPs by the wireless
178 portable fluorescence device. In optical images (Figure S1b), micro-and nano-plastics principates
179 showed a pink color in Zr4+/RhB and L-MPNs groups, indicating that RhB interacted with MNPs
180 when Zr4+ was present. When we used fluorescence to characterize RhB binding with 10 μm of
181 micro-plastics (Figure 1c) and 50 nm of nano-plastics (Figure 1f), the results showed that relatively
182 low fluorescence intensity occurred when MNPs were labeled with RhB, TA/RhB, and RhB/Zr4+
183 in comparison to L-MPNs (p < 0.00001). This outcome demonstrates the important role of
184 coordination networks of L-MPNs for more efficient fluorescence labeling.35 It was also
185 noteworthy that although the binding of RhB/Zr4+ with MNPs enabled separation and labeling of
186 MNPs, the resulting fluorescence intensity was not as strong as that of L-MPNs since TA can
187 combine with RhB through π-π interaction.40 The change in particle size of NPs following
188 centrifugation further indicated that NPs were concentrated by L-MPNs mainly through
189 aggregation (Figure S1c).
190 To further validate the L-MPNs labeling strategy for MNPs, we performed zeta-potential
191 measurement, Confocal Laser Scanning Microscopy (CLSM) and Differential Interference
192 Contrast (DIC) imaging. The formation of L-MPNs altered the zeta potential of the plastic particles
193 from -15.41 ± 0.42 to -20.16 ± 0.37 mV for 10 μm micro-plastics (p < 0.0005) and -15.63 ± 0.45
194 to -17.52 ± 0.73 mV for 50 nm nano-plastics (p < 0.05), respectively, due to deprotonation of TA,35
195 (Figure 1b). The CLSM images provided evidence of successful labeling of RhB onto the micro-
196 plastics (Figure 1d) and nano-plastics (Figure 1g) through MPNs. Furthermore, DIC images clearly
7
197 demonstrated the presence of a thin layer of L-MPNs on the surface of the micro-plastics (Figure
198 1e). In addition, cross-sectional CLSM images presented a stereoscopic representation of the
199 impact of the L-MPNs on the MPs labeling (Figure S2), demonstrating a uniform labeling process.
200 It was noteworthy that the L-MPNs@NPs exhibited large clusters (Figure 2g and 2h), which
201 supports a previous hypothesis that L-MPNs can facilitate the separation and concentrate nano-
202 plastics via aggregation following traditional centrifugation.
203 To elucidate the effiency of the separation process facilitated by the L-MPNs labeling method,
204 we employed a customized Electrophoretic Deposition (EPD)-Interferometric Scattering (iSCAT)
205 Microscope integrated with a high-speed image analysis approach as described in previous work.41
206 This configuration permits the detection and characterization of nanoparticles with dimensions as
207 diminutive as 5 nm. Specifically, we focused on testing 50 nm PS nanoplastics (1.37 × 1011 mL-1,
208 0.227 nM), due to the challenges other researchers faced in detecting smaller-sized nanoplastics.42
209 Following the labeling of nanoplastics with L-MPNs and subsequent centrifugation, we collected
210 the supernatant for concentration analysis. The separation efficiency was subsequently deduced by
211 computing the ratio of the number of separated nanoplastics to the initial quantity present in the
212 sample. As illustrated in Figure 1i, a particle tracking result was recorded, as evidenced in upper
213 left quadrant which demonstrates frame number (200 frames per second) within the designated
214 region of interest (10.6 µm x 10.6 µm). The precise location of particles and the respective number
215 of landings are underscored by a pink bounding box. Upon activation of the voltage, we observed
216 a linear progression in the landing number over time, contrasted by an absence of noticeable
217 landings when the system is off, as depicted in Figure 1j. The landing rate was calculated to be
218 (1.06 ± 0.09) × 10-2 s⁻¹ µm⁻² based on three replications. Drawing upon our preceding studies, we
219 ascertained a linear correlation between the landing rate and particle concentration with a
220 calculated slope value of 1.7 s⁻¹ µm⁻² nM⁻¹ for 50 nm PS particles.41 Consequently, the
221 concentration of the sample supernatant was determined to be 6.22 ± 0.53 pM, culminating in a
222 separation efficiency of 97.26 ± 0.23%. This performance is comparable to conventional
223 coagulation/flocculation separation techniques for PS nanoplastics, which demonstrate a
224 separation efficiency of 94.1%43.
225
226
227 Figure 1. Labeling mechanism of L-MPNs for micro-and nano-plastics. (a) Schematics of
228 formation of L-MPNs@MNPs via self-assembly. (b) Changes in zeta potentials after formation of
229 L-MPNs@MNPs. Effects of components from L-MPNs on formation of (c) L-MPNs@MPs and
230 (f) L-MPNs@NPs illustrated via changes in fluorescence intensities, as determined by
231 fluorescence spectroscopy. CLSM (d) and DIC (e) images of L-MPNs@MPs. CLSM (g) and DIC
232 (h) images of L-MPNs@NPs. The measurement of fluorescence intensity was conducted after
233 removal of supernatant and addition of 1 mL of distilled water. RhB/Zr4+@NPs and L-MPNs@NPs
234 solutions were diluted tenfold for the measurement of fluorescence intensity. (i) A frame extracted
235 from particle tracking video recorded during iSCAT measurement, depicting nano-plastics in
236 supernatant of L-MPNs@NPs solution after centrifugation. The upper left quadrant shows frame
237 information (200 frames per second) and the particles were tracked within the designated region
238 of interest (white box, 10.6 µm × 10.6 µm). The indicated scale bar represents 1 μm. (j) A plot
239 delineating the variation in number of landings (blue line) and voltage status (pink line) over time
240 during iSCAT measurement. 10 μm of MPs (8.78 × 105 mL-1) and 50 nm of NPs (1.37 × 1013 mL-
1
241 ) were chosen as plastic particle representatives for all measurements except during iSCAT
242 evaluations where 50 nm NPs were taken at a concentration of 1.37 × 10¹¹ mL⁻¹.Data are
243 represented as mean ± standard deviation (SD) of three technical replicates. *p < 0.05, **p <
244 0.0005, ***p < 0.00001 by two-tailed t test.
245 2.2. Design of Wireless Portable Device with Customized Data Processing
246 Concentrated L-MPNs@MNPs were used as target analytes to be detected by a wireless

247 portable device with rapid, sensitive capabilities for on-site/remote quantification of MNPs. The
248 device combined a mobile device, a digital microscope fitted with an emission filter, a green
249 flashlight equipped with an excitation filter, a nitrocellulose membrane as sample substrates, a
250 sample chamber, and a 3D-printed housing (Figure 2a). The actual appearance and compact size
251 (approximately 11 cm* 9 cm*15 cm) of the device is presented in Figure 2b. Prototypes of the
252 sample chamber and the 3D-printed housing are displayed in a disassembly view (Figure 2c) and
253 a perspective view (Figure 2d). Notably, the 3D-printed box included a hole for positioning the
254 light source, allowing for the facile alteration of the excitation light with varying wavelengths
255 using the same light source type. In our study, a green LED light was selected as the light source
256 due to its ability to effectively excite RhB fluorophores in the sample, while also minimizing
257 autofluorescence from substrates. Within the device, the green LED light source, spanning
258 wavelengths between 535 nm and 558 nm, uniformly excited the RhB on the stained MNPs. We
259 integrated a wireless digital microscope into this device to collect fluorescence signals owing to
260 its versatile functionality, such as the capability of connectivity to various mobile devices with
261 iOS/Android systems through WIFI, and remote detection within a range of approximately 10 m
262 (Figure 2a). The use of nitrocellulose substrates promoted the flow of aqueous solutions while
263 reducing autofluorescence. The resulting fluorescence was filtered through an emission filter with
264 a center wavelength of 591.5 nm and a full width at half maximum (FWHM) of 49 nm, which was
265 then detected by a digital microscope. The device provides a sufficient field of view (FOV) with
10
266 an effective pixel size of approximately 5.35 μm/pixel (Figure 2e). More details of the calculation
267 supporting information is presented in Supporting Note 1 and Figure S3. The scale bar in each
268 fluorescence image was presented as 500 μm according to the pixel count of approximately 93.46.
269 The entire process of image acquisition and analysis was streamlined using MAX-SEE
270 software and a custom machine learning code in MATLAB executed on the smartphone mobile
271 device. The image acquisition by the portable device is given in Video S1. As we moved the sample
272 chamber, fluorescent signals (orange circle) consistently appeared on the smartphone screen,
273 indicating the presence of MNPs. Remarkably, the sample chamber had the capacity to
274 accommodate dozens of samples, and the device allowed for rapid image acquisition (less than 5
275 seconds per sample). This demonstrated the potential for high throughput detection. The principal
276 goal of the imaging analysis was to translate the fluorescent signal from raw images into pixel
277 areas and established the relationship between pixel area and known quantities of MNPs with
278 varying sizes nanoparticles (e.g., 10 μm, 1 μm, 500 nm and 50 nm) for obtaining pre-training
279 dataset for quantitative analysis of MNPs. The imaging process consists of several steps (Figure
280 2f): (1) extraction and demosaicing of the red channel of each RGB image to produce a grayscale
281 image; (2) application of a threshold intensity of +25 to eliminate background noise and
282 subsequent image binarization; (3) determination of the MNPs quantities, based on the known
283 relationship between MNPs quantities and pixel areas. The determination of threshold intensity
284 was previously discussed into Section 2.3 (assay optimization). The output results are shown in
285 Figure 2f and Figure S4 which included: (i) a positive or negative signal indicating if MNPs are
286 present (Note that the value below the LOD is considered negative in this study); (ii) quantity
287 concentration of plastic particles assuming a specific particle size (10 μm, 1 μm, 500 nm and 50
288 nm); and (iii) notification of dilution is required (If the quantity concentration is higher than the
289 upper Limit of Quantification (LOQ), a dilution request is shown (Figure S4a)).
11
290
291 Figure 2. (a) Schematic presentation of the wireless portable device highlighting the illumination
292 and image acquisition components. (b) Actual appearance of the device. Depiction of the 3D-
293 printed box prototype: (c) view with disassembly, (d) view with assembly and perspective. (e) Raw
12
294 image (1280 × 720 pixels) of a gridded nitrocellulose membrane captured using the device under
295 white light. The scale bar 500 μm was determined based on a known pixel length (628 pixels) and
296 known side length (3.36 mm) of a gridded square unit, resulting in a resolution of 5.35 μm/pixel.
297 (f) Image processing steps and output results of fluorescence image in the device. 50 nm of nano-
298 plastics (1.10 × 1011 mL-1) labeled by L-MPNs (TA, 0.34 μM, RhB, 0.01 mM, Zr4+, 0.20 mM) are
299 chosen as the exemplary sample.
300 2.3. Assay optimization for reliable detection
301 The optimization of the device and the assay used to minimize interference was important to
302 achieve reliable and accurate detection of MPNs. In this study, we focused on optimizing TA/Zr4+
303 molar ratio in the self-assembled L-MPNs, because this ratio could influence the quantity of
304 unwanted precipitates (L-MPNs alone without labeled onto MNPs), potentially causing excessive
305 background noise when examined by the device. Additionally, this ratio could also influence the
306 binding affinity of RhB to MPNs, thus impacting the resultant fluorescence signals.44,45
307 To optimize the TA/Zr4+ molar ratio, we evaluated the fluorescence performance of
308 precipitated L-MPNs using traditional fluorescence spectroscopy (Figure S5) and fluorescence
309 microscopic images via the designed portable device (Figure 3a). The final concentration of Zr4+
310 in all sample solutions was kept constant at 0.20 mM, a value identified to be appropriate from
311 previous studies.46 As demonstrated in Figure S5a, the precipitate of L-MPNs did not exhibit
312 substantial visual changes initially but gradually diminished as the TA/Zr4+ molar ratio decreased
313 from 1:30 to 0:1 after centrifugation. At high TA/Zr4+ molar ratios ranging from 3:1 to 1:1, the
314 precipitate formed large aggregates that could incorporate significant amounts of RhB. This result
315 produced low fluorescence intensity (Figure S5b), possibly attributed to aggregation-induced
316 fluorescence quenching.47 Conversely, this phenomenon was found to be less pronounced as the
317 TA/Zr4+ molar ratio was reduced from 1:1 to 1:30; leading to an increase in the fluorescence
318 intensity. Further reduction of the TA/Zr4+ molar ratio (from 1:30 to 0:1) led to a reduction of the
319 L-MPNs precipitate, as evidenced by a change in fluorescence intensity from 33211 ± 734 to 649
320 ± 31 (Figure S5b). This indicated that the amount of TA has an important role in producing the
321 fluorescence intensity of precipitated L- MPNs.48,49
322 Optimal TA/Zr4+ molar raitos were required since it would be expected that a high ratios could
323 produce high background noise corresponding high pixel area values, whereas small ratios could
324 weaken the binding of RhB to MPNs for labeling of plastic particles. We determined an optimal
325 TA/Zr4+ molar ratio using systemic analysis of fluorescence microscopic images. A molar ratio
326 lower than 1:600, produced no orange color in microscopic images (Figure 3a), but when
13
327 standardized to 1:600, the frequency of red pixel intensities was increased at low red pixel
328 intensities (< +5), and a maximal red pixel intensity of +25 (Figure 3b). To remove possible
329 interference deriving from L-MPNs that remained uncapped onto MNPs, a threshold intensity of
330 +25 was used to effectively eliminate background noise. Settimg at this threshold showed no
331 detectable pixel area signals at TA/Zr4+ molar ratio of lower than 1:600 (Figure 3c). Thus a TA/Zr4+
332 molar ratios 1:600 was the optimal ratio used along with threshold intensity of +25 to deduct
333 background in the microscopic image.
334
335 Figure 3. Assay optimization for L-MPNs using the designed portable device. Zr4+ concentration
336 was selected as 0.20 mM. (a) Microscopic fluorescence images obtained from the portable device
337 depicting L-MPNs precipitates with varied TA/Zr4+ molar ratios ranging from 1:60 to 0.1. All raw
338 images are cropped to 600 × 600 pixels in regions exhibiting fluorescent signals and scale bar is
339 500 um. (b) Frequency distribution of red pixel color intensities for L-MPNs precipitates at a
340 TA/Zr4+ molar ratio of 1:600. (c) Pixel area signals derived from fluorescence microscopic images
341 of L-MPNs precipitates at TA/Zr4+ molar ratios from 1:60 to 0.1. Data are represented as mean ±
14
342 SD of three technical replicates in Figure c.
343 2.4. Quantification of MNPs
344 Following optimization of the assay, the relationship between pixel area signals and MNPs
345 concentrations for quantitative analysis was established. This relationship was critical to assure an
346 accurate analysis of MNPs. We determined the upper and lower limit of quantification (LOQ) of
347 MNPs using the portable device and formed a pre-training dataset for detecting unknown plastic
348 samples.
349 The LOQ of MNPs was based on the quantity number of plastic particles, rather than sample
350 concentration since MNPs were detected after centrifugation, and the sample volume before
351 centrifugation may vary and thus influenced the concentration of separated MNPs. Microscopic
352 images of various quantities of plastic particles with different sizes of 50 nm, 10 μm, 1 μm, 500
353 nm are shown in Figure 4, S6, S7 and S8, respectively. Increasing MNPs produced two distinct
354 phases in change of pixel area: a linear ascending phase (Phase 1) and a plateau phase (Phase 2)
355 (Figure 5a, 5d, 5g and 5j). Measured pixel area was linearly correlated (R > 0.95) with sample
356 MNPs content, for both micro- and nano-sized plastic particles (Figure 5b, 5e, 5h and 5k),
357 demonstrating feasibility for the portable device to perform quantitative analysis. The LOQ of the
358 portable device was determined at both upper and lower boundaries of Phase 1 using an iterative
359 algorithm, whereby the mean and deviation were calculated to assess whether a higher quantity of
360 plastic particles fell within a linear ascending phase (Method S1). Exceeding the upper LOQ,
361 typically indicates that an increase in aggregation of MNPs occurred which lead to inaccurate
362 results.25 For example, the degree of aggregation of L-MPNs@NPs (50 nm) increased as the NPs
363 quantity increased (Figure S9). When the NPs quantity exceeded an upper LOQ (Figure S9a–S9b),
364 numerous large aggregates with size over 5 μm were observed, resulting in a saturated fluorescent
365 signal in all NPs sample regions on nitrocellulose substrates (Figure 4). This in effect resulted in
366 inaccuracy to quantity of NPs. The lower LOQ was established by progressively reducing the
367 quantities of MNPs until minimal fluorescent signals were detectable. As shown in Figures 4 and
368 S6–S8, respectively, negligible fluorescence signals occurred for MNPs when the quantities were
369 less than 330 for 10 μm MPs; 2.1 × 105 for 1 μm MPs; 3.08×106 for 500 nm NPs; 2.58 × 108 for 50
370 nm NPs, respectively. Additionally, the pixel area corresponding to MNPs quantities below the
371 lower LOQ showed values greatly beneath the pixel area signals of LOQ (< 150) (Figure S10a–
372 S10d). Such ultralow signals cannot be recognized as plastic signals, confirming that the LOD of
373 this assay was equal to the lower LOQ. This phenomenon aligned with reported smartphones-
374 enabled fluorescence techniques.22,25,45
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375 Method validation was conducted using fluorescence spectroscopy to determine the change in
376 average fluorescence intensity of different MNPs groups (Figure 5c, 5f, 5i and 5l) at the same
377 quantity levels when detected by the wireless portable device. Results produced a positive
378 correlation between fluorescence intensity and quantitiy of MNPs within detection ranges. This
379 outcome confirmed the feasibility of quantifying MNPs using the portable device through L-MPNs
380 supramolecular labeling. It was noteworthy that the fluorescence spectroscopy used in our study
381 had an upper detection limit of approximately 60,000 fluorescence units. The LOD determined by
382 the portable device corresponded to a fluorescence intensity of approximately 10,000 fluorescence
383 units. The LOD of MPNs obtained using fluorescence spectroscopy was higher than the portable
384 fluorescence microscope, since there was no detectable change in fluorescence intensity at low
385 MPNs quantities. The discrepancy between the pixel area and fluorescence intensity versus MNPs
386 quantities can be attributed to the different detection principles of fluorescence spectroscopy and
387 the fluorescence imaging systems. For example, the portable device selectively captured the
388 fluorescence signal from our target analytes (L-MPNs@MNPs) by modifying light illumination
389 and establishing appropriate color intensity thresholds.50,51 Fluorescence spectroscopy, on the other
390 hand, measures the average fluorescence emission from the entire sample, including not only the
391 L-MPNs@MNPs, but also other substances such as L-MPNs, TA/RhB, Zr/RhB, and free RhB,
392 respectively. This makes accurate quantification of L-MPNs@MNPs challenging, particularly
393 when MNPs quantities are low. Evidence of this is shown in Figure S5, were substances containing
394 RhB appeared to interfere with L-MPNs@MNPs fluorescent signal. Given that L-MPNs@MNPs
395 demonstrated a higher fluorescence intensity relative to non-specific, interfering materials, setting
396 a color intensity threshold effectively eliminated background signals using the portable device.
397 The comparison of the portable device with fluorescence spectroscopy revealed a superior
398 reliability and sensitivity for MNPs quantification. Moreover, the established set of four linear
399 relationships provides capacity to effectively span a broad size range of MNPs contaminants,
400 enabling accurate estimation of MNPs quantities within real-world scenarios.
16
401
402 Figure 4. Fluorescence microscopic images of various quantities of 50 nm nano-plastics labeled

403 by L-MPNs obtained from the portable device. Scale bars represent 500 μm. All raw images have
404 been cropped to 600 × 600 pixels to highlight regions displaying fluorescent signals.
17
405
406 Figure 5. Comparison of the portable device with fluorescence spectroscopy for MNPs
407 quantification. Relationship between pixel area detected by the portable device and MNPs
408 quantities with particle sizes of 10 μm (a), 1 μm (d), 500 nm (g) and 50 nm (j). Linear relationship
409 of pixel area as a function of MNPs quantities with particle sizes of 10 μm (b), 1 μm (e), 500 nm
410 (h) and 50 nm (k) determined by the portable device (p < 0.000001 by ANOVA analysis for all
411 groups). Relationship between fluorescence intensity detected by fluorescence spectroscopy and
412 MNPs quantities with particle sizes of 10 μm (c), 1 μm (f), 500 nm (i) and 50 nm (l). Data are
413 represented as mean ± SD of three technical replicates.
18
414 2.5. Analysis of MNPs Released from Commercially Available Plastic Cups
415 Detection of MNPs in typical agri-food system samples is a substantial challenging due to the
416 irregular shapes, various particle types and sizes of MNPs fragments that exist in the matrix. In
417 addition, those fragments are liable to reduce to smaller particles or, alternatively aggregate with
418 other particles, making isolation and subsequesnt quantative analysis problematic. Consequently,
419 most studies have focused on detecting template MNPs that are added to environmental samples
420 as a referencae, rather than attempting to extracting and quantifying MNPs from real-world
421 samples.52–54 In this study, we used our portable device to detect MNPs released from six different
422 commercial polystyrene (PS) drinking cups to test the feasibility of using our device.
423 Quantification analysis was performed of the released MNPs from three different PS cups that
424 included an opaque cup (PS 1), foam cup (PS2) and clear cup (PS3), respectively. We also extended
425 our analysis to detect MNPs transported from cups manufactured with other sources of plastic,
426 including polypropylene (PP), polylactic acid (PLA) and polyethylene terephthalate (PET). To
427 replicate typical consumer exposure scenarios of with hot beverages, such as tea and coffee, the
428 cups were filled with 50 mL of boiling water and allowed to cool naturally for 30 minutes prior to
429 the monitoring of MNPs release using the device.
430 The fluorescence microscopic images of the released MNPs from six cups and the
431 corresponding pixel area are depicted in Figure 6a–6b, respectively. Results showed that plastic
432 particles were released and could be captured for analysis using the portable device. Figure 6c
433 shows that the fluorescence intensity of release samples corresponded to the pixel area. Specifically,
434 fluorescence intensity gradually decreased from PS1, PS2, PS3, PP, and PLA, while it actually
435 increased for PET. Due to the fact that the different plastic samples tested may contain a wide size
436 range of plastic particles,55 the selection of an appropriate linear curve was deemed critical for the
437 precise quantification of MNPs. To determine the suitable linear curve that can be used for
438 quantification, we used Dynamic Light Scattering (DLS) techniques to analyze the particle size
439 distribution of MNPs released from the six cups (Figure 6e). The pattern of released MNPs showed
440 a relatively homogeneous particle size distribution between 300 nm and 900 nm. This result was
441 consistent with other studies where the plastic particles released from common single-use
442 consumer plastic products under hot water induction were concentrated in a nanometer size
443 range.16 We quantitatified plastic particle released from the three PS cups using the established
444 linear curve as shown in Figure 5. According to our DLS results, the fitting standard curve for 1
445 µm particles was applied to PS1, while the curve for 500 nm particles was utilized for PS2 and
446 PS3. This was attributed to the fact that PS1, PS2, and PS3 particles exhibited the strongest particle
447 size peaks at 879 nm, 636 nm, and 391 nm, respectively. To further quantify MNPs quantity
19
448 analysis, we captured the fluorescence images from the portable device and inputed this data into
449 a MATLAB linear curve code processed on a mobile device to calculate average pixel area (see
450 Section 2.2). The total sample volume (e.g., 940 μL in this experiment) was also inputed for the
451 quantification calculation. Using this protocal, we showed that three PS samples gave positive
452 signals and pixel areas that were within the linear curve range. Table 1 gives the the concentration
453 of released particles from PS1, PS2 and PS3 cups were respectively using the mobile device. These
454 results were consistent with other studies that reported plastic packaging could release hundred-
455 million levels of plastic fragments in hot water.16 It’s worth noting that the device reported herein,
456 exhibits the potential to expand its capabilities towards quantitative analysis of various other
457 plastic types, such as PP, PLA, PET, based upon the establishment of suitable linear relationships.
458 These results indicate that L-MPNs labeling strategies when coupled with the portable device
459 developed have a capaciaty to determine the released MNPs from real-world samples.
20
460
461 Figure 6. Assessment of plastic release from six types of commercial cups made from PS, PP, PLA,
462 and PET. (a) Fluorescence microscopic images of the released plastic particles obtained using the
463 portable device. All raw images are cropped to 600 × 600 pixels in regions exhibiting fluorescent
464 signals. Error bar is 500 µm. (b) Pixel area of plastic particles released from six cups, as determined
465 by the portable fluorescence microscope. (c) Fluorescence intensity of the released plastic particles
466 from six cups as measured by fluorescence spectroscopy. (d) Particle size distribution of released
467 plastic particles, as determined by DLS techniques. PS1: Polystyrene opaque cups. PS2:
468 Polystyrene foam cups. PS3: Polystyrene clear cups. PP: Polypropylene cups. PLA: Polylactic acid
469 cups. PET: Polyethylene terephthalate cups. Data are represented as mean ± SD of three technical
470 replicates in bar charts.
21
471
472 Table 1. Assay results for released plastic particles from three commercially available PS cups by
473 the portable microscope.
Quantity
PS Cup Samples Size Signal
concentration
(1.55 ± 0.01) ×
PS1 1 μm Positive
108/mL
(7.86 ± 1.14) ×
PS2 500 nm Positive
108/mL
(6.32 ± 0.99) ×
PS3 500 nm Positive
108/mL
474 *PS1: Polystyrene opaque cups; PS2: Polystyrene foam cups; PS3: Polystyrene clear cups. Data
475 are represented as mean ± SD of three technical replicates.
476 A comprehensive decision tree model was established to decide on the steps necessary to
477 determine the applicability of our device for analyzing MNPs across diverse samples from agri-
478 food or environmental systems. We relied on using the linear correlation between pixel area and
479 MNPs quantities to indicate positive/negative signals and the quantity concentration of MNPs. As
480 depicted in Figure 7, we first input the fluorescence image and sample volume into the MATLAB
481 software, and positive or negative signals are shown here. We define samples as “negative” if the
482 detected pixel area falls below the LOD/lower LOQ, implying the absence of MNPs in the sample.
483 If the pixel area exceeds the LOD, a “positive” is indicated, leading to two potential outcomes: (1)
484 when the pixel area is within the linear range, the result is labeled as "positive" along with a
485 corresponding quantity concentration; (2) if the pixel area exceeds the upper LOQ, the outcome
486 remains "positive" but is accompanied by a note indicating the need for sample dilution. Following
487 the dilution process, operators can input new images and volume to more accurately determine the
488 concentration MNPs. By integrating the linear curve with each size of PS MNPs into the MATLAB
489 software, the model shows potential to serve as a comprehensive tool for accurately assessing
490 concentrations of plastic particles at diverse sizes. We noted that in order to obtain highly accurate
491 results, this assay could also involve DLS measurement; however, this may not be necessary if
492 estimates on the potential size range of MNPs were obtained beforehand. For example, water
493 samples originating from single-use food-grade bags may contain MNPs with average particle
494 diameters ranging from 30 to 80 nm, with rare instances of particles exceeding 200 nm.16 In such
495 a scenario, the value derived from the 50 nm NPs equation would likely be highly accurate and
496 relevant. Future studies will focus on building a MNPs linear curve database on the MATLAB
22
497 software to determine various types of MNPs quantity for a wide range of real-world applications.
498
499
500 Figure 7. Decision Tree Model illustrating the detection and quantification process for plastic
501 particles from unknown samples.
502 2.6. Comprehensive Assessment of the wireless portable device
503 Given the substantial challenges posed by nano-plastic detection, our device has demonstrated
504 robustness, sensitivity, and rapidness in detection capabilities. To highlight the merits of our assay,
505 we conducted a comparative assessment of the our portable device for nano-plastic analysis against
506 recently established methods, considering factors such as nano-plastic types, pretreatment, LOD,
507 and detection time (Table 2). A common challenge faced by many previous methods was the
508 requirement for sample pretreatment, such as extraction, separation, digestion, and staining. These
509 steps are time-consuming and can delay obtaining results as much as 24 h. Although some
510 techniques such as surface-enhanced Raman scattering (SERS) assays eliminate the demand for
511 sample pretreatment, preparation of the SERS substrate is required which is costly and consists of
512 time-consuming steps to create gold or silver nanostructures.56 Our assay, however, using the L-
513 MPNs labeling strategy, greatly reduced the pretreatment time, resulting in a total operation time
514 of approximately 20 min. Furthermore, our platform enabled the analysis of various types of MNPs
515 (e.g., PS, PP, PLA, PET) released from different plastic packaging materials, making it more
516 applicable to real-world settings. To compare LOD performance, the LOD of the portable device
517 was calculated as quantity concentrations based on results from Section 2.4 to facilitate a more
518 effective comparison with other methods. Our method showed a capability to achieve comparable
23
519 LOD as reported by other established methods, including RM-FFF and FMR57,58. Although our
520 current LOD had not yet reached the levels achieved by GC-MS, SPT, and ICP-MS techniques,
521 however, it is noteworthy that this was mainly due to the advantage that our assay requireing a low
522 sample volume. Our method allowed us to detect the number of plastic particles in liquid samples
523 by L-MPN labeling, followed by separation through centrifugation. The LOD of our assay could
524 be greatly improved by increasing sample volumes to enable larger amounts of plastic particle
525 labeling and separation. Moreover, GC-MS, SPT, and ICP-MS enable assays require longer
526 operation time (>1h),17,59,60 while our device can analyze samples much shorter, such as within 20
527 min. In addition to these distinctive features, we calculated that our platform will provide results
528 at a cost of approximately $500 for each reusable device and $0.015 per assay (Table S1). Our
529 portable device exhibited compatibility with a range of mobile devices and enabled remote
530 detection up to a distance of 10 m (Scheme 1). Additionally, with the implementation of
531 customized image processing methodologies, the analysis can be directly executed on various
532 mobile devices, thereby enhancing wireless information transfer capabilities. These detection and
533 analysis procedures are user-friendly and can be conducted effectively even by individuals lacking
534 specialized training. Since one limitation could involve identification of plastic types and
535 differentiation of plastic sizes, future studies will focus on optimizing the assay further to
536 overcome these challenges. More importantly, our platform can be extended to detect various
537 particle analytes without inherent fluorescence through simple L-MPNs supramolecular labeling
538 strategy, an innovation that will pave the way toward for high through-put and rapid assay in
539 diverse agri-food or environmental systems.
540
24
541 Table 2. Comparison of the portable device with other established assays for nano-plastic detection
Nano-plastic Operation
Method Pretreatment LOD
Type Time
Our PS, PET, L-MPNs 2.74 ×1010 mL–1 (50 nm PS);
~20 min
method PLA, PP labelling 3.28 ×108 mL–1 (500 nm PS)
Cloud-Point 11.5 fM (66.2 nm PS); 2.5 fM
GC-MS59 PS, PMMA ~3.5 h
Extraction (86.2 nm PMMA)
Fluorescence
SPT60 PS 2 ×106 mL–1 (105 nm PS) >2 h
staining
RM-FFF57 PS, PMMA FFF separation 4.5 ×1013 L–1 (200 nm PS); 6.5 >1 h
×109 L–1 (500 nm PMMA)
SERS56 PS / 0.26 μg mL–1 (100 nm PS) ~15 min
Alkaline
Py-GC- digestion and 0.03 μg g–1 (100 nm PS); 0.03
PS, PMMA >24 h
MS61 protein μg g–1 (100 nm PMMA)
precipitation
Synthesis of
ICP-MS17 PS AuNPs-nano- 8.4 × 105 L–1 /
plastic
Centrifugation
FMR58 PS 2.43 × 1013 L–1 (49 nm PS) >24 h
and Digestion
542 *GC-MS: Gas Chromatography–Mass Spectrometry; SPT: Single Particle Tracking; RM-FFF:
543 Raman Microscopy and Field-Flow Fractionation; SERS: Surface Enhanced Raman Scattering;
544 Py-GC-MS: Pyrolysis–Gas Chromatography–Mass Spectrometry; ICP-MS: Inductively Coupled
545 Plasma Mass Spectroscopy; FMR: Fluorescent Molecular Rotor. PS1: Polystyrene. PP:
546 Polypropylene. PLA: Polylactic acid. PET: Polyethylene terephthalate. PMMA: Poly(methyl
547 methacrylate).
548 3. CONCLUSION
549 In summary, a novel wireless portable device was developed for rapid, sensitive and on-site
550 quantification of MNPs that range in multiple size (e.g., 10 μm, 1 μm, 500 nm, and 50 nm). L-
551 MPNs constructed from zirconium ions, tannic acid, and rhodamine B were employed to
552 functionalize MNPs for fluorescence labeling and MNPs separation. The formation of L-
553 MPNs@MNPs was confirmed by fluorescence and zeta potential measurements, CLSM, and DIC
554 imaging. The effective quantification of MPNs was achieved by customized fluorescence image
25
555 processing on a mobile device app with machine learning algorithms coding. A customized
556 Decision Tree Model embedded in the moble APP was designed for decision-making for rapid
557 quantitative analysis of MNPs. We demonstrated that the device allowed the detection of plastics
558 that were present numbers as low as 330 for 10 μm MPs, 2.1 × 105 for 1 μm MPs, 3.08 ×106 for
559 500 nm NPs and 2.58 × 108 for 50 nm NP. The analysis of MNPs released from six commercially
560 available consumer drinking cups composed of PS, PP, PLA, and PET, respectively, were also
561 validated using the device. This analytical platform exhibited rapid detection (approximately 20
562 minutes), wireless data communication, remote data processing, high-efficient data management,
563 low cost for device and conduction assays, and high sensitivity comparable to previously
564 established methods. This approach has the potential to serve as a preliminary assessment tool for
565 early detection of MNPs in real-world samples, facilitating the accurate assessment of potential
566 risks to MNPs exposure that affect both terrestrial and aquatic organisms and ultimately
567 contributing to the safety and sustainability of ecosystems.
568 4. EXPERIMENTAL SECTION
569 4.1. Chemical and Materials
570 Polystyrene micro-plastics and nano-plastics with four sizes (10 μm, 1 μm, 500 nm and 50
571 nm) were purchased from Phosphorex (Massachusetts, USA). Tannic acid (ACS reagent ≥99%),
572 Rhdamine B (ACS reagent ≥99%), and zirconyl chloride octahydrate (ZrOCl2·8H2O, 98%) were
573 purchased from VWR (Alberta, Canada). Commercial drinking cups consisting of polystyrene,
574 polyproline, polylactic acid and polyethylene terephthalate were purchased from Amazon. A
575 digital microscope was purchased from SKYBASIC (Houston, USA). Emission filter (550 nm,
576 FWHM 33 nm, D25 mm) was purchased from Bock Optronics (Toronto, Canada) and Excitation
577 filter (591.5 nm, FWHM 43 nm, D 12.5 mm) was purchased from Edmund Optics (Barrington,
578 USA). A green LED Light was purchased from RaySoar (Jiaxing, China). Cellulose nitrate
579 membrane filters were purchased from Fisher Scientific (Waltham, USA). Double distilled (DD)
580 water was obtained in Food, Nutrition and Health building at the University of British Columbia,
581 and it was used throughout the experiment.
582 4.2. Preparation of L-MPNs@MNPs
583 PS microspheres with various particle sizes (10 μm, 1 μm, 500 nm, and 50 nm) were diluted
584 to obtain the quantity concentration ranges (17553 – 4.39 × 106 mL-1 for 10 μm MPs, 2.23 × 106 –
585 1.12 × 109 mL-1 for 1 μm MPs, 1.64 ×107 – 8.19 × 109 mL-1 for 500 nm NPs and 2.74 × 109 – 1.37
586 × 1013 mL-1 for 50 nm NPs). The standard procedure for preparing L-MPNs@MNPs was outlined
26
587 below. 20 μL of TA (0.017 mM), 20 μL of RhB (0.5 mM), and 20 μL of ZrOCl2·8H2O (10 mM)
588 were added into 940 μL of the aqueous MNPs suspension, resulting in final concentrations of 0.34
589 μM of TA, 0.01 mM of RhB, and 0.20 mM of Zr4+. The mixture was then vortexed for 60 s. Next,
590 the solution was centrifuged at 7500 rpm for 10 min using a mini-centrifuge (VWR, Alberta,
591 Canada) to precipitate the L-MPNs@MNPs. After that, the supernatant was carefully removed to
592 eliminate free RhB. 100 μL of DD water was added to the original centrifuge tube and the
593 suspension was gently agitated using a pipette tip. This was followed by transferring to a new
594 centrifuge tube to reduce the amounts of liquid residues that could potentially remain on the
595 centrifuge tube wall during centrifugation. The solution was then vortexed for 60 s to ensure
596 homogeneity. Control group (L-MPNs solution) without adding MNPs was prepared using the was
597 same procedure as above. All experiments were repeated in triplicate.
598 4.3. Optimization of L-MPNs Labeling Strategy
599 L-MPNs were prepared by adding different small volumes (e.g., 20 μL) of TA, RhB (0.5 mM),
600 and ZrOCl2·8H2O (10 mM) to 940 μL of DD water. To optimize the L-MPNs, the concentration
601 of TA was varied by adjusting the TA/Zr4+ molar ratio of 3:1, 2:1, 1:1, 1:2, 1:3, 1:6, 1:10, 1:30,
602 1:60, 1:120, 1:300, 1:600, 1:900, 1:1200 and 0:1. The mixture was vortexed for 60 seconds and
603 then centrifuged at 7500 rpm for 10 minutes. Post-centrifugation photos of the solutions were
604 captured using a smartphone camera. After that, the removal of supernatant and the collection of
605 precipitate were used the same procedure as described in Section 4.2. The resultant solution was
606 first analyzed using fluorescence spectroscopy (Tecan Infinite 200Pro, Morrisville, USA), with
607 excitation at 550 nm and emission at 595 nm to determine fluorescence intensity. The subsequent
608 evaluation was performed using the designed portable device to convert fluorescent signals into
609 pixel area values. For the L-MPNs with a TA/Zr4+ molar ratio of 1:600, the distribution of red pixel
610 intensity was processed using ImageJ Software. All experiments were repeated in triplicate.
611
612 4.4. Characterization of L-MPNs@MNPs
613 The dynamic light scattering (DLS) analysis and zeta potential measurements were
614 determined using a Litesizer 500 instrument from Anton Paar (Graz, Austria). Fluorescence
615 intensity measurements were conducted with a fluorescence spectroscopy (Tecan infinite 200Pro
616 plate reader, Morrisville, USA), with excitation at 550 nm and emission at 595 nm. Confocal laser
617 scanning microscopy (CLSM) was performed with a Leica TCS SP5 laser scanning confocal
618 microscope (Wetzlar, Germany) using an HCX PL APO 100x/1.4 OIL objective, 561 nm laser,
619 PMT detectors, and operated with Leica Application Suite AF software. Fluorescence microscopic
620 images were obtained from the designed portable device with excitation at 550 nm and emission
27
621 at 591.5 nm.
622 4.5. EPD-iSCAT measurements
623 Electrophoretic Deposition (EPD)-Interferometric Scattering (iSCAT) measurements were

624 performed on a custom-built microscope described in full in our previous work41 and a brief
625 summary is provided herein. The supernatant of L-MPNs@NPs (50 nm PS, 1.37 × 1011 mL-1)
626 following centrifugation separation were selected as sample solutions to determine the
627 concentration. 7 µL of deionized water followed by 7 µL of sample solutions are pipetted onto the
628 coverslip of the EPD-iSCAT device. A 532 nm Laser (Laser Quantum GEM 532 nm Diode-
629 Pumped Solid State Laser) at 150 mW illuminates the sample and video is collected on a CMOS
630 camera (Point Grey Grasshopper GS3-U3-51S5M) at 200 frames per second with a resolution of
631 256 x 256 pixels. A 1 V potential is applied to the device to initiate electrophoresis and deposition
632 events are recorded as a function of time to obtain the deposition rate.
633 4.6. Detection of MNPs by the Portable Device
634 Prior to device operation, 1 μL of the sample solution was deposited onto a square sample cell
635 on gridded nitrocellulose membranes and allowed to evaporate naturally for 1 min. The prepared
636 nitrocellulose substrates were then placed into the sample chamber of the portable device. Upon
637 establishing the connection from a mobile device to the microscope via a WIFI hotspot, raw images
638 (720 × 1280 pixels) were captured using the MAX-SEE software (Shenzhen Joyhonest Technology
639 Co., Ltd) and analyzed utilizing a custom MATLAB code (Supporting Method 2) executed on the
640 mobile device.
641 4.7. Quantitative Analysis of MNPs
642 For quantitative evaluation, L-MPNs@MNPs were assessed over linear detection ranges as
643 follows: 3.51 × 106 to 5.27 × 105 mL−1 for 10 μm PS MPs, 2.23 × 107 to 1.17 × 108 mL−1 for 1 μm
644 PS MPs, 3.28 × 108 to 1.92 × 109 mL−1 for 500 nm PS NPs, and 2.74 × 1010 to 5.49 × 1011 mL−1
645 for 50 nm PS nano-plastics. This range establishment aids in determining the relationship between
646 the fluorescence signals recorded from the portable device and the plastic concentrations.
647 Fluorescent signals were processed and converted to pixel area values. This conversion involved
648 the extraction of red channel intensity, followed by grayscale transformation and binarization,
649 applying a threshold of +25. All these processing steps were accomplished using MATLAB app
650 integrated within the mobile device. Subsequently, a linear function was used to fit the relationship
651 between the pixel area and MNPs quantities, yielding the coefficient of determination, R2.
28
652 4.8. Detection of MNPs Released from Commercial Plastic Cups
653 The portable device was applied to evaluate the MNPs released from six commercially
654 available plastic cups consisting of PS, PP, PLA and PET. Three types of PS cups, including opaque
655 cups (PS1), foam cups (PS2), and clear cups (PS3), were chosen to represent the range of PS cup
656 varieties available in the market. Prior to analysis, each cup was thoroughly washed with DD water
657 to remove any potential contaminants that may have accumulated during the manufacturing,
658 storage, transport, or unstacking process. 50 mL of heated DD water (100 °C) was then added to
659 each plastic cup and allowed to cool down naturally for 30 min at room temperature. The PLA cup,
660 which shrinks when exposed to hot water, was submerged in a beaker filled with 50 mL of boiling
661 DD water (100 °C) followed by the same procedure as other cups. After that, each released sample
662 was analyzed by the portable device, fluorescence spectroscopy and DLS measurement. All
663 experiments were repeated in triplicate.
664 ASSOCIATED CONTENT
665 The Supporting Information is available free of charge on the ACS Publications website
666
667 Method for determination of upper LOQ; image processing algorithm; note for
668 determination of device parameters; Influence of L-MPNs labeling on MNPs following
669 centrifugation; cross-sectional z-slice CLSM images of L-MPNs@MPs; Estimation of the
670 microscope camera's scale bar; displayed output results for representative plastic samples;
671 assessment of L-MPNs precipitates by fluorescence spectroscopy; fluorescence microscopic
672 images of L-MPNs@MNPs by portable fluorescence microscope; CLSM images of L-
673 MPNs@NPs; cost analysis of device and assay(PDF)
674 Movie of assay procedure for micro- and nano-plastic using portable fluorescence microscope
675 (MP4)
676 AUTHOR INFORMATION

677 Corresponding Author
678 *E-mail:tianxi.yang@ubc.ca
679 Present Addresses
680 Food, Nutrition and Health, Faculty of Land and Food Systems, The University of British
681 Columbia, 2205 East Mall, Vancouver BC, V6T 1Z4 Canada
682 Author Contributions
29
683 The manuscript was written through contributions of all authors. All authors have given approval
684 to the final version of the manuscript.
685 Notes
686 The authors declare no competing financial interest.
687 ABBREVIATIONS
688 MNPs, Mico- and nano-plastics; L-MPNs, Luminescent metal phenolic networks; MPs,
689 Micro-plastics; NPs, Nano-plastics; UV, Ultraviolet; TEM, Transmission Electron Microscopy;
690 CLSM, Confocal Laser Scanning Microscopy; AFM, Atomic Force Microscopy; PTA, Particle
691 Tracking Analysis; ICP-MS: Inductively Coupled Plasma Mass Spectroscopy; GC-MS, Gas
692 Chromatography–Mass Spectrometry; MPNs, metal phenolic networks; NIR, near-infrared region;
693 TA, tannic acid; RhB, Rhdamine B; PS, Polystyrene; PP, Polypropylene; PLA, Polylactic acid;
694 PET, Polyethylene terephthalate; PMMA, Poly(methyl methacrylate); SPT, Single Particle
695 Tracking; RM-FFF, Raman Microscopy and Field-Flow Fractionation; SERS: Surface Enhanced
696 Raman Scattering; Py-GC-MS: Pyrolysis–Gas Chromatography–Mass Spectrometry; FMR:
697 Fluorescent Molecular Rotor.
698 ACKNOWLEDGMENT
699 This work was supported by the UBC Faculty of Land and Food Systems Fund (AWD-
700 020249), Natural Sciences and Engineering Research Council of Canada (NSERC) Discovery
701 Grant (RGPIN-2023-04100, RYY RGPIN 04598) and NSERC Discovery Launch Supplement
702 (DGECR-2023-00386). Imaging was performed in the LSI Imaging Core Facility of the Life
703 Sciences Institute at the University of British Columbia, supported by Life Sciences Institute, the
704 UBC GREx Biological Resilience Initiative. The infrastructure within LSI Imaging Core Facility
705 is funded by the Canadian Foundation of Innovation, BC Knowledge Development Fund, Natural
706 Sciences and Engineering Research Council Research Tools and Instruments, and UBC Research
707 Facility Support Grants as well as a Strategic Investment Fund (Faculty of Medicine, UBC). We
708 thank UBC rapid team for their support in 3D-printing techniques.
30
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Rapid Detection of Micro Nanoplastics Via Integration of Luminescent Metal Phenolic Networks Labeling and Quantitative Fluorescence Imaging in A Portable Device

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Rapid Detection of Micro Nanoplastics Via Integration of Luminescent Metal Phenolic Networks Labeling and Quantitative Fluorescence Imaging in A Portable Device

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1 Rapid Detection of Micro/Nanoplastics Via

2 Integration of Luminescent Metal Phenolic

80 The rapidly advancing field of developing fluorescence-enabled portable microscopy presents

154 2. RESULTS AND DISCUSSION

155 2.1. Labeling Mechanism of Micro-and Nano-Plastics with L-MPNs

246 Concentrated L-MPNs@MNPs were used as target analytes to be detected by a wireless

300 2.3. Assay optimization for reliable detection

343 2.4. Quantification of MNPs

402 Figure 4. Fluorescence microscopic images of various quantities of 50 nm nano-plastics labeled

502 2.6. Comprehensive Assessment of the wireless portable device

SERS56 PS / 0.26 μg mL–1 (100 nm PS) ~15 min

568 4. EXPERIMENTAL SECTION

569 4.1. Chemical and Materials

582 4.2. Preparation of L-MPNs@MNPs

597 same procedure as above. All experiments were repeated in triplicate.

598 4.3. Optimization of L-MPNs Labeling Strategy

622 4.5. EPD-iSCAT measurements

623 Electrophoretic Deposition (EPD)-Interferometric Scattering (iSCAT) measurements were

633 4.6. Detection of MNPs by the Portable Device

641 4.7. Quantitative Analysis of MNPs

664 ASSOCIATED CONTENT

676 AUTHOR INFORMATION

686 The authors declare no competing financial interest.

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