Highly Water-Stable Dye@Ln-MOFs for Sensitive and Selective

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Highly water-stable dye@Ln-MOF for sensitive and selective detection toward antibiotics in water Mingke Yu, Ying Xie, Xinyu Wang, Yuxin Li, and Guangming Li ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.9b05815 • Publication Date (Web): 22 May 2019 Downloaded from http://pubs.acs.org on May 30, 2019

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ACS Applied Materials & Interfaces

Highly water-stable dye@Ln-MOF for sensitive and selective detection toward antibiotics in water Mingke Yu, Ying Xie, Xinyu Wang, Yuxin Li,* Guangming Li* Key Laboratory of Function Inorganic Material Chemistry (MOE), School of Chemistry and Material Science, Heilongjiang University, Harbin 150080, P. R. China. E-mail: [email protected]; [email protected] KEYWORDS. Excitation-wavelength independence; yellow light; lanthanide metal-organic framework; luminescent detection; antibiotics

ABSTRACT. The host-guest composite, RhB@Tb-dcpcpt, is synthesized by trapping

Rhodamine

B

(RhB)

into

the

channels

of

[Me2NH2][Tb3(dcpcpt)3(HCOO)]∙DMF∙15H2O (Tb-dcpcpt) via ion-exchange process. Photophysical property of RhB@Tb-dcpcpt exhibits stable co-luminescence of RhB and Tb3+ ion in the whole excitation range of 300–390

nm,

yellow-light

realizing emission.

PXRD

excitation-wavelength-independent and

photoluminescence

ACS Paragon Plus Environment

1

analysis

ACS Applied Materials & Interfaces 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 2 of 34

illustrates the outstanding stabilities of RhB@Tb-dcpcpt on structure and

photophysical

property

in

water

medium.

Subsequently,

a

bifunctional sensing process toward antibiotics is designed in terms of luminescent intensity and color. As a result, RhB@Tb-dcpcpt could realize

sensitive

and

selective

detection

toward

nitrofuran

antibiotics (nitrofurazone and nitrofurantoin) via luminescent quenching process and toward quinolone antibiotics (ciprofloxacin and

norfloxacin)

via

luminescence-color-changing

process.

Systematical analysis on sensing mechanism reveals that photo-induced electron

transfer

and

inner

filter

effect

contribute

to

the

realization of sensing process. Introduction Lanthanide metal-organic frameworks (Ln-MOFs), self-assembled from polydentate linkers and inorganic nodes of lanthanide ions through coordination bonds, are crystalline organic/inorganic hybrid materials with characteristic properties of photoluminescence.1-5 In Ln-MOFs, multi-emitting properties could be readily obtained by tuning the energy transfer from ligand to lanthanide ions, thereby providing a sensitive platform in terms of luminescent color and intensity.6-11 Moreover, the sensitivity to coordinate environment leads to the luminescent mutability of Ln-MOFs. Taking advantage of this phenomena, Ln-MOFs could serve as sensors toward circumstance factors such as temperature, pH value, solvent effect, which have


2

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been widely reported and acted as sensitive thermometers, pH indicators and solvent probes.12-17 However, another significant luminescent

instability,

excitation-wavelength

dependence,

is

rarely settled and utilized. Porosity is a defining characteristic of Ln-MOFs, and helpful to encapsulate excellent fluorophores guests, especially dye molecules with excitation-wavelength-independent performance, to construct co-luminescent composite through ion-exchange process and/or spatial confining effect.18-22 Thus, dual- even multi-emitting dye@Ln-MOF composites could be obtained, not only affording a novel path to design luminescent material independent on excitation wavelength, but also providing an opportunity to obtain durable and sensitive sensors through photon-induced electron transfer and inner filter effect.23-25 Considering the alternation of luminescent color and intensity, multiplexed detection could be readily realized. Up to now, several researches on multiplexed detection are reported. In 2017, a white-light-emitting lanthanide coordination complex was firstly prepared as a dual-selective sensor toward Ag+ and Mn2+ ions in water through


white-light-emitting sensibility

toward

Ln-MOF HS-

exhibited

ion,


process.26

Ag+

excellent

ion

mechanism

and under

THF

In

2018,

a

tri-selective molecule

three

via

excitation

wavelength.27 Although some progresses have been made in this regard,


3


the

multi-selective

materials

or

composites

Page 4 of 34

based

on

Ln-MOFs

independent on excitation wavelength is rarely reported, meanwhile the cogent system analysis for sensing mechanism is still a great challenge for the development of this type of sensors. Antibiotics are significant drugs to prevent and treat certain diseases, especially for resistance to bacterial infections in aquaculture.28-32

However,

widespread

application

causes

that

increased antibiotic residues appears in the grain, animals, even drinking water.33-35 Long-term intakes of these contaminated food could result in severe diseases such as immunity decline, allergic reactions, hereditary genetic defects and various types of cancers.36-39 At present, various expensive and complicated methods to determine antibiotics have been developed such as chromatographic techniques, optical sensors, electrochemical sensors, and biosensors.40-45 Despite great advantages on sensitivity necessarily

require

and selectivity, these technologies

professional

instruments,

cumbersome

pretreatment, and high operating costs. Therefore, as luminescent sensors, dye@Ln-MOF can provide an alternative to easily detect antibiotic with high sensitivity. In addition, in the real world, mixtures of antibiotics often exist. As a result, multiplexed detection for antibiotics in water solution is significant but challenging.


4

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Bearing

these

in

our

mind,

we

design

and

fabricate

an

excitation-wavelength-independent chemosensor to detect antibiotics in water. Anionic framework of [Me2NH2][Tb3(dcpcpt)3(HCOO)]∙DMF∙15H2O (Tb-dcpcpt, H3dcpcpt=3-(3,5-dicarboxylphenyl)-5-(4-carboxylphenl) -1H-1,2,4-triazole) and cationic dye of Rhodamine B (RhB) are selected to

prepare

RhB@Tb-dcpcpt

composite

by

ion-exchange

process.

Structural and luminescent stability in water medium is tested. Luminescent detection toward fourteen commonly-used antibiotics is examined by monitoring the luminescent alternation on intensity and color. Most importantly, detection mechanism is systematically studied. Experimental Section Materials and Instrumentations Tb(NO3)3∙6H2O was obtained by the reaction of Tb2O3 and nitric acid. The H3dcpcpt was purchased from commercial sources and used with recrystallization. Other chemicals and antibiotics were purchased from J&K Scientific Ltd. without purification. Fourier Transform Infrared (FT-IR) spectra were conducted in the range of 4000–450 cm-1 by using KBr disks on a Perkin-Elmer Spectrum 100 spectrophotometer. Ultra-violet (UV) spectra were collected on a Perkin-Elmer Lambda 35 spectrometer. Thermogravimetric analyses (TG) were performed on a Perkin-Elmer STA 6000 in 30–800 oC with 10


5


oC∙min-1.

Page 6 of 34

Powder X-ray diffraction (PXRD) data were recorded on a Rigaku

D/Max-3B X-ray diffractometer with Cu Kα in the angular range of 2θ = 5–50°. Nitrogen absorption-desorption isotherms were measured at the liquid nitrogen temperature (77 K), using a Quantachrome Autosorb iQ analyzer. Elemental analyses of C, H, O and N were conducted on a Perkin-Elmer 2400 analyzer. The photoluminescence spectra were measured with an Edinburgh FLS 920 fluorescence spectrophotometer. The corrected spectra were obtained via a calibration curve supplied with the instrument. Synthesis of Tb-dcpcpt According

to

the

previous

report,

the

crystal

sample

of

[Me2NH2][Tb3(dcpcpt)3(HCOO)]∙DMF∙15H2O (Tb-dcpcpt) was prepared by solvothermal reactions of 0.1 mmol Tb(NO3)3∙6H2O, 0.10 mmol H3dcpcpt, 8 mL DMF and 2 mL H2O sealed in a Teflon-lined autoclave at 160 oC for 72 hours.46 The resulting crystals were obtained and washed by ethanol and H2O for three times. Yield: 1.6 mg (2.02 wt%). Anal. Calcd. for C57H67N11O36Tb3 (wt%): C, 34.94; H, 3.45; O, 29.40; N, 7.86. Found (wt%): C, 34.68; H, 3.48; O, 29.44; N, 8.03. IR (KBr pellet, cm-1): 3414(s), 1676(s), 1585(s), 1421(m), 1375(s), 759(m). UV-vis (MeOH, nm): 203. Preparation of RhB@Tb-dcpcpt


6

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The colorless crystals of as-synthesized Tb-dcpcpt (1.6 mg) were immersed into 2 mL 10-3 mol∙L-1 (M) aqueous solution of RhB and kept standing for 24 hours at room temperature. After decanting the solution, the pink crystals obtained were washed with deionized water and dried in air. Luminescence Sensing Methodology 10.0 mg of RhB@Tb-dcpcpt sample was weighed, finely grounded, and then added to a cuvette containing 10 mL of deionized water under stirring. The fluorescence upon the excitation of 300–390 nm of RhB@Tb-dcpcpt suspension was measured in situ after the addition of freshly prepared analyte solutions. The mixture was stirred at a constant rate during experiment to maintain its homogeneity. All the experiment was performed in triplicate, and consistent results were reported. In a selective experiment, luminescence of the obtained suspension was recorded. Then, aqueous solution of antibiotics with certain

concentration

was

alternatively

introduced

into

the

suspension. After the addition, the luminescence property of the suspension was monitored. DFT calculation All of antibiotic molecule is optimized based on the previously reported method embedded in the Dmol3 code.47 For all spin-polarized calculations, the exchange-correlation functional was treated by the


7


Page 8 of 34

BLYP form within the generalized gradient approximation (GGA) framework, and the double numerical plus polarization (DNP) basis set

was

applied.48

To

obtain

a

converged

structure,

geometry

optimization procedure was repeated until the average force on the atoms was less than 0.05 eV∙A-1 and the energy change less than 2.0×10-5 eV/atom. RESULTS AND DISCUSSION Synthesis of RhB@Tb-dcpcpt Tb-dcpcpt is synthesized from Tb(NO3)3∙6H2O and H3dcpcpt in H2O and DMF mixed solution under solvothermal conditions at 160 oC for 72 hours (Figure 1a and 1b).46 In addition to semblable lattice parameter, the as-prepared crystal shows an identical PXRD pattern to that simulated from the single crystal structure reported previously (Figure 1c and Table S1). Based on the previous report, Tb-dcpcpt possesses 1D open channel with the size of 15.34×12.13 Å2 and the porosity is 49.8%.46 N2 sorption isotherm confirms the existence of porous structure of as-synthesized Tb-dcpcpt, and its BET surface area is up to 801 m2∙g-1 (Figure 1d). The anionic


8

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Figure 1 (a) 3D framework of Tb-dcpcpt and RhB@Tb-dcpcpt; (b) the photographs of Tb-dcpcpt (left) and RhB@Tb-dcpcpt (right) under day light (upper) and 365 nm UV lamp (down); (c) PXRD patters of simulated Tb-dcpcpt, examined Tb-dcpcpt and RhB@Tb-dcpcpt; (d) N2 sorption isotherm of Tb-dcpcpt and RhB@Tb-dcpcpt; (e) UV-vis spectra of Tb-dcpcpt, RhB and RhB@Tb-dcpcpt.

framework is balanced by protonated [Me2NH2]+ originating from decomposition of DMF during the reaction. FT-IR, TG and UV-vis further confirm the structure of Tb-dcpcpt (Figure S1, S2 and 1e). In addition, Tb-dcpcpt has striking stability. The crystallinity and morphology can remain intact in aqueous solutions or air for at least three months. We could still obtain the structure via the single crystal X-ray


9


diffraction

pattern.

TG

curve

reveals

that

Page 10 of 34

the

decomposition

temperature of Tb-dcpcpt is about 500 oC (Figure S2). According to these aforementioned features, Tb-dcpcpt is an anionic Ln-MOF with porous structure and good stability, which encourages us to employ it as a host to encapsulate cationic dye. RhB is an outstanding cationic fluorophore for chem/bio-sensing applications.49-52 However, its widespread application is limited by the aggregation-induced quenching and photo-induced degradation. Herein, an encapsulating strategy is utilized by capturing and restraining the RhB molecule into the porous framework of Tb-dcpcpt (Figure 1a). After encapsulation, the crystal color under day light obviously turns from transparent to pink; the luminescent color under UV lamp turns from green to yellow (Figure 1b). PXRD patterns before and after trapping RhB illustrate the identical pattern, meaning that the framework remains intact during encapsulation (Figure 1c). Sharp decrease of absorbed quantity in N2 sorption isotherm further confirms the introduction of RhB (Figure 1d). Several factors prompt the successful encapsulation. On one hand, the kinetic size of RhB (15.9×11.8×5.6

Å3) rivals with the

window

scale of Tb-dcpcpt

(15.34×12.13 Å2), thereby providing the potential to trap RhB into the pores. On the other hand, the anionic Tb-dcpcpt framework could attract the RhB cation, resulting in the ion-exchange process. Both of the fast encapsulation (1 day) without ultrasonic assist and low


10

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RhB concentration of immerging solution (10-3 M) reveal the facility to trap RhB into Tb-dcpcpt. FT-IR spectra display obvious RhB peaks, accounting for the triumph of ion-exchange process, and indirectly stating that RhB is not degraded in the process of encapsulation (Figure S1). Meanwhile, the ion-exchange process could be monitored by UV-vis spectroscopy. The molar ratio of RhB versus Tb-dcpcpt is determined as about one seventh (0.15 μmol:1.00 μmol). In other words, the exchange percentage of [Me2NH2]+ is 15 %. TG data and elementary analysis further confirm the guest percentage in RhB@Tb-dcpcpt (Figure S2 and Table S2). Based on the concentrations of RhB in the solution before and after the encapsulation of Tb-dcpcpt via UV-vis test, we estimate the RhB exchange percentage is 17.3 %, very similar to the result of UV-vis. Water stability of RhB@Tb-dcpcpt Given that the as-synthesized composite will detect antibiotics in aqueous solution, the stability of the fresh sample in water medium are checked. The finely ground sample of RhB@Tb-dcpcpt is suspended into water by stirring 30 minutes. PXRD patterns of RhB@Tb-dcpcpt filtered from suspension perform the same profile with the initial sample,

illustrating

the

framework

remains

integrated

after

suspending in water (Figure S3). The filtrate could be detected little RhB through UV-vis spectra, revealing that RhB is well confined in the channels of the framework. RhB@Tb-dcpcpt could even remain the


11


structural stability in 0.1 M phosphate buffer saline (PBS) solution (Figure S3). These aforementioned results indicate the excellent stability of RhB@Tb-dcpcpt in water medium, revealing that nanoporous channels of Tb-dcpcpt could generate the confining effect against the dissociation of RhB aggregation, and largely enhancing the stability of composites. The results also confirm that RhB@Tb-dcpcpt facilitates the application in chem-/bio-sensing in aqueous solution. Photoluminescence of Tb-dcpcpt and RhB@Tb-dcpcpt H3dcpcpt ligand performs little emission upon excitation at 300– 320 nm and emits gradually increasing blue-green light at 400–650 nm in the excitation of 320–390 nm (Figure S4). For Tb-dcpcpt, green-light emission in the whole excitation range of 300–390 nm is realized according to CIEx-y chromaticity diagram of Tb-dcpcpt (Figure S5). As shown in Figure 2a, Tb-dcpcpt displays the sharp characteristic peaks of the Tb3+ ion at 489, 545, 581 and 619 nm corresponding to the

5D

4→

7F

J

(J = 6, 5, 4 and 3) transitions,

respectively. The presence of Tb3+ emission and the absence of emission from H 3 dcpcpt ligand implies that antenna effect takes place. According to the Dexter theory, the luminescent property in luminescent lanthanide complex is significantly determined by the energy transfer from ligand triplet state to lanthanide receiving energy level.53 In other words, energy migration occurs upon ligand absorption, followed by intersystem crossing and antenna energy


12

Page 12 of 34

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transfer, and then generating f-f emissions of Tb3+ ion. Based on this, the singlet and triplet energy levels of H3dcpcpt is calculated as 30800 cm -1 and 23700 cm -1 , respectively. 54 The 7100 cm -1 energy difference states the effectiveness of intersystem crossing process according to Reinhoudt’s empirical rule.55 In addition, according to the Latva’s empirical rule, 2500–4500 cm-1 are the most optimal energy d

i

f

f

e

r

e

n

c

e

s

d

u

r

i

n

g

Figure 2 (a) 3D solid-state photoluminescence spectrum of Tb-dcpcpt; (b) 3D solid-state photoluminescence spectrum of RhB@Tb-dcpcpt; (c) CIE chromaticity diagram showing the emissions of RhB@Tb-dcpcpt in solid state and in aqueous solution upon different excitation wavelength; (d) Spectral overlap between the absorption of RhB and the emission of Tb-dcpcpt.

energy transfer process from ligand triplet to Tb3+ ions.56 Therefore, the energy difference of 3200 cm-1 between triplet energy level of


13


Page 14 of 34

H3dcpcpt and the resonance energy level of Tb3+ ions (20500 cm-1) explains the reason why Tb3+ ion is well-sensitized by H3dcpcpt ligand. Comparing

with

the

luminescence

of

Tb-dcpcpt,

solid-state

RhB@Tb-dcpcpt weakens Tb3+ emission centered at 545 nm and emerges broad emission around 630 nm corresponding to RhB fluorescence (Figure 2b).57 The luminescent mechanism of RhB@Tb-dcpcpt is investigated. Given that the Tb-dcpcpt framework and RhB are ionic, one possible mechanism can be proposed to be the photo-induced electron transfer: the electrons from the electron-rich framework are transferred to the electro-deficient RhB molecules. The energy levels are calculated by density functional theory (DFT), accordingly, for Tb-dcpcpt and RhB. Although the lowest unoccupied molecular orbitals (LUMO) of Tb-dcpcpt is slightly lower than that of RhB, excited high-energy level of Tb-dcpcpt is higher than LUMO of RhB, resulting in the photo-induced high-energy electron transfer (Scheme S1).58 Another possible mechanism is fluorescence resonance energy transfer. UV-vis absorbance of RhB shows a main band around 545 nm which holds a spectral overlap to the emission band of Tb-dcpcpt, meaning that there is an efficient fluorescence resonance energy transfer from the framework to RhB (Figure 2d).59,60 As a result, the coexistence of fluorescence resonance energy transfer and photo-induced high-energy electron transfer makes RhB@Tb-dcpcpt show co-luminescence of Tb-dcpcpt and RhB. Remarkably and interestingly, luminescent color maintains stable


14

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yellow light in the whole excitation wavelength ranged from 300 to 390 nm (Figure 2c). This contribution significantly resolves the problem

on

the

excitation-wavelength-dependent

instability

on

luminescent color for a lanthanide-based sensor in water medium. It also illustrates that the Tb-dcpcpt framework displays good and stable sensitizing ability toward RhB dye, resulting from the short distance between Tb3+ ions and RhB molecules through encapsulation process.61 In a control experiment, Tb-dcpcpt and RhB is simply mixed with a ratio of 1.00 μmol:0.15 μmol. The photoluminescent spectra display that it keeps the same profile as that of Tb-dcpcpt in 400–600 nm and weak emission of RhB around 630 nm (Figure S6). Its FRET efficiency of 4.6% is much lower than that of RhB@Tb-dcpcpt (22.4%) (Table S3).62 Most importantly, its luminescent-color changes between green and yellow, without excitation-wavelength-independence stability. Water molecule often acts as luminescence quenching reagent for the luminescent lanthanide complexes. However, water medium is necessary for luminescent sensing toward pollutants existing in drinking water or

industrial waste

water.

In

this work, the

luminescent behavior of RhB@Tb-dcpcpt existing in aqueous solution is examined. In water medium, the emission intensity and quantum yield are slightly decreased (Figure S7 and Table S4). The emission around 440 nm corresponding to H3dcpcpt ligand is emerged. All of these phenomena

suggest

that

water

molecules


15

slightly

affect

the


Page 16 of 34

intra-molecular energy transfer from H3dcpcpt to Tb3+ ion. By comparison, Tb-dcpcpt without RhB encapsulation in aqueous solution presents the same pattern of luminescent behavior (Figure S8). The slight decrease on luminescent intensity of Tb-dcpcpt framework in water medium suggests excellent luminescent stability against water and overcomes most of luminescent Tb-based complexes in previous reports.63 For RhB@Tb-dcpcpt in water, the emission of RhB shifts from 630 nm in solid state to 580 nm in aqueous solution, deriving from the concentration effect of RhB and the high dispersion of RhB in Tb-dcpcpt framework (Figure S7).64,65 This phenomenon reveals that the problem of aggregation-induced quenching for RhB molecules is resolved by encapsulation process. Interestingly, RhB@Tb-dcpcpt in aqueous solution remains stable yellow-light emission in the whole range

of 300–390nm

(Figure

2c).

As our best

knowledge, this

excitation-wavelength-independence luminescence in water medium is the first report for lanthanide-based complexes, polymers and composites. Detection of Nitrofurans Antibiotics In order to explore the sensibility of the sensor (RhB@Tb-dcpcpt) toward analytes (antibiotics) in water medium, aqueous solutions containing 0.01 M concentrations of various antibiotics were added into the 1 g/L well-dispersed suspension of RhB@Tb-dcpcpt in water. Fourteen commonly-used antibiotics in six classes were checked,


16

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including β-lactams (penicillin, PCL; amoxicillin ACL; cefixime CFX; cephradine CFD), aminoglycosides (gentamicin GTM; kanamycin KNM), macrolides

(roxithromycin

ROX;

azithromycin

AZM),

quinolones

(ciprofloxacin CPFX; norfloxacin NFX), nitrofurans (nitrofurazone NZF; nitrofurantoin NFT) and others (vancomycin VCC; lincomycin LCC). According to Figure 3a, nitrofuran antibiotics (NZF and NFT) present obvious luminescent quenching to the sensor, while others exhibit low even little quenching effect. The alternation of excitation wavelength has little influence on the value of quenching efficiencies by monitoring the luminescent intensity at 545 nm (Figure 3b). In order to assess the sensing sensitivity of RhB@Tb-dcpcpt toward NZF and NFT, quantitative luminescent titration experiments are carried out. As shown in Figure 3c and 3d, the emission intensity of

the

sensor

decreased

dramatically

when

the

nitrofuran

concentration increased from 0 mM to 0.10 mM, featuring heavy dependence on the concentration of the nitrofuran antibiotics. The luminescent quenching efficiency can be quantitatively expressed by using the Stern-Volmer (SV) equation: I0/I = 1+KSV×[C], where KSV is the quenching constant (M-1), [C] is the molar concentration of the analyte (M), I0 and I are the luminescence intensities at certain wavelength in the absence and presence of the analyte, respectively. Based on the KSV values, the limitation of detection (LOD) of RhB@Tb-dcpcpt toward NZF and NFT could be


17


Figure 3 (a) Effect on the emission spectra of 1 g/L RhB@Tb-dcpcpt well-dispersed in water with isovolumetric 0.01 M antibiotics aqueous solution; (b) fluorescence quenching of RhB@Tb-dcpcpt by different antibiotics under different excitation wavelength at room temperature; (c) effect on the emission spectra of 1 g/L RhB@Tb-dcpcpt well-dispersed in water with different concentrations of NZF at room temperature; (d) effect on the emission spectra 1 g/L RhB@Tb-dcpcpt well-dispersed in water with different concentrations of NFT at room temperature. (e) luminescence quenching efficiency of RhB@Tb-dcpcpt with 1 mM antibiotics aqueous solution upon adding different concentration of NZF. (f) luminescence quenching efficiency of RhB@Tb-dcpcpt with 1 mM antibiotics aqueous solution upon adding different concentration of NFT. The inset spectra are Sterm-Volmer plots.


18

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Table 1. KSV, R2 and LOD of RhB@Tb-dcpcpt toward NZF and NFT at room temperature

NZF

NFT

@491 nm

@545 nm

@583 nm

@491 nm

@545 nm

@583 nm

Ksv (×104 M-1)

4.45

5.98

3.78

4.53

6.69

3.99

R2

0.99297

0.99615

0.99534

0.99320

0.99388

0.99354

LOD (×10-7 M)

6.79

5.02

7.93

6.62

4.48

7.53

LOD (ppb)

134

99

157

158

107

179

Table 2. Comparison of luminescent materials for sensing nitrofuran and quinolone antibiotics

Materials

Methods

Objectives

Ksv

LOD (ppb)

Ref.

Cd-tbaed

Quenching

NZF

5.06 × 104

162

67

Cd-tbaed

Quenching

NTF

3.57 × 104

274

67

PVD

Enhancement

CPFX

1.40 × 105

2350

68

CdTe QDs

Quenching

NFX

N/A

31

69

NZF

5.98 × 104

99

NFT

6.69 × 104

107

CPFX

1.67 × 104

716

NFX

5.71 × 104

201

Quenching RhB@Tb-dcpcpt LCC* *LCC: Luminescence-color-changing


19

This work


calculated according to the formula of 3σ/KSV, where σ is the standard deviation for three repeated luminescent measurement. By monitoring luminescent intensities at 491, 545 and 483 nm, the values of KSV, R2 and LOD are determined and listed in Table 1. A detailed SV analysis further reveals that there exists near linear correlations between the quenching efficiency and the amount of nitrofuran antibiotics, indicating that either static or dynamic mechanism exists in the quenching process (Figure 3c, 3d, S9 and S10). By monitoring 545 nm, the LOD toward NZF and NFT are as low as 0.502 μM (99 ppb) and 0.448 μM (106 ppb), respectively. According to Table 2, the sensitivity in this work are far superior to most of reported fluorescence probes for NZF and NFT and meets the standard of World Health Organization (WHO) and occupational safety and health administration (OSHA) for the maximum allowable level of antibiotics in drinking water.66 It is also much higher than that of Tb-dcpcpt (32.5 ppm for NZF and 42.1 ppm for NFT, Figure S11 and S12). The excellent sensitivity toward NZF and NFT demonstrates that RhB@Tb-dcpcpt holds high quenching efficiencies toward nitrofurans, but poor toward other categories of antibiotics. Based on this, we further checked the detection selectivity for nitrofurans in the presence of other antibiotics. In a control experiment, a 1 mM aqueous solution of each antibiotic (PCL, ACL, CFX, CFD, GTM, KNM, ROX, AZM, CPFX, NFX, VCC, LCC) was initially added into the 1g/L RhB@Tb-dcpcpt


20

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aqueous suspension. Then NZF or NFT were added piece by piece. The luminescence intensity of RhB@Tb-dcpcpt shows slight changes in the presence of excess other antibiotics (Figure 3e and 3f). Upon introducing nitrofurans into the mixture of the RhB@Tb-dcpcpt and other antibiotics, the luminescence was significantly quenched, convincing the high quenching selectivity of RhB@Tb-dcpcpt toward nitrofurans. To further elucidate the selectivity of this composite, number of interfering analytes (serine, threonine, aspartic acid, ascorbic acid, glucose and GSH) are each added to the system, which shows no obvious changes in the luminescence of the sensor (Figure S13). Additionally, we find that RhB@Tb-dcpcpt can be regenerated and reused for a significant number of cycles by centrifugation of the suspension after use and washing several times with water, implying the good recyclability of luminescence detection toward nitrofurans (Figure S14). Detection of Quinolone Antibiotics Up to now, myriad luminescent materials have shown excellent performance of sensitivity based on their turn-on/-off process.9-17 However, most of them focus on luminescence intensity, not on luminescence color. Remarkably, RhB@Tb-dcpcpt presents obvious luminescence-color-changing process from yellow to blue after adding quinolones such as CPFX and NFX, while other antibiotics remain yellow-light

emission

(Figure

4a).

Like


21

those

in

detecting


Page 22 of 34

nitrofurans, quantitative titration experiments of RhB@Tb-dcpcpt toward CPFX and NFX are performed. According to the Figure 4b–4d, the luminescent color of the samples obviously turns from yellow to white, then to blue. With the increase of CPFX and NFX concentration, the intensities of the Tb3+ and RhB components decrease rapidly, but the ligand component remains for NFX and even increases for CPFX (Figure 4b and 4d). Therefore, the blue-light emission gradually dominates the emission with continuous addition of CPFX and NFX, which results in luminescence-color-changing process from yellow to white to blue. According to Figure 4f, the luminescent color of the samples turns to white when the CPFX or NFX concentration of 4 mM and to blue when 7 mM, which is a relatively low visual LOD. In addition, the plots of relative intensities (I441/I583) versus the concentration of quinolone antibiotics in Figure S15 and S16 reveal good linear relationship (R2=0.99878 for CPFX and 0.99306 for NFX). The LODs are estimated to be 0.21 μM (69 ppb) and 0.17 μM (53 ppb) for CPFX and NFX, respectively. The results suggest that RhB@Tb-dcpcpt has low LODs toward CPFX and NFX, even lower than the threshold limit suggested by the WHO and OSHA.66 Interestingly, the Tb-dcpcpt framework possesses little sensitivity toward NFX and CPFX (Figure S17 and S18). To the best of our knowledge, this is also the first report for sensing quinolone

antibiotics

based

on

Ln-MOFs

through

luminescence-color-changing process (Table 2). In addition, the


22

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alternation of excitation wavelength has little influence on the luminescence-color-changing process.

Figure 4 (a) Effect on the luminescence color of 1 g/L RhB@Tb-dcpcpt well-dispersed in water with isovolumetric 0.01 M antibiotics aqueous solution; (b) effect on the emission spectra of 1 g/L RhB@Tb-dcpcpt well-dispersed in water with different concentrations of NFX; (c) the luminescence color of RhB@Tb-dcpcpt with different concentration of NFX and CPFX; (d) effect on the emission spectra of 1 g/L RhB@Tb-dcpcpt well-dispersed in water with different concentrations of CPFX. The inset spectra are CIE diagrams. The inset photographs are RhB@Tb-dcpcpt under 365 nm UV lamp after adding quinolone antibiotics with certain concentration.

The detection selectivity for quinolones in the presence of other antibiotics is subsequently conducted. Saturated aqueous solution of each antibiotic (PCL, ACL, CFX, CFD, GTM, KNM, ROX, AZM, VCC, LCC) was initially added into the 1g/L RhB@Tb-dcpcpt aqueous suspension. Then 0.01 M CPFX or NFX were added. As can be seen from Figure S19,


23


Page 24 of 34

the luminescence color of RhB@Tb-dcpcpt shows indiscernible changes in the presence of other antibiotics. Upon introducing quinolones into the mixture of the RhB@Tb-dcpcpt and other antibiotics, the luminescence color significantly changes to blue, convincing the high selectivity of RhB@Tb-dcpcpt toward quinolones on luminescence color. Interfering analytes (serine, threonine, aspartic acid, ascorbic acid, glucose and GSH) also possess little alternation (Figure S20). In addition,

RhB@Tb-dcpcpt

also

present

good

recyclability

of

luminescence sensing Sensing mechanism toward antibiotics Changes on structure, charge and energy transfer are three significant factors causing luminescent sensing behavior. Based on this, the underlying mechanism of the RhB@Tb-dcpcpt (sensor) in response to the presence of nitrofuran and quinolone antibiotics (analytes) in water is systematically explored. For structural analysis, it is characterized that the filtered powder and filtrate prepared from the RhB@Tb-dcpcpt aqueous suspensions in the absence and presence of analytes. The powder presents identical PXRD patterns with the as-synthesized RhB@Tb-dcpcpt, meaning that the framework of Tb-dcpcpt does not collapse (Figure S21). The analytes are not absorbed, encapsulated or degraded by the sensor in that the filtrate possesses nearly same UV-vis absorption, photophysical properties and liquid chromatogram.


24

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Through the encapsulation of RhB, the composite system enhances the electron transfer ability, helpful for luminescent quenching toward conjugate compounds such as antibiotics.62 Given this, one possible

sensing

mechanism

toward

nitrofuran

and

quinolone

antibiotics can be proposed to be the photo-induced electron transfer; that is, the photo-induced excited electrons could be transferred from the sensor to the LUMO of the analytes, not to the ground state of the sensor. The lower the LUMO energy of the analytes, the easier the electrons are transferred. Accordingly, LUMOs and HOMOs of fourteen antibiotic analytes are all calculated by DFT, as shown in Figure 5a. NZF and NFT have lowest LUMO energy level, which explains the reason of luminescent quenching. For other antibiotics with lower quenching efficiency, however, the order of observed quenching efficiency is not fully in accordance with the LUMO energy, indicating that photo-induced electron transfer is not the only mechanism for the luminescence sensing mechanism in this system.

Figure 5 (a) HOMO-LUMO energy levels and molecule frontier orbital energy level diagram of each antibiotic; (b) the absorption spectra of each antibiotic.


25


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Another possible mechanism is energy allocation and transfer, including FRET and inner filter effect. The UV-vis absorption of all the antibiotics analytes have little spectral overlap with the emission of RhB@Tb-dcpcpt sensor, implying the inexistence of FRET (Figure 6b). In addition, inner filter effect plays central role on the sensitivity of RhB@Tb-dcpcpt toward nitrofuran and quinolone antibiotics. The peak-fitting analysis for RhB@Tb-dcpcpt after sensing

reveals

that

the

ligand-center

emission

produced

a

bathochromic shift with the increase of CPFX and NFX (Figure S22 and Table S5–S7). NZF, NFT, NFX and CPFX possess absorption at 300–390 nm in the order of NZF≈NFT>NFX>CPFX, which is in accordance of the order of quenching efficiency (Figure 5b). After absorption, NFX and CPFX could emit blue light, but NZF and NFT have no obvious emission in visible-light region, explaining that the luminescent quenching process toward nitrofurans and luminescent-color-changing process toward quinolones. (Figure S23).70 CONCLUSIONS Fabrication of RhB@Tb-dcpcpt demonstrates that cationic RhB could be introduced successfully into the channels of anionic Tb-dcpcpt framework. The composite RhB@Tb-dcpcpt presents significant chemical stability and excitation-wavelength-independent yellow luminescence in water medium. Photophysical analysis supports that RhB@Tb-dcpcpt is an excellent bifunctional sensor able to detect nitrofuran


26

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antibiotics (NZF and NFT) via luminescent quenching process and quinolone antibiotics (NFX and CPFX) via luminescence-color-changing phenomenon in long range of excitation wavelength. These results indicate that the as-synthesized RhB@Tb-dcpcpt is a favorable material for simultaneous detection toward nitrofuran and quinolone antibiotics in water, being potential sensor in monitoring water quality. ASSOCIATED CONTENT Supporting Information Supporting Information. PXRD, FT-IR, TG and photoluminescence data (PDF). AUTHOR INFORMATION Corresponding Author * E-mail: [email protected] * E-mail: [email protected] Notes The authors declare no competing financial interest. ACKNOWLEDGMENT We thank Special Postdoctoral Funding of Heilongjiang Provincial (LBH-TZ19), University Nursing Program for Young Scholars with Creative Talents in Heilongjiang Province


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(2017-KYYWF-0449) and Basic Scientific Research Expenses of Heilongjiang Provincial Universities (KJCXZD201706). REFERENCES (1). Kreno L.; Leong K.; Farha, O.; Allendorf M.; Van Duyne, R.; Hupp, J. Metal-Organic Framework Materials as Chemical Sensors Chem. Rev. 2012, 112, 1105–1125. (2). Liu, C.; Zhang, R.; Lin, C.; Zhou, L.; Cai, L.; Kong, J.; Yang, S.; Han, K.; Sun, Q. Intraligand Charge Transfer Sensitization on Self-Assembled Europium Tetrahedral Cage Leads to Dual-Selective Luminescent Sensing toward Anion and Cation J. Am. Chem. Soc. 2017, 139, 12474–12479. (3). Wu, S.; Lin, Y.; Liu, J.; Shi, W.; Yang, G.; Cheng, P. Rapid Detection of the Biomarkers for Carcinoid Tumors by a Water Stable Luminescent Lanthanide Metal-Organic Framework Sensor Adv. Funct. Mater. 2018, 28, 1707169. (4). Cui, Y.; Chen, B.; Qian, G. Lanthanide Metal-Organic Frameworks for Luminescent Sensing and Light-Emitting Applications Coord. Chem. Rev. 2014, 273–274, 76–86. (5). Kovacs, D.; Lu, X.; Meszaros, L. S.; Ott, M.; Andres, J.; Borbas, K. E. Photophysics of Coumarin and Carbostyril-Sensitized Luminescent Lanthanide Complexes: Implications for Complex Design in Multiplex Detection J. Am. Chem. Soc. 2017, 139, 5756–5767. (6). Bünzli, J. On the Design of Highly Luminescent Lanthanide Complexes Coord. Chem. Rev. 2015, 293–294, 19–47. (7). Zhang, X.; Wang, W.; Hu, Z.; Wang, G.; Uvdal, K. Coordination Polymers for Energy Transfer: Preparations, Properties, Sensing Applications, and Perspectives Coord. Chem. Rev. 2015, 284, 206–235. (8). Qin, X.; Liu, X.; Huang, W.; Bettinelli, M.; Liu, X. Lanthanide-Activated Phosphors Based on 4f-5d Optical Transitions: Theoretical and Experimental Aspects Chem. Rev. 2017, 117, 4488–4527. (9). Chen, B.; Xiang, S.; Qian, G. Metal-Organic Frameworks with Functional Pores for Recognition of Small Molecules Acc. Chem. Res. 2010, 43, 1115–1124. (10). Sava Gallis, D.; Rohwer, L.; Rodriguez, M.; Barnhart-Dailey, M.; Butler, K.; Luk, T.; Timlin, J.; Chapman, K. Multifunctional, Tunable Metal-Organic Framework Materials Platform for Bioimaging Applications ACS Appl. Mater. Interfaces 2017, 9, 22268–22277. (11). Xu, G.; Wu, Y.; Dong, W.; Zhao, J.; Wu, X.; Li, D.; Zhang, Q. A Multifunctional Tb-MOF for Highly Discriminative Sensing of Eu3+ /Dy3+ and as a Catalyst Support of Ag Nanoparticles Small 2017, 13, 1602996. (12). Cai, H.; Lu, W.; Yang, C.; Zhang, M.; Li, M.; Che, C.; Li, D. Tandem Forster Resonance Energy Transfer Induced Luminescent


28

Page 28 of 34

Page 29 of 34 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Ratiometric Thermometry in Dye-Encapsulated Biological Metal-Organic Framework Adv. Optical Mater. 2018, 1801149. (13). Zhou, Y.; Yan, B.; Lei, F. Postsynthetic Lanthanide Functionalization of Nanosized Metal-Organic Frameworks for Highly Sensitive Ratiometric Luminescent Thermometry Chem. Commun. 2014, 50, 15235–15238. (14). Lu, Y.; Yan, B. A Ratiometric Fluorescent pH Sensor based on Nanoscale Metal-Organic Frameworks (MOFs) Modified by Europium(III) Complexes Chem. Commun. 2014, 50, 13323–13326. (15). Xia, T.; Cui, Y.; Yang, Y.; Qian, G. Highly Stable Mixed-Lanthanide Metal-Organic Frameworks for Self-Referencing and Colorimetric Luminescent pH Sensing ChemNanoMat 2017, 3, 51–57. (16). Dou, L.; Bu, T.; Zhang, W.; Zhao, B.; Yang, Q.; Huang, L.; Li, S.; Yang, C.; Wang, J.; Zhang, D. Chemical-Staining based Lateral Flow Immunoassay: A Nanomaterials-Free and Ultra-Simple Tool for a Small Molecule Detection Sens. Actuators B Chem. 2019, 279, 427–432. (17). Lin, R.; Xiang, S.; Xing, H.; Zhou, W.; Chen, B. Exploration of Porous Metal-Organic Frameworks for Gas Separation and Purification Coord. Chem. Rev. 2019, 378, 87–103. (18). Furukawa, H.; Cordova K.; O’Keeffe, M.; Yaghi, O. The Chemistry and Application of Metal-Organic Frameworks Science 2013, 341, 123044. (19). Xu, X.; Lian, X.; Hao, J.; Zhang, C.; Yan, B. A Double-Stimuli-Responsive Fluorescent Center for Monitoring of Food Spoilage based on Dye Covalently Modified EuMOFs: From Sensory Hydrogels to Logic Devices Adv. Mater. 2017, 29, 1702298. (20). Zhou, H.; Kitagawa, S. Introduction. Metal-Organic Frameworks (MOFs) Chem. Soc. Rev. 2014, 43, 5415–5418. (21). Lin, X.; Gao, G.; Zheng, L.; Chi, Y.; Chen, G. Encapsulation of Strongly Fluorescent Carbon Quantum Dots in Metal-Organic Frameworks for Enhancing Chemical Sensing Anal. Chem. 2014, 86, 1223– 1228. (22). Dong, Y.; Cai, J.; Fang, Q.; You, X.; Chi, Y. Dual-Emission of Lanthanide Metal-Organic Frameworks Encapsulating Carbon-Based Dots for Ratiometric Detection of Water in Organic Solvents Anal. Chem. 2016, 88, 1748–1752. (23). Hao, J.; Yan, B. Simultaneous Determination of Indoor Ammonia Pollution and its Biological Metabolite in the Human Body with a Recyclable Nanocrystalline Lanthanide-Functionalized MOF Nanoscale 2016, 8, 2881–2886. (24). Zhao, S.; Song, X.; Zhu, M.; Meng, X.; Wu, L.; Feng, J.; Song, S.; Zhang, H. Encapsulation of Ln(III) Ions/Dyes within a Microporous Anionic MOF by Post-Synthetic Ionic Exchange Serving as a Ln(III) Ion Probe and Two-Color Luminescent Sensors Chem. Eur. J. 2015, 21, 9748–9752. (25). Yao, C.; Xu, Y.; Xia, Z. A Carbon Dot-Encapsulated UiO-Type Metal Organic Framework as a Multifunctional Fluorescent Sensor for


29


Temperature, Metal Ion and pH Detection J. Mater. Chem. C 2018, 6, 4396–4399. (26). Li, Y.; Li, S.; Yan, P.; Wang, X.; Yao, X.; An, G.; Li, G. Luminescence-Color-Changing Sensing of Mn2+ and Ag+ Ions based on a White-Light-Emitting Lanthanide Coordination Polymer Chem. Commun. 2017, 53, 5067–5070. (27). Wang, X.; Yao, X.; Huang, Q.; Li, Y.; An, G.; Li, G. Triple-Wavelength-Region Luminescence Sensing based on a Color-Tunable Emitting Lanthanide Metal Organic Framework Anal. Chem. 2018, 90, 6675–6682. (28). Li, W.; Zhu, J.; Xie, G.; Ren, Y.; Zheng, Y. Ratiometric System based on Graphene Quantum Dots and Eu3+ for Selective Detection of Tetracyclines Anal. Chim. Acta 2018, 1022, 131–137. (29). Wang, J.; Cheng, R.; Wang, Y.; Sun, L.; Chen, L.; Dai, X.; Pan, J.; Pan, G.; Yan, Y. Surface-Imprinted Fluorescence Microspheres as Ultrasensitive Sensor for Rapid and Effective Detection of Tetracycline in Real Biological Samples Sens. Actuators B Chem. 2018, 263, 533–542. (30). Geng, Y.; Guo, M.; Tan, J.; Huang, S.; Tang, Y.; Tan, L.; Liang, Y. A Fluorescent Molecularly Imprinted Polymer Using Aptamer as a Functional Monomer for Sensing of Kanamycin Sens. Actuators B Chem. 2018, 268, 47–54. (31). Yang, J.; Li, Z.; Zhu, H. Adsorption and Photocatalytic Degradation of Sulfamethoxazole by a Novel Composite Hydrogel with Visible Light Irradiation Appl. Catal. B-Environ. 2017, 217, 603–614. (32). Zhang, Q.; Lei, M.; Yan, H.; Wang, J.; Shi, Y. A Water-Stable 3D Luminescent Metal-Organic Framework based on Heterometallic [EuIII6ZnII] Clusters Showing Highly Sensitive, Selective, and Reversible Detection of Ronidazole Inorg. Chem. 2017, 56, 7610–7614. (33). Wang, B.; Lv, X.; Feng, D.; Xie, L.; Zhang, J.; Li, M.; Xie, Y.; Li, J.; Zhou, H. Highly Stable Zr(IV)-Based Metal-Organic Frameworks for the Detection and Removal of Antibiotics and Organic Explosives in Water J. Am. Chem. Soc. 2016, 138, 6204–6216. (34). Jin, W.; Chen, W.; Xu, P.; Lin, X.; Huang, X.; Chen, G.; Lu, F.; Chen, X. An Exceptionally Water Stable Metal-Organic Framework with Amide-Functionalized Cages: Selective CO2 /CH4 Uptake and Removal of Antibiotics and Dyes from Water Chem. Eur. J. 2017, 23, 13058–13066. (35). Song, Y.; Duan, F.; Zhang, S.; Tian, J.; Zhang, Z.; Wang, Z.; Liu, C.; Xu, W.; Du, M. Iron Oxide@Mesoporous Carbon Architectures Derived from an Fe(ii)-based Metal Organic Framework for Highly Sensitive Oxytetracycline Determination J. Mater. Chem. A 2017, 5, 19378–19389. (36). Li, S.; Zhang, X.; Huang, Y. Zeolitic Imidazolate Framework-8 Derived Nanoporous Carbon as an Effective and Recyclable Absorbent for Removal of Ciprofloxacin Antibiotics from Water J. Hazard. Mater. 2017, 321, 711–719.


30

Page 30 of 34

Page 31 of 34 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(37). Chen, C.; Chen, D.; Xie, S.; Quan, H.; Luo, X.; Guo, L. Absorption Behaviors of Organic Micropollutants on Zirconium Metal-Organic Framework UiO-66: Analysis of Surface Interactions ACS Appl. Mater. Interfaces 2017, 9, 41043–41054. (38). Khoshbin, Z.; Verdian, A.; Housaindokht, M.; Izadyar, M.; Rouhbakhsh, Z. Aptasensors as the Future of Antibiotics Test Kits-a Case Study of the Aptamer Application in the Chloramphenicol Detection Biosens. Bioelectron. 2018, 122, 263–283. (39). Lu, W.; Jiao, Y.; Gao, Y.; Qiao, J.; Mozneb, M.; Shuang, S.; Dong, C.; Li, C. Bright Yellow Fluorescent Carbon Dots as a Multifunctional Sensing Platform for the Label-Free Detection of Fluoroquinolones and Histidine ACS Appl. Mater. Interfaces 2018, 10, 42915–42924. (40). Munawar, A.; Tahir, M.; Shaheen, A.; Lieberzeit, P.; Khan, W.; Bajwa, S. Investigating Nanohybrid Material based on 3D CNTs@Cu Nanoparticle Composite and Imprinted Polymer for Highly Selective Detection of Chloramphenicol J. Hazard. Mater. 2018, 342, 96–106. (41). Zhou, T.; Halder, A.; Sun, Y. Fluorescent Nanosensor based on Molecularly Imprinted Polymers Coated on Graphene Quantum Dots for Fast Detection of Antibiotics Biosensors 2018, 8, 82. (42). Chen, M.; Gan, N.; Zhou, Y.; Li, T.; Xu, Q.; Cao, Y.; Chen, Y. A Novel Aptamer-Metal ions Nanoscale MOF based Electrochemical Biocodes for Multiple Antibiotics Detection and Signal Amplification Sens. Actuators B Chem. 2017, 242, 1201–1209. (43). Liu, H.; Chen, L.; Ding, J. A Core-Shell Magnetic Metal Organic Framework of Type Fe3O4@ZIF-8 for the Extraction of Tetracycline Antibiotics from Water Samples Followed by Ultra-HPLC-MS Analysis. Microchim Acta 2017, 184, 4091–4098. (44). Rosati, G.; Ravarotto, M.; Scaramuzza, M.; Toni, A.; Paccagnella, A. Silver Nanoparticles Inkjet-Printed Flexible Biosensor for Rapid Label-Free Antibiotic Detection in Milk Sens. Actuators B Chem. 2019, 280, 280–289. (45). Nie, J.; Yuan, L.; Jin, K.; Han, X.; Tian, Y.; Zhou, N. Electrochemical Detection of Tobramycin based on Enzymes-Assisted Dual Signal Amplification by Using a Novel Truncated Aptamer with High Affinity Biosens. Bioelectron. 2018, 122, 254–262. (46). Yang, Y.; Jiang, F.; Chen, L.; Pang, J.; Wu, M.; Wan, X.; Pan, J.; Qian, J.; Hong, M. An Unusual Bifunctional Tb-MOF for Highly Sensitive Sensing of Ba2+ Ions and with Remarkable Selectivities for CO2–N2 and CO2–CH4 J. Mater. Chem. A 2015, 3, 13526–13532. (47). Zhou, S.; Gweon, G.; Fedorov, A.; First, P.; de Heer, W.; Lee, D.; Guinea, F.; Castro Neto, A.; Lanzara, A. Substrate-Induced Bandgap Opening in Epitaxial Graphene Nat. Mater., 2007, 6, 770–775. (48). Lee, C.; Yang, W.; Parr, R. Development of the Colle-Salvetti Correlation-Energy Formula into a Functional of the Electron Density Phys. Rev. B 1988, 37, 785–789.


31


(49). Fu, H.; Yan, L.; Wu, N.; Ma, L.; Zang, S. Dual-Emission MOF⊃dye Sensor for Ratiometric Fluorescence Recognition of RDX and Detection of a Broad Class of Nitro-Compounds J. Mater. Chem. A 2018, 6, 9183–9191. (50). Shen, B.; Qian, Y. Building Rhodamine-BODIPY Fluorescent Platform Using Click Reaction: Naked-Eye Visible and Multi-Channel Chemodosimeter for Detection of Fe3+ and Hg2+ Sens. Actuators B Chem. 2018, 260, 666−675. (51). Sorsak, E.; Volmajer Valh, J.; Korent Urek, S.; Lobnik, A. Design and Investigation of Optical Properties of N-(Rhodamine-B)-Lactam-Ethylenediamine (RhB-EDA) Fluorescent Probe Sensors 2018, 18, 1201. (52). Liu, L.; Chen, L.; Liang, J.; Liu, L.; Han, H. A Novel Ratiometric Probe Based on Nitrogen-Doped Carbon Dots and Rhodamine B Isothiocyanate for Detection of Fe3+ in Aqueous Solution J. Anal. Methods Chem. 2016, 2016, 4939582. (53). Borges, A.; Dutra, J.; Freire, R.; Moura Jr, R.; Da Silva, J.; Malta, O.; Araujo, M.; Brita, H. Synthesis and Characterization of the Europium(III) Pentakis(picrate) Complexes with Imidazolium Countercations: Structural and Photoluminescence Study Inorg. Chem. 2012, 51, 12867–12878. (54). Yu, M.; Yao, X.; Wang, X.; Li, Y.; Li, G. White-Light-Emitting Decoding Sensing for Eight Frequently-Used Antibiotics Based on a Lanthanide Metal-Organic Framework Polymers 2019, 11, 99. (55). Cui, Y,; Yue, Y.; Qian, G.; Chem, B. Luminescent Functional Metal-Organic Framework Chem. Rev. 2011, 112, 1126–1162. (56). Zhang, H.; Shan, X.; Zhou, L.; Lin, P.; Li, R.; Ma, E.; G, X.; Du, S. Full-Color Fluorescent Materials Based on Mixed-Lanthanide(III) Metal-Organic Complexes with High-Efficiency White-Light Emission J. Mater. Chem. C 2013, 1, 888–891. (57). Das, S.; Manam, J. Fluorescein Isothiocyanate and Rhodamine B Dye Encapsulated Mesoporous SiO2 for Applications of Blue LED Excited White LED Opt. Mater. 2018, 79, 259–263. (58). Fu, X.; Xie, M.; Luan, P.; Jing, L. Effective Visible-Excited Charge Separation in Silicate-Bridged ZnO/BiVO4 Nanocomposite and Its Contribution to Enhanced Photocatalytic Activity ACS Appl. Mater. Interfaces 2014, 6, 18550–18557. (59). Geissler, D.; Linden, S.; Liermann, K.; Wegner, K.; Charbonniere, L.; Hildebrandt, N. Lanthanides and Quantum Dots as Forster Resonance Energy Transfer Agents for Diagnostics and Cellular Imaging Inorg. Chem. 2014, 53, 1824–1838. (60). Hildebrandt, N.; Wegner, K.; Algar, W. Luminescent Terbium Complexes: Superior Förster Resonance Energy Transfer Donors for Flexible and Sensitive Multiplexed Biosensing Coord. Chem. Rev. 2014, 273–274, 125–138. (61). Xu, J.; Corneillie, T.; Moore, E.; Law, G.; Butlin, N.; Raymond, K. Octadentate Cages of Tb(III) 2-Hydroxyisophthalamides:


32

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A New Standard for Luminescent Lanthanide Lables J. Am. Chem. Soc 2011, 133, 19900–19910. (62). Van Der Meer, B.; Medintz, I.; Hildebrandt, N. FRET-Forster Resonance Energy Transfer. From Theory to Applications Wiley-VCH, Weinheim, Germany, 2013. (63). Rajapakse, H.; Reddy, D.; Mohandessi, S.; Butlin, N.; Miller, L. Luminescent Terbium Protein Labels for Time-Resolved Microscopy and Screening Angew. Chem. Int. Ed. 2009, 48, 4990–4992. (64). Cheng, Y.; Li, L.; Wei, F.; Wong, K. Alkynylplatinum(II) Terpyridine System Coupled with Rhodamine Derivative: Interplay of Aggregation, Deaggregation, and Ring-Opening Processes for Ratiometric Luminescence Sensing Inorg. Chem. 2018, 57, 6439–6446. (65). Tian, L.; Dai, Z.; Liu, X.; Song, B.; Ye, Z.; Yuan, J. Ratiometric Time-Gated Luminescence Probe for Nitric Oxide Based on an Apoferritin-Assembled Lanthanide Complex-Rhodamine Luminescence Resonance Energy Transfer System Anal. Chem. 2015, 87, 10878–10885. (66). Xu, X.; Yan, B. Eu(III)-Fuctionalized ZnO@MOF Heterostructures: Integration of Pre-Concentration and Efficient Charge Transfer for the Fabrication of a ppb-Level Sensing Platform for Volatile Aldehyde Gases in Vehicles J. Mater. Chem. A 2017, 5, 2215–2223. (67). Zhao, D.; Liu, X.; Zhao, Y.; Wang, P.; Liu, Y.; Azam, M.; Al-Resayes, S.; Lu, Y.; Sun, W. Luminescent Cd(ii)-Organic Frameworks with Chelating NH2 Sites for Selective Detection of Fe(iii) and Antibiotics J. Mater. Chem. A 2017, 5, 15797–15807. (68). Pawar, M.; Tayade, K.; Sahoo, S.; Mahulikar, P.; Kuwar, A.; Chaudhari, B. Selective Ciprofloxacin Antibiotic Detection by Fluorescent Siderophore Pyoverdin Biosens. Bioelectron. 2016, 81, 274–279. (69). Wei, X.; Zhou, Z.; Hao, T.; Li, H.; Dai, J.; Gao, L.; Zheng, X.; Wang, J.; Yan, Y. Simple Synthesis of Thioglycolic Acid-Coated CdTe Quantum Dots as Probes for Norfloxacin lactate Detection J. Lumin. 2015, 161, 47–53. (70). Zdunek, J.; Benito-Pena, E.; Linares, A.; Falcimaigne-Cordin, A.; Orellana, G.; Haupt, K.; Moreno-Bondi, M. Surface-Imprinted Nanofilaments for Europium-Amplified Luminescent Detection of Fluoroquinolone Antibiotics Chem. Eur. J. 2013, 19, 10209–10216.


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A RhB@Tb-dcpcpt composite with highly water-stable for sensitive and selective detection toward antibiotics in water 170x85mm (300 x 300 DPI)


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Highly Water-Stable Dye@Ln-MOFs for Sensitive and Selective

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