Eu,Sm,Mn-doped CaS Nanoparticles with 59.3% Upconversion

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Eu,Sm,Mn-doped CaS Nanoparticles with 59.3% Upconversion-Luminescence Quantum Yield: Enabling UltraSensitive and Facile Smartphone-based Sulfite Detection Jikai Wang, Yanli Zhu, Craig Alan Grimes, Zhou Nie, and Qingyun Cai Anal. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.analchem.8b02001 • Publication Date (Web): 22 Jun 2018 Downloaded from http://pubs.acs.org on June 23, 2018

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Analytical Chemistry

Eu,Sm,Mn-doped CaS Nanoparticles with 59.3% UpconversionLuminescence Quantum Yield: Enabling Ultra-Sensitive and Facile Smartphone-based Sulfite Detection Jikai Wang,1 Yanli Zhu,1 Craig A. Grimes,2 Zhou Nie,*,1 and Qingyun Cai*,1 1 2

State Key Laboratory of Chem/Bio-sensing and Chemometrics, Hunan University, Changsha 410082, P. R. China. Flux Photon Corporation, 6900 Darcy Lane, Raleigh, North Carolina, 27606 United States

*Corresponding authors: Qingyun Cai, Zhou Nie Email: [email protected] (Q.Y.Cai) Email: [email protected] (Z. Nie)

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Eu,Sm,Mn-doped CaS Nanoparticles with 59.3%UpconversionLuminescence Quantum Yield: EnablingUltra-Sensitive and Facile Smartphone-based Sulfite Detection Jikai Wang,1 Yanli Zhu,1 Craig A. Grimes,2 Zhou Nie,*,1 and Qingyun Cai*,1 1 2

State Key Laboratory of Chem/Bio-sensing and Chemometrics, Hunan University, Changsha 410082, P. R. China. Flux Photon Corporation, 6900 Darcy Lane, Raleigh, North Carolina, 27606 United States

ABSTRACT: Eu,Sm,Mn-doped CaS (ESM-CaS) nanoparticles demonstrate a remarkable upconversion luminescence (UCL) efficiency with a quantum yield of nearly 60%, enabling many new applications and devices. We describe an ESM-CaS nanoparticlebased paper test strip for one-shot quantitative measurement of sulfite concentration using a smartphone-based reader. The integrated UCL-based sulfite detection system features high sensitivity and facile operation without the need forseparation and pretreatment. Moreover, the design principles are general in nature, and so can be tailored for the detection and quantification of a variety of other analytes.

Recently we reported highly-luminescent Eu,Sm,Mn-doped CaS upconversion nanoparticles, denoted as ESM-CaS UCNPs, with anupconversion luminescence (UCL) quantum yield of approximately 60%1. Of all reported UCL materials that we are aware of (Table 1), our ESM-CaS UCNPs have by far the highest quantum efficiencies due to the novel electrontrapping UCL mechanism and high transition probability of excited state electrons1. The ESM-CaS UCNPs are stable, and readily dispersed in aqueous solutions enabling their use as energy donors for fluorescence resonance energy transfer (FRET)9,10 based probes, one application of which, sulfite detection, is described herein. We believe the ultra-high UCL quantum yield of the ESM-CaS UCNPs, intense UCL emission without auto-fluorescence, and small particle size should enable a wide range of new applications. Sulfite is a primary oxidative metabolite in bio-organisms. Neurodegenerative disease including migraine and stroke are associated with sulfite accumulation in tissue11,12. Sulfite has been found to affect both respiratory and digestive systems and, moreover, there appears to be potential carcinogenic affects13. Never-the-less sulfite is a widely used additive in food and crude drugs, with desired functions including bleaching, anti-oxidation, and bacterial inhibition. Analytical methods for sulfite detection, which include electrochemical14, chromatography15,16, and biosensing17 techniques, generally require expensive laboratory equipment and relatively complicated sample pretreatment of extended duration. Recently, increasing attention has been paid to the use of smartphones as a sensing platform due to its convenience, portability, and wide-spread availability18,19, while paper-strip based ion detection by fluorescence analysis, particularly metal ions, has been reported20-24, see Table S1. In this work we first synthetize ESM-CaS UCNPs modified with 1-dodecanethiol and 11-mercaptoundecanoic acid, denoted as DT/MUA@ESM-CaS UCNPs; these are used in an upconversion FRET system in combination withmethyl green (MG)dye on an inexpensive paper test strip for sulfite detection, see Figure 1a, with a smart-phone used to quantify concentration. The ESM-CaS UCNPs provide a strong UCL signal under low-power (100 mW, 980 nm) excitation, allow-

ingthe fluorescence signals of the test strip to be easily captured and analyzed by a smartphone. The UCL signal does not suffer from issues associated with autofluorescence and background interferences, resulting in signal-to-noise ratios of sufficient magnitude that sample-conditioning pre-treatment procedures are not required. The integrated system is inexpensive, 16.5cm×9cm×5.5cm in size and thusreadily portable, and enables rapid onsite determination of analyte concentration with great sensitivity. Said differently, the integrated system enables point-of-care testing (POCT). EXPERIMENTAL SECTION Synthesis of DT/MUA@ESM-CaS UCNPs. The ESM-CaS UCNPs were prepared by adding 2.75 mmol hexadecyltrimethyl ammonium bromide (CTAB) and 1.5 mL 1-pentanol to 20 mL cyclohexane, then mixed with 0.5 mL aqueous solution of Ca(NO3)2 (0.1 M), 0.1 mL Eu(NO3)3 (1.5 mM), 0.1 mL Sm(NO3)3 (1.5 mM), and 0.26 mL Mn(CH3COO)2 (1.5 mM). The mixture was stirred vigorously for 30 min forming a water-oil emulsion, and then left to stand for 1 h. Into this was mixed a water-oil emulsion containing (NH4)2SO4 (0.55 mL, 0.1 M), followed by slow agitation for 3 min. After aging for 10 min, 10 mL acetone was added to the mixture. The resultant particles were isolated by centrifuge, 10000 rpm for 10 min, and alternately washed with acetone and ethanol. The precipitate was dried in vacuum and annealed at 850 °C for 60 min under CO flow to acquire the ESM-CaS UCNPs. Under a dry nitrogen atmosphere the as-prepared ESM-CaS UCNPs were then modified with 1-dodecanethiol (DT) by dispersing them in 10 mL absolute ethanol containing 20 µL Tergitol NP-10. After sonication for 30 min, the mixture was added into 5 mL absolute ethanol containing 0.5 mL DT at pH 8.5, obtained by drop-wise addition of 0.1 M NaOH solution in ethanol. The solution was stirred at 50 °C for 24 h, then centrifuged and washed with ethanol, and finally dispersed in 2 mL cyclohexane. The DTmodified CaS UCNPs were then encapsulated by 3mercaptoundecanoic acid (MUA). For this purpose, DT@ESMCaS UCNPs in cyclohexane were added into 8 mL absolute ethanol, and sonicated for 10 min. Then 150 mg MUA and 10 µL 3mercaptopropionic acid (MPA) were dissolved in 5 mL absolute ethanol adjusted to pH 9.0 with a 0.1 M NaOH ethanol solution. After stirring for 30 min the solution was added to the


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Figure 1: Illustration of: (a) UCL-based detection scheme. (b) Fabrication of UCL paper test stripfor sulfite detection. (c) Smartphonebased portable UCL reader and operation. Table 1: Typical quantum yield (QY) of reported UCNPs under 980 nm laser excitation UCNPs CaS:Eu,Sm,Mn1 LiLuF4:Yb,Tm2 NaYF4:Yb,Er3 NaYF4:Yb,Tm4 NaLuF4:Yb,Tm5 NaYbF4:Tm@CaF26 NaYF4:Yb,Er@NaYF43 NaYF4:Yb,Tm@NaYF47 NaYF4:Yb,Tm,Ca@NaYbF4:Ca@NaNdF4: Gd,Ca8

Size (nm) 30 50 30 33 8 27 100 42 10

Power (W/cm2) 0.5 127 150 3.8 17.5 0.3 150 78 7.5

QY (%) 59.3 5.0 0.1 0.45 0.47 0.6 0.3 3.5 0.46

cyclohexane solution containing the DT@ESM-CaS UCNPs, and stirred vigorously for 48 h. The DT and MUA modified ESMCaS UCNPs (DT/MUA@ESM-CaS UCNPs) were collected by centrifuge at 10000 rpm and washed with ethanol. Fabrication of the UCL Paper Test Strip. Office printing paper was immersed in a solution containing periodic acid (2 %) and Triton X-100 (5 %) for 60 min, then washed with deionized water three times and dried at 40 °C (Figure 1b). The paper was subsequently soaked in n-octadecyltrichlorosilane cyclohexane solution (1 %) for 2 h, and washed with cyclohexane and ethanol twice, then dried at 40 °C. The resulting hydrophobic paper substrate was covered by an opaque piece of plastic in which a series of circular holes were cut, and irradiated under UV lamp for 5 h, making the exposed circular regions hydrophilic. Into the circular regions 20 µL of the DT/MUA@ESM-CaS UCNPs solution (2 mg/mL) was pipetted and incubated for 60 min. After washing with deionized water,20 µL of methyl green ethanol solution (0.33 µg/mL) was added to the circular regions and allowed to incubate for 40 min. The test strip was then allowed to dry under ambient conditions. UCL Measurements on Paper Test Strip. 10 µL sodium sulfite solutions of various concentrations (0.005, 0.01, 0.05,0.1, 0.5, 1, 10 µg/mL) were added to the circular hydrophilic regions of the

UCL paper test strip and allowed to react for 15 min. To record and analyze the UCL signal, on the paper test strip, a portable reader (16.5cm×9cm×5.5cm) was designed,consisting of a miniature 100 mW 980 nm laser powered by a rechargeable battery (output 5V, 1A), and an ordinary smartphone (Figure 1c). The smartphone was placed on top of the box to capture and display the UCL image data; the measured red, green, and blue values could also be transferred to Image J software. Real Sample Analysis. Four different samples, edible fungi, preserved fruit, granulated sugar, and dried vegetable (day lily), selected for theanalysis werepurchased from a local market. For sulfite detection in a food sample 2.9 mL ultra-pure water and 0.1 mLsodium carbonate (0.001 M) were added to 1.0 g of crushed sample, mixed thoroughly and sonicated for 30 min; ultra-pure water was then added to obtain a total volume of 25 mL, then 10 µL of extract was added to the UCL paper test strip and allowed to react for 15 min,finally the paper test strips were measured by the smartphone-based UCL reader. All spiked sampleswere prepared by adding three different sulfite concentrations into sample extracts. Sulfite concentrations were determined using the UCL reader, with values confirmed using micro-titrimetry25 (National Standard reference GBT5009.34-2016).

RESULTS AND DISCUSSION The Detection Principle. The underlying principle of the sulfite-detecting UCL paper test strip was that the highly luminescent DT/MUA@ESM-CaS UCNPs could be used as energy donors in the FRET process, with energy transferred from the DT/MUA@ESM-CaS UCNPs to the energy-acceptor MG dye (Figure 1a). MG dye was chosen as the energy acceptor because of the large overlap between its absorption band and the UCL emission spectrum of the DT/MUA@ESM-CaS UCNPs, see Figure 2a. The MG dye was assembled with DT/MUA@ESM-CaS UCNPs on the paper substrate via electrostatic interaction between the carboxyl group of DT/MUA@ESM-CaS UCNPs and the quaternary ammonium structure of MG. In the presence of



Figure 2: (a) The emission spectrum of the DT/MUA@ESM-CaS UCNPs closely matches the methyl green absorption spectrum, both in the absence and presence of sulfite. (b) Contact angle characterization of the paper substrate. (c) Luminescence images, and (d) Normalized UCL intensity of UCL paper test strip after three washing cycles. sulfite the MG was bleached, reducing absorption, which in turnsuppressed the FRET process and saw a recovery in the UCL signal. The UCL signal onthe paper test strip became invisible when incubated with MG, recovering with sulfite addition.As illustrated in Figure 1b, the paper test strip was patterned using a photolithography strategy with hydrophilic circular regions surrounded by a hydrophobic boundary, see Figure 2b. The DT/MUA@ESM-CaS UCNPs were firmly attached tothe hydrophilic circular region of the patterned paper substrate, Figure 2c and 2d; after three washing cycles no significant decline in UCL intensity was found. The DT/MUA@ESM-CaS UCNPs were first prepared by 1dodecanethiol and 11-mercaptoundecanoic acid encapsulationto ensure stability and dispersibility in solution. Transmission electron microscope (TEM) images show theaverage size of the DT/MUA@ESM-CaS UCNPs are≈ 30 nm, without significant change in shape and excellent monodispersity after ligand coating (Figure S1a, S1b). The cubic phase of the CaS UCNPs was verified by X-ray diffraction (XRD) (Figure S1c). Fourier transform infrared spectroscopy (FT-IR) confirmed the presence of DT and MUA on the surface of the CaS UCNPs (Figure S1d). Optical Response of MG to sulfite. As indicated by Figure 3a MG dye shows intense absorption at 630 nm, a behavior determined by the flat, rigid and large conjugation structure. MG dye combines with SO32- to form MG·SO32-; the nucleophilic reaction of SO32- to the centricbridgingC=C bondslargely destroys the πconjugation structure (Figure 1a) that, in turn, eliminates the noted absorption properties. As seen in Figure 3a and 3b the 630 nm absorbance peak gradually decreases with the addition of

Figure 3: (a) UV-Vis spectrum and (b) absorbance at 630 nm of methyl green upon gradual addition of sulfite solution (from 0 to 1.0 µg/mL). Inset shows photographs of corresponding solutions.

Figure 4: (a) Quenching efficiency in the presence of different amounts of methyl green. (b) Incubation time dependence of quenching efficiency. (c) Time dependence of UCL signal recovery. (d) Normalized UCL intensity upon the addition of various anions and molecules. increasing amounts of sulfite. Reaction mechanisms were further characterized by spectroscopic techniques. Fourier transform infrared (FTIR) spectroscopy, see Figure S2a, shows new peaks at 968 cm-1, 636 cm-1, and 490 cm-1 that arise from S=O bonds. A new peakat 715 cm-1, attributed to C-S stretching, confirms reaction between sulfur and carbon atoms. Raman, FTIR (Figure S2b), and 1HNMR (Figure S2a, S2b) confirm that the MG dye molecular structure is unchanged with SO32- addition. The peak-signature 1 HNMR spectrum of MG is identical to that of the product; the product shows a chemical shift of 3.26 ppm that is assigned to the methyl protons being in close proximity to the positively charged nitrogen atom (labeled red in Figure S3). Further evidence of the proposed reaction mechanism is given by mass spectroscopy (Figure S4); the mass-to-charge ratio (m/z) increment of 80 matches the molecular weight of SO32-. Spectroscopy results verify that the chemical reactions between MG and sulfite are as depicted in Figure 1a. To validatethe reaction specificity to MG, commonly used food additives (benzoate, sorbate, nitrite) and oxidizers (ClO-, H2O2) were tested as competing interferents; only a distinct change of absorption was observed for sulfite, with negligible decreases observed for other anions and molecules (Figure 4d, Figures S5, S6). Our results suggest that MG dye, against other food additives and oxidizers, displays a high degree of selectivity to sulfite. Detection of Sulfite with the Portable UCL Reader. The UCL signal is gradually quenched with increasing amounts of MG and incubation time, as shown in Figure 4a and 4b. Figure 4c demonstrates the time-dependent UCL intensity of the completed probe; the UCL intensity stabilizes in 15 min, suggesting its suitability for in-field measurements. Figure 5a plots sulfite concentration versus relative UCL intensity F-F0, where F and F0 represent RGB intensity in the presence and absence of sulfite, respectively, measured by the smartphonereader. Relative UCL intensity linearly correlates to the logarithm of sulfite concentration in the range 0.005 to 10 µg/mL (F-F0 =71.94·logC+176.24 [R2 = 0.983]). For comparison, the sulfite concentration-dependent UCL signal measured by a fluorescence spectrometer is given in Figure 5b; the luminescent signal recovered with stepwise addition of increasing amounts of sulfite show a logarithmic relationship with sulfite concentration, the same as that obtained with the UCL reader, although with a better match


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Figure 5: (a) A linear relationship is found between relative fluorescence intensity (F − F0) and the logarithm of sulfite concentration. (b) UCL emission of paper test strip measured by fluorescence spectrometer (under 980 nm fiber laser excitation). (c) Photographs of ESM-CaS UCNPs (left) and NaYF4:Yb,Er,Mn UCNPs (right) under identical 980 nm laser illustration. Images of the UCL paper test strip loaded with (d)ESM-CaS UCNPs and (e) NaYF4:Yb,Er,Mn UCNPs, respectively.(f) Photographs of commercial sulfite detection test strips. For (d-f) the sulfite concentrations are, left to right: 0, 0.005, 0.01, 0.05,0.1, 0.5, 1,10 µg/mL. coefficient (R2 = 0.997). The shape of the UCL emission peak varies slightly with fluorescence recovery, presumably due to shifts in the spectral overlap between FRET donor and receptors. It is noteworthy that the sulfite detection limit of 2 ng/mL of our smartphone-based UCL detection systemis several orders of magnitude lower than that of most previous laboratory methods1417 . The low detection limit is primarily attributed to the application of the DT/MUA@ESM-CaS UCNPs with an extremely high UCL quantum yield of ≈ 60 %. As seen in Figure 5c, under 980 nm (100 mW) illumination the DT/MUA@ESM-CaS UCNPs show an extremely strong UCL that can readily be observed by the naked eye; in contrast the UCL emission from the NaYF4:Yb,Er,Mn nanoparticles26 is barely discernable. As illustrated in Figure 5d and 5e, the NaYF4 UCNPs were also employed as energy donors in the sulfite-detecting paper strips, with a significantly poorer detection limit (0.5 µg/mL) than that based ESM-CaS UCNPs. Historically, application of inorganic UCNPs has been limited due to low quantum yield and insufficient luminescence intensities. Likewise, we compared performances between the proposed UCL paper strips and commercially available sulfite test strips based on visual colorimetry. As shown in Figure 5f, the commercial test strips showed a detection limit of ~0.05 µg/mL. Real Sample Analysis. Our smartphone-based UCL device has, we believe, excellent prospects for analyte detectionin heterogeneous and bulk samples, without any need for pretreatment procedures such as centrifugation and decolorization, thus enabling rapid, facile, and on-site detection techniques. Unprocessed food samples usually contain suspended, insoluble, and coloredsubstances27-29, as well as agents30-33 susceptible to down-conversion luminescence (DCL) that can prevent a sensitive and reliable assay. For example, analyses based upon test-strip colorimetry, including a commercial sulfite detection test strip, see Figure 6a, are readily affected by suspensions and pigments within the extracts. In contrast the UCL-based assay operates independently of substrate interferents, including auto-fluorescence, precluding the

Figure 6: (a) Photographs and luminescence images of paper test strips/commercial sulfite test strips with different edible fungi extracts; Extract 1: filtered and centrifuged; Extract 2: without pretreatment; Extract 3: without pretreatment to which red pigment was added to simulate colored matrix. (b) Photograph of UCL detection system packed within a small brief-case. need for sample preprocessing. Given that pretreatment and laboratory equipmentare not required a fully integrated platform containing the UCL reader and associated materials easily fits within a small brief-case, see Figure 6b. Food sample extracts, and extracts then spiked with three different sulfite concentrations, were analyzed using our portable UCL device and micro-titrimetry; see Table 2. The recovery rates were in the range of 97.5-118.0 % with relative standard deviations (RSD) of 0.8-8.8 % for the UCL portable device, and 102.5118.3 % with relative standard deviations (RSD) of 0.3-3.3 % for the micro-titrimetry method. There is no significant difference between the results obtained by the two methods, demonstrating the utility of our smartphone-based UCL system.

CONCLUSIONS Em,Sm,Mn-doped CaS UCNPs1 are applied to chemical detection for the first time. A UCL paper test strip, based upon ESMCaS UCNPs, and a smartphone-based portable UCL reader were designed and constructed for rapid in-field detection of sulfite concentrations. The compact and low cost nature of the integrated device suggests its excellent potential as a general platform for food and drug analysis. The ultra-high quantum yield and superbright upconversion luminescence of the ESM-CaS UCNPs enable a 2 ng/mL sulfite detection limit, and make pretreatment procedures unnecessary. The design principles can be readily modified to enable detection of diverse analytes. Future applications in the life sciences, including clinical diagnostics, are anticipated.



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Table 2. Detection of sulfite in food samples. Portable UCL Device Sample

Measured level (µg/mL)

Edible fungi 0.52

Preserved fruit

Crystal sugar

Dried day lily

0.35

0.40

0.57

Spike (µg/mL)

Found level (µg/mL)

Micro-Titrimetry

Recovery(%)

RSD(%)

0.25

0.75

94.7

8.0

0.5

1.04

106.0

7.3

1

1.52

101.0

7.9

0.25

0.63

113.3

7.1

0.5

0.85

100.7

8.0

1

1.32

97.0

8.7

0.25

0.65

101.3

6.9

0.5

0.91

103.3

7.1

1

1.39

99.7

3.9

0.25

0.82

104.0

8.9

0.5

1.09

106.0

6.1

1

1.47

91.0

6.5

ASSOCIATED CONTENT Supporting Information Experimental materials; TEM, XRD, FTIR characterizations of ESM-CaS UCNPs (Figures S1); detailed experimental results of reaction mechanism (Figures S2-S4); results of interfering test (Figures S5-S6) were supplied in Supporting Information. The Supporting Information is available free of charge on the ACS Publications website.

AUTHOR INFORMATION

Corresponding Authors * E-mail: [email protected]. * E-mail: [email protected]. Author Contributions All authors have given approval to the final version of the manuscript.

Notes The authors declare no competing financial interest.

ACKNOWLEDGMENT The authors are thankful to the National Science Foundation of China (Grant no. 21235002) for providing financial support.

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0.53

0.39

0.41

0.61

Spike (µg/mL)


Recovery(%)

RSD(%)

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96.0

4.9

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0.66

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100.7

4.4

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1.37

95.7

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0.86

98.7

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109.3

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1.69

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3.8

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Insert Table of Contents artwork here CaS:Eu,Sm,Mn nanoparticles with ultra-high UCL quantum yield(~60%), and a smartphone,are applied to in-field food analysis.


Eu,Sm,Mn-doped CaS Nanoparticles with 59.3% Upconversion

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