Literature DB >> 34205199

Highly-Efficient Sulfonated UiO-66(Zr) Optical Fiber for Rapid Detection of Trace Levels of Pb2.

Marziyeh Nazari1,2, Abbas Amini3,4, Nathan T Eden5, Mikel C Duke2, Chun Cheng6, Matthew R Hill5,7.   

Abstract

Lead detection for biological environments, aqueous resources, and medicinal compounds, rely mainly on either utilizing bulky lab equipment such as ICP-OES or ready-made sensors, which are based on colorimetry with some limitations including selectivity and low interference. Remote, rapid and efficient detection of heavy metals in aqueous solutions at ppm and sub-ppm levels have faced significant challenges that requires novel compounds with such ability. Here, a UiO-66(Zr) metal-organic framework (MOF) functionalized with SO3H group (SO3H-UiO-66(Zr)) is deposited on the end-face of an optical fiber to detect lead cations (Pb2+) in water at 25.2, 43.5 and 64.0 ppm levels. The SO3H-UiO-66(Zr) system provides a Fabry-Perot sensor by which the lead ions are detected rapidly (milliseconds) at 25.2 ppm aqueous solution reflecting in the wavelength shifts in interference spectrum. The proposed removal mechanism is based on the adsorption of [Pb(OH2)6]2+ in water on SO3H-UiO-66(Zr) due to a strong affinity between functionalized MOF and lead. This is the first work that advances a multi-purpose optical fiber-coated functional MOF as an on-site remote chemical sensor for rapid detection of lead cations at extremely low concentrations in an aqueous system.

Entities:  

Keywords:  aqueous quality; nano-bio detectors and sensors; nano-bio systems; nanobiotechnology; optical fiber vesicle; sulfonated MOFs

Mesh：

Substances：

Year:  2021        PMID： 34205199      PMCID： PMC8200020          DOI： 10.3390/ijms22116053

Source DB:  PubMed          Journal:  Int J Mol Sci        ISSN： 1422-0067            Impact factor:   5.923


1. Introduction

Lead (Pb) and other small-scale substances (e.g., soot aerosol, ammonia, and arsenic) [1,2] are known as deadly widespread toxic pollutants in the environment at macro- to nano-scale due to recent industrialization and agricultural activities [3,4]. A serious concern has raised for Canadian [5], the U.S. [6], and old European mega-cities [7] with high amounts of lead nano-substances found in drinking water which are originated from old pipes or chemical reactions occurred in corroded plumbing components [8]. According to American Academy of Family Physicians (AAFP), any level of detectable lead in human blood is abnormal [9]. Recurring exposure to low levels of Pb creates serious health issues for infants and children such as slow development and permanent intellectual disability [10,11]. In addition to various sources, lead can be taken up by fishes and other aquatic organisms from water accumulating in humans tissues after consumption [12], and then resulting in neurological [13], hematopoietic [14], musculoskeletal [15], cardiac function [16] and reproductive damages [17,18]. Despite the detrimental properties of lead to living objects, there is yet a significant gap to efficiently and abruptly detect and characterize lead at extremely small levels in bioactive compounds [19,20]. Methodologically, atomic absorption spectroscopy (AAS), atomic emission spectroscopy (AES), X-ray fluorescence (XRF), and inductively coupled plasma-optical emission spectrometry (ICP-OES) are the commonly used laboratory techniques for measuring lead contents in drinking water [21]. To use the above expensive and complicated equipment, water samples should be collected on-site, transported to a laboratory, and tested by trained professionals. This process for a large-scale determination of lead concentration is costly, time-consuming, and effortful. As yet, there are considerable efforts to develop sensors to allow discrete measurements of lead contents at-the-source for home-users. The existing detection mechanisms are based on colorimetry [22,23], biosensing [24], and electrochemical configurations [25], which, in addition to their low detection limits, have many other constraints. For instance, matrix interferences in the colorimetric method either disrupt the reaction between the reagent and the analyte or interfere the spectrometric light measurement [21]. In the biosensing method, more complex biological molecules, e.g., Daphnia magna, are needed with higher selectivity and less interference for reagents [26]. In the electrochemical sensing technique, lead-selective membranes are utilized on electrodes, where the response can be impacted by the interference from other ions presented in the water sample, effecting the solution ionic strength and potential drift [21]. Thus, an accessible, fast, sustainable, and efficient technology can fill this gap to detect Pb in aqueous resources at low ppm and ppb levels [27]. So far, there are increasing interests in recent years to take advantage of advanced materials to adsorb Pb nanoparticles at deficit concentrations from aqueous resources [28,29,30,31,32,33]. Metal-organic frameworks (MOFs) are highly porous 3D-materials made of metal ions linked with organic ligands. The size and shape of pores are affected by the coordination geometry of metals (e.g., tetrahedral, octahedral) that dictates the number of bounded ligands. Proper selection of metal ions and ligands can yield crystals with ultrahigh porosity as well as high thermal and chemical stability. Among MOFs, UiO-66(Zr) or ZrO(OH) has a stable crystalline structure in water, introducing it as a promising candidate for sensing the aqueous contaminants and purification purposes [34]. Our recent studies have shown the favorable capability of UiO-66 for removing rhodamine-B [35], methyl viologen [36], and 4-aminopyridine [37] from water contents. The functionalization of UiO-66(Zr) with proper chemical groups is suggested to enhance its low affinity with Pb ions. In this work, a new setup is introduced via functionalization of UiO-66(Zr) with SOH to capture Pb at low ppm levels in aqueous environments. Due to the strong coordination of Pb with SO group, a small quantity of lead (<0.5 ppm) was left in the solution. To create a remote sensing setup for rapid detection within the range of a few milliseconds, the functionalized MOF was coated at the end-face of an optical fiber (single-mode fiber, SMF-28) and used as an in-fiber Fabry–Perot interferometer (FPI) [38]. The changes to the MOF optical properties due to adsorption of Pb were detected via wavelength shifts in the interference spectrum.

2. Methods

SOH-UiO-66(Zr) sensing element was synthesized through a growth solution proposed by Okoro et al. [24] with some modifications. Briefly, ZrCl (1.93 g, 8.3 mmol) and monosodium 2-sulfoterephthalate (NaSO-BDC, 2.2 g, 8.2 mmol) were dissolved under stirring with N,N-dimethylformamide (DMF, 100 mL) and concentrated HCl (37%, 1.3 mL). Then, glacial acetic acid (100%, 16.6 mL; 35 equiv.) was added as a modulator. The mixture was continuously stirred for 2 h and left for 24 h at 120 °C in a pre-heated oven. After naturally cooling down to room temperature, the SOH-UiO-66(Zr) nanoparticles were centrifuged at 20,000 rpm for 10 min and washed with fresh DMF (at least three times), then with pure methanol (at least three times), and kept under constant stirring with dichloromethane (DCM) overnight. They were dried for 5 h at 60 °C under reduced pressure. The SMF-28 optical fiber was made of molten silica glass heated up to 2200 °C and drawn into tubes with varied diameters. In this work, fibers with a cladding diameter of 125 ± 0.7 m and a core diameter of 8.2 m were utilized. Before coating, the optical fiber made of SiO glass was treated with hydroxyl (OH) functional groups. A piranha solution was prepared from a 3:1 mixture of sulfuric acid (98%) and hydrogen peroxide (30%), into which optical fibers were cleaved at a right angle and incubated for 30 min. To grow the MOF sensing element on the exposed surface of the optical fibers, the OH-functionalized optical fibers were placed in an untreated precursor solution of SOH-UiO-66(Zr), heated at 120 °C for 24 h. After this procedure, the fibers were gently washed with DMF, methanol and DCM, to remove unreacted reagents. Fabry–Perot interferometry (FPI) was used as the optical detection method. When the light is propagated down to the core of fiber, it interacts with the sensing element. The element is in contact with lead-contaminated water, and by capturing the Pb, its optical thickness and refractive index change. The reflected light sends this information to the detector, where a custom-written software (MATLAB [39]) processes it [35,36,37]. The resultant FPI spectrum (interferograms) is obtained in correlation with the lead concentration in distilled (DI) water. To test the lead uptake capacity of as-synthesized MOF, different amounts of SOH-UiO-66(Zr) (10, 15, 20 and 25 mg) were separately added to 5 mL diluted solution with 25.2 (0.12 mM), 43.5 (0.21 mM) and 64.0 (0.31 mM) ppm lead under constant stirring for 10, 30 and 60 min (impregnation). Before taking a sample (aliquot) from the middle of the vial, the solid was separated by centrifuging at 20,000 rpm for 5 min, then resting for 4 h at room temperature. The adsorption mechanism of Pb onto SOH-UiO-66(Zr) was characterized by X-ray diffraction (XRD), N gas porosimetry, and Fourier-transform infrared spectroscopy (FT-IR) methods (Appendix A).

3. Results and Discussion

3.1. Pb Uptake by SOH-UiO-66(Zr) Powder

Figure 1a displays the XRD pattern of SOH-UiO-66(Zr) and SOPb-UiO-66(Zr) powder. A change in the XRD pattern of the amorphous SOH-UiO-66(Zr) sample occurrs by appearing the additional peaks in the SOPb-UiO-66(Zr) sample (prescribed to PbSO post-adsorption through peak matching in crystallographic database (Figure A1)). This suggests the formation of a material that matches with the crystallographic geometry of PbSO. The cleavage energy of the sulfonate group is prohibitively high under the adsorption conditions (pH = 5.6, room temperature/pressure, and in aqueous environment), and Pb(NO) is soluble in water with different crystallographic geometries. The pH was achieved by atmospheric carbon dioxide dissolving into the DI water as a natural process. To avoid addition of interferent compounds to the water/Pb context, the pH was not regulated. Therefore, we conclude that Pb cation is absorbed onto the sulfonate groups of SOH-UiO-66(Zr) structure where the tetrahedral R-SO of the 2-sulfoterephthalate linker replaces the tetrahedral SO of PbSO.
Figure 1

(a) XRD curves, (b) Pore size distribution, (c) N adsorption/desorption isotherms, and (d) FT-IR spectra of SOH-UiO-66(Zr) and SOPb-UiO-66(Zr) powder.

Figure A1

Diffractogram pattern of SOPb-UiO-66(Zr) at 2 region (5°–65°), superimposed over the simulated diffractograms of UiO-66 and PbSO anglesite.

Standard N gas porosimetry measurements confirm the uptake of lead within SOH-UiO-66(Zr), where the Brunauer-Emmett-Teller (BET) surface area decreases from 491 m/g to 12 m/g upon the lead uptake. Figure 1b shows the pore size distribution of SOH-UiO-66(Zr) before/after the lead uptake; this is associated with the additional mass of Pb incorporated into the compound as well as the reduction of internal pore volume. The adsorption/desorption isotherms of SOH-UiO-66(Zr) before/after the lead uptake are shown in Figure 1c. Upon the uptake of Pb, significant changes in the observed transmittance reflect the change of dipole moment due to the adsorbed Pb. Unchanged peak positions associated with the UiO-66(Zr) framework indicate that the structure does not undergo significant changes while the crystallinity increases (Figure 1d). For instance, the characteristic S=O stretching at 1375 cm and 1167 cm become weaker in the SOPb-UiO-66(Zr) sample, while C−H stretching peak at 1251 cm has a very low intensity. Defects in SOH-UiO-66(Zr) reduces the density of functional groups that interact with the laser. The reduced transmittance is seen in the figure in the gesture of smaller peaks.

3.2. Pb Uptake of SOH-UiO-66(Zr) Powder

Inductively coupled plasma-optical emission spectrometry (ICP-OES) was conducted to determine the trace level of lead in the aliquots after its impregnation. By nonlinear regression modelling, the equilibrium/optimized level of lead uptake capacity of as-synthesized MOF was determined as 33.7 mg with a maximum 94% uptake (r-squared fit of 99.7%). Langmuir and Freundlich models are used to investigate the adsorbent/adsorbate interaction in MOFs. Langmuir isotherm assumes that in the uptake process, the adsorbent places itself as a monolayer on the surface of the material. This model can be linearly expressed in the form of Equation (1): where C is the equilibrium solution concentration (mg/L or ppm), is the amount of Pb at the equilibrium (mg/g), is the Langmuir adsorption constant related to the energy of adsorption, and is the maximum adsorption capacity of the MOF (mg/g). A plot of / (y-axis) vs. (x-axis) allows the calculation of and parameters (Figure 2a). Another model, empirical Freundlich isotherm, assumes that the distribution of active sites in the MOF is homogeneous and is linearly expressed in the form of Equation (2): here, is the equilibrium solution concentration (mg/L or ppm), is the amount of Pb at the equilibrium (mg/g), is the Freundlich adsorption constant, and n is an empirical value. A plot of (y-axis) vs. (x-axis) determines the magnitudes of and n (Figure 2b).
Figure 2

Adsorption isotherms fitted by linearized form of (a) Langmuir and (b) Freundlich model for adsorbed Pb by SOH-UiO-66(Zr)。

Regression analysis of the data, the average values of K, K, q and n are shown in Table 1. In this study, the Freundlich model shows a better predictor than the Langmuir model with slightly higher R, suggesting that the uptake of lead cations occurrs mainly and homogeneously throughout the entire of MOF framework. Moreover, the calculated average n value for the adsorption of Pb is 1.66, showing a good efficiency of SOPb-UiO-66(Zr) for the lead adsorption [40,41].
Table 1

Langmuir and Freundlich isotherm constants for the uptake of lead (II) cation at room temperature.

Langmuir ConstantsFreundlich Constants
qm (mg/g) KL (mg/L) R 2 Kf n R 2
32.776.070.955.511.660.99
To determine whether a high degree of crystallinity affected the lead uptake, the untreated precursor solution of SOH-UiO-66(Zr) was heated at 120 °C for 48 h (rather 24 h); a highly crystallized as-synthesized MOF was achieved. As seen in the XRD patterns (Figure A2b), more defined Bragg peaks were observed for the MOF heated for 48 h in comparison to the one heated for 24 h. Based on the ICP-OES results, 10 mg of this highly formed MOF led to <0.5 ppm (2.4 M) left-over lead in the initial 25.2 ppm-solution (99.99% uptake) for all impregnation ranges (10, 30 and 60 min). In contrast, non-functionalized UiO-66(Zr) MOF reduced the lead content from 25.2 ppm to 23.1 ppm after 60 min constant stirring.
Figure A2

(a) N adsorption/desorption isotherms and (b) XRD curves of SOH-UiO-66(Zr) [24 h] and SOH-UiO-66(Zr) [48 h] powder.

3.3. Optical Fiber Sensing

After successfully validating the impregnation of lead within SOH-UiO-66(Zr), the coated element at the tip of optical fiber was utilized as a chemical sensor for the rapid (a few milliseconds) detection of lead in DI water. Figure 3a illustrates the SEM image of a deposited sensing element of sulfonated SOH-UiO-66(Zr) at the tip of optical fiber adjacent to a bare optical fiber in Figure 3b. The interference of two reflected beams was recorded using an optical spectrum analyzer (OSA, Ando Japan, AQ6317B, 600–1750 nm). An Agilent 83438A Erbium ASE (Agilent Technologies, Santa Rosa, CA, USA) was used as the light source with the wavelength range of 1500–1600 nm. The OSA was set on a continuous scan mode to record the interference signals every 5 s with a high sensitivity and 0.1 nm resolution.
Figure 3

SEM images of (a) SOH-UiO-66(Zr) optical fiber sensing element, and (b) bare optical fiber, (c) Interferograms in correlation with a lead concentration in DI water, and (d) EDX spectra of SOH-UiO-66(Zr) optical fiber sensing element after the lead uptake.

The average of all signals (100 trials) for each concentration was used as the final interference signal for a specific concentration. The fast response of the sensing element towards lead uptake was withdrawn by comparing the shape of signals at different sweeps. Figure 3c shows the spectral positions of the interferogram peak (normalized denoised interference intensity vs. wavelength) generated by SOH-UiO-66(Zr) sensing element at different lead concentrations. Briefly, the sensor was first placed in DI water for 5 min to observe the pattern of sensing element upon the exposure to DI water. The same procedure was repeated after immersing the sensor in different lead solutions (“water 2” and “water 3” with 25.2 ppm and 43.5 ppm lead contents, respectively). Upon the introduction of lead nitrate solutions, the position of interferogram peak shifted to longer wavelengths. This indicated an increase in the lead adsorption by SOH-UiO-66(Zr) sensing element and, thus, the optical thickness. Energy-Dispersive X-ray (EDX) analysis was performed on the optical fiber sensing element after the lead uptake process, in order to confirm the attachment of lead with SOH-UiO-66(Zr). As shown in Figure 3d, despite some detection difficulty due to the similarity of the energy of S-K and Pb-M (2.309 vs. 2.342 keV, respectively), zirconium (Zr) (as the main constituent of Zr-based MOF SOH-UiO-66) had 21.3% weight while Pb possessed 9.6% level in the samples with higher ppm. The presence of sulfur (S) confirmed the SOH-UiO-66(Zr) structure. As the reference for lead level in drinking water is 5 µg/L (5 ppb) [42], precision evaluation studies should be conducted to further overcome the detection limit. Nevertheless, optical fibers and SOH-UiO-66(Zr) are stable within the range of pH 2–9 [43,44]. Yet, the remaining challenge is to consider the sensor in very harsh environments for prolonged periods of time where the wastewater might be extremely acidic or basic. Although the optical fiber sensors were not designed explicitly for this purpose, there is an opportunity to trigger the release of the guest species (Pb) using light at a specific wavelength [45]. The pH change [46], ligand exchange [47], and ethanol regeneration solvent [48] have been proposed to recycle MOFs for further usages.

3.4. Mechanism of Pb Adsorption

Figure 4 shows the chemistry mechanism where the sensing material coordinates with Pb ions via n sulfonate groups, n≤ 6.
Figure 4

Diagram of adsorption of [Pb(OH)] on SOH-UiO-66(Zr) in water

As per our data, Pb adsorption occurrs in a S-O-Pb bonding manner. There are 10 lone pairs of electrons present in the oxygens of sulfonic acid group, where the tetrahedral R-SO geometry would prohibit the direct S-Pb bonding. In fact, the presence of a crystalline phase identical to Pb(SO) is due to the coordination of Pb to SO group with the O-carbon of 2-sulfonoterepthalic acid replacing one O in Pb(SO). The rapid uptake of Pb, shown from both the batch adsorption measurements and the optical fiber results, leads to both weak coordination and strong electrostatic attraction between Pb and R-O. The speciation of Pb(NO) in aqueous solutions at the native pH of ∼5 is mainly Pb, that exists within a solvation shell of approximately 6 HO molecules. The adsorptions would, therefore, have the following predominant reactions [49]: Equation (3) demonstrates an electrostatic attraction to a singular sulfonate O, while Equation (4) presents the coordination between the delocalized sulfonate e and Pb. These are shown as a three-step process. The immersion of the MOF into water dissociates the sulfonic acid H rapidly, after which lead is attracted to the sulfonate groups of SOH-UiO-66(Zr). Due to the rapid uptake, it is not expected that Pb(O.H.) is adsorbed onto the sulfonates, as its fractional abundance at pH 5–6 is low relative to the adsorption phenomenon [50].

4. Conclusions

The rapid detection of Pb by MOF-coated optical fibers was introduced for the first time. A solvothermal synthesized sulfonic acid functionalized MOF, SOH-UiO-66(Zr), demonstrated the rapid uptake of lead from Pb(NO) solution. The analysis of ICP-OES intensities showed the uptake capacity of SOH-UiO-66(Zr) as 32.77 mg/g (R = 0.997). This MOF was grown on an OH-functionalized SMF-28 conventional single-mode optical fiber that acted as a detector for Pb at the ppm-level concentrations. Spectral interferograms indicated the detection of Pb down to 25.2 ppm. Such a MOF optical fiber can be implemented as a device for simple/abrupt on-site detection of aqueous Pb or possibly other ions at ppm or sub-ppm levels. We envisage that this type of sensor would offer a novel and more effective composite to harvest heavy metals from contaminated water for clean water supply. Further studies are currently undergoing to investigate the interference effects of a matrix containing more than one cation and anion in water, as other transition metal (II) ions may give a ’false’ Pb detection reading.
Table A1

Phase summary of SOH-UiO-66(Zr).

Lattice ParameterCrystallite SizePhase
24 h NP (amorphous)NP (amorphous)UiO-66, except the (0 2 2) peak at ∼12° 2θ
48 h 20.678 ± 0.001 Å170 ± 11 nmUiO-66, except the (0 2 2) peak at ∼12° 2θ
Table A2

Normalized denoised interference intensity (NDII).

WavelengthNDIINDIINDIINDIINDIINDII
nm mW mW mW mW mW mW
DI Water 25.2 ppm Water 2 43.5 ppm Water 3 64.0 ppm
1524.90.517530.498440.479350.477010.459390.49888
1525.020.509410.495440.481470.473170.462540.49268
1525.140.504860.491110.477360.470440.458530.49062
1525.260.513750.495040.476330.472430.461960.49004
1525.380.517850.497330.476810.473220.462540.49151
1525.50.522340.501840.481340.478850.47030.49534
1525.6190.527470.503580.479690.476260.464830.49888
1525.7390.523650.501360.479070.472430.465120.49652
1525.8590.518430.500330.482230.477310.46540.49681
1525.9790.522160.502710.483260.475070.466550.49859
1526.0990.513760.50120.488640.483260.469430.49947
1526.2190.52330.506520.489740.48140.47030.50036
1526.3390.525290.504930.484570.48140.467990.49918
1526.4580.528520.509860.49120.482560.470010.50273
1526.5780.523890.506680.489470.479550.468280.50066
1526.6980.52530.509460.493620.486820.469430.50333
1526.8180.529450.512890.496330.484660.473470.50749
1526.9380.529490.512250.495010.485810.473760.506
1527.0580.532340.513290.494240.486670.47550.50541
1527.1780.533250.514650.496050.486570.47550.506
1527.2980.538730.519370.500010.492410.478980.51137
1527.4180.541710.521940.502170.493060.482180.51316
1527.5370.536980.519370.501760.493160.482760.51047
1527.6570.542210.522260.502310.494630.482470.51257
1527.7770.54670.524680.502660.494120.482180.51346
1527.8970.546720.526370.506020.498380.483340.51436
1528.0170.544670.526850.509030.498830.486840.51766
1528.1370.541230.523870.506510.497670.483630.51406
1528.2570.54410.524920.505740.497260.481880.51496
1528.3770.544420.526690.508960.497410.483920.51466
1528.4960.546980.530570.514160.504370.486840.51856
1528.6160.549760.531780.51380.503350.488890.52006
1528.7360.551040.531370.51170.50310.486840.51856
1528.8560.549440.531130.512820.504520.487720.52036
1528.9760.550470.532350.514230.5030.488010.52006
1529.2160.558520.538840.519160.509620.494750.527
1529.3360.5550.536480.517960.508040.491820.52338
1529.4560.56080.54030.51980.510240.493870.52579
1529.5750.56630.544710.523120.512340.496810.52942
1529.6950.566680.544050.521420.512750.495050.5273
1529.8150.567860.54560.523340.513570.498880.53003
1529.9350.562460.542260.522060.512850.495930.52821
1530.0550.559920.541770.523620.511110.495930.5264
1530.1750.566070.546830.527590.516130.500940.52851
1530.2950.564290.54740.530510.518860.501530.53063
1530.4150.568960.54970.530440.518190.50360.53154
1530.5340.565630.547570.529510.518750.500940.53033
1529.0960.553310.534050.514790.505750.491230.52277
1530.6540.568910.549780.530650.518390.502720.53185
1530.7740.56860.550840.533080.520560.50420.53215
1530.8940.574010.554290.534570.524320.505380.53549
1531.0140.576610.55470.532790.523290.505090.53549
1531.1340.570670.552730.534790.522470.505680.53428
1531.2540.575970.55520.534430.522210.506860.5361
1531.3740.580320.558660.5370.524430.507460.5361
1531.4940.577780.55750.537220.525930.507460.53702
1531.6130.580550.560640.540730.527840.510730.53885
1531.7330.577080.558080.539080.525820.508350.53732
1531.8530.581310.561130.540950.52650.510430.53732
1531.9730.579060.560720.542380.529090.511320.53915
1532.0930.583060.564770.546480.533560.514310.54129
1532.2130.585730.568090.550450.536160.518490.54435
1532.3330.580180.564770.549360.535120.516990.54129
1532.4530.582710.565350.547990.533970.51640.54098
1532.5720.589620.570.550380.536790.519690.54496
1532.6920.58820.571750.55530.541960.522390.54619
1532.8120.593010.575750.558490.544680.52570.55141
1532.9320.589860.5720.554140.540760.520890.5465
1533.0520.59020.571410.552620.539290.522390.54588
1533.1720.593370.575750.558130.543110.52570.5468
1533.2920.594980.576080.557180.544740.524490.5468
1533.4120.595030.576580.558130.543640.52630.54926
1533.5310.59450.575660.556820.542380.523590.54742
1533.6510.592420.574330.556240.542690.522990.54496
1533.7710.596480.579010.561540.547360.529010.54711
1533.8910.596990.579340.561690.54820.528710.54803
1534.0110.599120.583030.566940.551420.532040.55111
1534.1310.600680.582860.565040.551790.532040.54895
1534.2510.599380.582610.565840.5530.533550.5508
1534.3710.603380.586220.569060.556280.535980.55234
1534.490.6040.586970.569940.555530.535980.55234
1534.610.606760.589670.572580.558080.539620.5545
1534.730.606370.58790.569430.558660.536890.55326
1534.850.607730.587480.567230.556010.537190.55203
1534.970.605910.588070.570230.557490.537190.55234
1535.090.609280.590340.57140.557390.538410.55265
1535.210.612460.592960.573460.559980.541450.55419
1535.330.613540.591190.568840.558450.537190.55111
1535.450.610250.588740.567230.555750.536890.54772
1535.5690.612550.591610.570670.557920.539320.54895
1535.6890.617920.596680.575440.563760.543280.55357
1535.8090.617680.598290.57890.566470.547560.5579
1535.9290.614270.595410.576550.564290.54420.55296
1536.0490.615920.596930.577940.563860.546030.55357
1536.1690.620220.600150.580080.56930.547860.55419
1536.2890.619620.601770.583920.572560.552470.5579
1536.4090.619450.602020.584590.572670.553390.55914
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1570.3350.985840.988170.99050.994760.993040.98444
1570.4550.987410.990850.994290.995810.997540.98975
1570.5740.986620.989890.993160.996090.996310.9877
1570.6940.987880.990850.993820.99720.997130.99097
1570.8140.986690.989780.992870.99860.997950.99302
1570.9340.990660.990960.991260.996090.996720.99261
1571.0540.984010.988060.992110.997970.999590.99466
1571.1740.981350.986350.991350.996310.99548
1571.2940.983140.987960.992780.993160.999590.99589
1571.4140.988060.989140.990220.994480.999180.99753
1571.5330.979410.982070.984730.989330.997130.99261
1571.6530.978320.982280.986240.991280.999590.99425
1571.7730.977410.981540.985670.991770.999590.99507
1571.8930.973340.979080.984820.990930.998360.99753
1572.0130.970690.977380.984070.989960.997540.99548
1572.1330.972260.976420.980580.987450.997130.99384
1572.2530.971580.976740.98190.989330.998360.99794
1572.3730.971910.976950.981990.990240.997950.99753
1572.4930.972580.977380.982180.992040.999180.99959
1572.6120.964650.970780.976910.985230.996310.99836
1572.7320.965420.972480.979540.98690.997951
1572.8520.962620.968870.975120.987520.997540.99877
1572.9720.960640.96760.974560.984890.996310.99794
1573.0920.956020.964630.973240.984750.994260.99877
1573.2120.953670.961770.969870.981080.990590.99794
1573.3320.952020.959350.966680.977830.990180.9963
1573.4520.94680.95660.96640.974790.988960.99589
1573.5710.945770.955340.964910.976650.9910.9963
1573.6910.950320.957660.9650.97720.993450.9963
1573.8110.950380.957550.964720.976240.992220.99753
1573.9310.940290.950920.961550.9730.987330.99548
1574.0510.936840.94840.959960.970170.988140.99179
1574.1710.940190.95040.960610.974030.989360.99589
1574.2910.937870.949660.961450.971760.988960.99548
1574.4110.940570.95050.960430.9750.990181
1574.5310.932970.944420.955870.969690.988550.99794
1574.650.932650.942120.951590.966390.982850.99179
1574.770.932950.943060.953170.968870.98610.99753
1574.890.929620.941070.952520.967770.98610.99712
1575.010.92440.938460.952520.967080.984880.9963
1575.130.925080.936070.947060.961120.983260.99425
1575.250.914930.92910.943270.955440.975550.98689
1575.370.916530.928790.941050.955650.977570.98689
1575.490.909740.924430.939120.952720.975150.98444
1575.6090.91040.922780.935160.951420.977170.98648
1575.7290.905840.919260.932680.94660.97070.98118
1575.8490.906250.918640.931030.9470.968280.98281
1575.9690.899110.91360.928090.943550.969090.98077
1576.0890.893480.909690.92590.944090.968680.97833
1576.2090.891420.908660.92590.938670.968680.97955
1576.3290.895930.908770.921610.941310.965860.97833
1576.4490.891890.906610.921330.937660.962250.97996
1576.5680.880460.898530.91660.931520.957430.97428
1576.6880.878870.896190.913510.933070.957830.97387
1576.8080.8780.893440.908880.925810.953430.97144
1576.9280.877220.893230.909240.92930.954230.97104
1577.0480.875590.890290.904990.925540.953030.97144
1577.1680.861780.879960.898140.919650.946250.9674
1577.2880.864260.878950.893640.914310.944270.96337
1577.4080.855090.875220.895350.911450.943470.96055
1577.5270.859920.878040.896160.915240.945460.96296
1577.6470.849690.870590.891490.910520.939110.95814
1577.7670.842040.862780.883520.90540.93080.95292
1577.8870.83720.859380.881560.901360.930410.94892
1578.0070.835830.857490.879150.898320.928830.94733
1578.1270.837870.858380.878890.899710.929620.95052
1578.2470.839120.855890.872660.898060.926080.94613
1578.3670.830330.850520.870710.893050.925290.94493
1578.4870.825360.845470.865580.888180.917840.93936
1578.6060.824650.843880.863110.887920.917840.93976
1578.7260.818450.840030.861610.88490.914320.93737
1578.8460.815830.838060.860290.883920.915490.93737
1578.9660.814430.83560.856770.876730.911980.93381
1579.0860.808730.827840.846950.871460.905750.92788
1579.2060.804860.824510.844160.866850.90070.92315
1579.3260.801340.822660.843980.867760.899150.92354
1579.4460.798020.821090.844160.865230.898770.92118
1579.5650.785030.81020.835370.858570.893740.91608
1579.6850.784220.806330.828440.853420.890270.91255
1579.8050.782720.805360.8280.852780.88720.91099
1579.9250.777120.800920.824720.849630.884130.90592
1580.0450.774610.797640.820670.846040.880290.90202
1580.1650.770840.794380.817920.845020.877620.90241
1580.2850.767610.789680.811750.839840.876470.89931
1580.4050.755760.781360.806960.832970.869230.89272
1580.5250.758660.780890.803120.827890.866190.88847
1580.6440.750280.776320.802360.827450.864290.88847
1580.7640.747050.7730.798950.82460.86240.88539
1580.8840.743280.769210.795140.821130.860510.88308
1581.0040.743830.765340.786850.816150.85070.87656
1581.1240.733450.757710.781970.809940.84770.86702
1581.2440.727560.754050.780540.807370.842450.86588
1581.3640.729690.755830.781970.807120.844330.86778
1581.4840.718350.745550.772750.79870.837230.86094
1581.6030.715620.740430.765240.794670.832390.85602
1581.7230.711430.737460.763490.791380.827930.84885
1581.8430.709270.732730.756190.785260.825710.84584
1581.9630.70580.731160.756520.786310.826080.84546
1582.0830.697310.724890.752470.781260.821640.84208
1582.2030.696550.722410.748270.779530.81980.84096
1582.3230.686910.714340.741770.772660.811340.83348
1582.4430.690470.715710.740950.769610.81060.83199
1582.5620.684050.710780.737510.766490.806210.82901
1582.6820.687870.711140.734410.765330.805110.82641
1582.8020.677070.704310.731550.758040.798180.81863
1582.9220.680580.703950.727320.756160.797820.81494
1583.0420.666950.695430.723910.752470.793460.80942
1583.1620.665290.693180.721070.749150.79020.80722
1583.2820.659030.689930.720830.74740.79020.80649
1583.4020.653190.683820.714450.743970.787670.80282
1583.5210.65240.681490.710580.740730.782620.80026
1583.6410.647820.675950.704080.734560.775790.79625
1583.7610.643090.671230.699370.728780.773990.7908
1583.8810.635880.665550.695220.723370.767560.78319
1584.0010.633810.661650.689490.719750.763990.7803
1584.1210.627730.656710.685690.715680.761860.77814
1584.2410.618530.648360.678190.710370.75370.76916
1584.3610.609920.641540.673160.704390.747350.76415
1584.480.602540.633620.66470.695970.739620.75845
1584.60.60220.631890.661580.694220.736820.75596
1584.720.594310.625920.657530.690390.733330.75135
1584.840.593870.623760.653650.687490.728450.74711
1584.960.588450.617650.646850.68090.725330.73972
1585.080.577250.609430.641610.67290.717710.73445
1585.20.576350.606870.637390.672330.716680.72921
1585.320.569720.603210.63670.669350.714610.72851
1585.440.563210.598880.634550.665970.712880.72607
1585.5590.558660.592370.626080.658110.705330.71913
1585.6790.551650.586130.620610.651820.699520.71255
1585.7990.548010.579510.611010.646680.694410.70636
1585.9190.546680.578170.609660.643920.693390.70567
1586.0390.539690.573660.607630.64330.692370.70361
1586.1590.534130.566680.599230.63260.683240.69642
1586.2790.527380.559320.591260.626410.67550.68791
1586.3990.522110.55150.580890.618090.66780.6781
1586.5180.519730.550680.581630.619750.66780.67911
1586.6380.509320.545030.580740.617490.665130.67844
1586.7580.508630.541850.575070.609990.658810.67339
1586.8780.498810.532910.567010.603410.651860.66401
1586.9980.497030.529760.562490.597890.649220.65901
1587.1180.49390.526450.5590.596590.643630.65735
1587.2380.489470.522420.555370.591690.63970.65138
1587.3580.484670.518970.553270.589960.640350.65138
1587.4780.477550.514250.550950.585580.636760.64675
1587.5970.477580.511130.544680.580670.631860.64312
1587.7170.472390.504770.537150.575290.626020.63557
1587.8370.470510.50390.537290.57320.623420.63427
1587.9570.472510.503580.534650.572080.622130.631
1588.0770.464620.496070.527520.566470.615680.62709
1588.1970.459140.489220.51930.559140.608940.62059
1588.3170.450840.481480.512120.549050.600950.61381
1588.4370.451410.480150.508890.547840.598090.60995
1588.5560.445470.475640.505810.543530.595870.60834
1588.6760.434710.467120.499530.539340.587640.5997
1588.7960.42730.458420.489540.53090.579780.59269
1588.9160.420470.452450.484430.524070.57290.58478
1589.0360.416250.447730.479210.519270.568850.57974
1589.1560.412910.44370.474490.513770.564190.5766
1589.2760.41090.440750.47060.511160.559860.57096
1589.3960.402960.433650.464340.502690.5540.56721
1589.5160.395740.427570.45940.498430.54940.56069
1589.6350.392270.421960.451650.488830.543890.55357
1589.7550.383840.41630.448760.489130.539930.55111
1589.8750.383510.412960.442410.481850.535670.54558
1589.9950.381480.410150.438820.478260.530520.54435
1590.1150.376010.40330.430590.471680.52510.53946
1590.2350.367260.394580.42190.463220.51640.53154
1590.3550.365010.39260.420190.460610.51520.52821
1590.4740.362990.38940.415810.45540.509840.52368
1590.5940.357320.386790.416260.456180.509240.52247
1590.7140.349830.38070.411570.450020.502420.51646
1590.8340.340060.371560.403060.443050.493290.50809
1590.9540.333740.364980.396220.435640.486550.50066
1591.0740.332530.363060.393590.431640.483630.49357
1591.1940.332180.361280.390380.430680.481880.49475
1591.3140.331360.359720.388080.427420.476950.49062
1591.4340.318750.350450.382150.418860.472890.48417
1591.5530.314710.343140.371570.410030.461960.47427
1591.6730.311830.340060.368290.409510.459670.47166
1591.7930.308520.336710.36490.404930.455960.46674
1591.9130.304910.333370.361830.399440.45340.4653
1592.0330.299430.327820.356210.393590.444890.46041
1592.1530.291430.318860.346290.384290.43870.4544
1592.2730.293930.317490.341050.37990.434490.44927
1592.3930.291090.315850.340610.382860.434210.4487
1592.5120.29360.317970.342340.380040.432810.44728
1592.6320.289310.313520.337730.377270.427230.44331
1592.7520.283690.307040.330390.369930.423610.43597
1592.8720.272340.298840.325340.363130.414760.42783
1592.9920.27320.298510.323820.361090.412830.42449
1593.1120.268260.296010.323760.360040.410910.42142
1593.2320.268650.29460.320550.356010.407340.42059
1593.3520.261160.288020.314880.351410.401330.41504
1593.4720.252450.278630.304810.342920.393460.40842
1593.5910.245610.273930.302250.337170.388870.40294
1593.7110.249930.273270.296610.334060.383760.3972
1593.8310.246020.269510.2930.329050.379740.39529
1593.9510.236590.261440.286290.32170.370680.38959
1594.0710.234070.254920.275770.31360.3630.37962
1594.1910.224270.246830.269390.30470.355380.37213
1594.3110.223830.24580.267770.298490.35120.3692
1594.4310.217260.239430.26160.298880.344440.36442
1594.550.214330.234130.253930.290860.340550.35781
1594.670.210650.229930.249210.286430.336430.35334
1594.790.202360.222580.24280.28010.325660.34472
1594.910.200050.218920.237790.275590.323110.34134
1595.030.192010.214280.236550.274490.318040.33693
1595.150.186870.211150.235430.269660.315510.33409
1595.270.186410.208150.229890.264770.309460.32869
1595.390.177140.199840.222540.257450.305190.32433
1595.510.170030.193740.217450.251420.297460.31643
1595.6290.167370.189630.211890.245340.293740.3091
1595.7490.170250.189810.209370.243370.289290.30733
1595.8690.164650.185590.206530.239450.287570.30557
1595.9890.157770.179750.201730.234210.279710.30181
1596.1090.159170.177330.195490.228140.273620.29556
1596.2290.152050.170750.189450.223280.267080.28737
1596.3490.14830.167990.187680.220510.26490.28416
1596.4690.151420.170090.188760.219710.265150.2817
1596.5880.147250.165590.183930.214530.259610.27851
1596.7080.13980.158560.177320.209680.252210.27167
1596.8280.136350.153870.171390.203130.246030.2656
1596.9480.130610.150680.170750.201910.244610.26245
1597.0680.130240.149680.169120.200220.243910.26149
1597.1880.133610.150150.166690.199910.240370.25836
1597.3080.121010.143220.165430.193960.234970.25523
1597.4280.1230.140290.157580.189680.231230.24854
1597.5470.111680.133250.154820.182750.225880.24118
1597.6670.113530.131690.149850.178210.221010.23858
1597.7870.109590.127990.146390.176060.218020.23434
1597.9070.112960.127590.142220.170980.215260.22989
1598.0270.108720.125110.14150.167670.209080.22779
1598.1470.103070.118350.133630.160960.204520.22057
1598.2670.097680.11390.130120.153180.197960.21387
1598.3870.095880.112420.128960.154350.196150.21526
1598.5060.09780.114470.131140.154870.196380.21364
1598.6260.098740.114180.129620.154310.193680.21203
1598.7460.090540.107270.1240.144130.185850.20243
1598.8660.090310.103490.116670.141420.178960.19698
1598.9860.086170.101070.115970.142090.177860.19291
1599.1060.084950.102140.119330.14120.175430.19359
1599.2260.084230.09990.115570.139170.173230.19133
1599.3460.081950.096590.111230.1360.170810.18729
1599.4660.076590.091630.106670.126820.162080.18237
1599.5850.070360.086980.10360.123510.160990.17726
1599.7050.073070.086980.100890.121510.156010.1746
1599.8250.074670.088640.102610.121870.157740.17526
1599.9450.074560.08620.097840.118940.152130.17018
1600.0650.066580.080910.095240.113760.150620.16535
1600.1850.061770.076090.090410.105990.142930.16011
1600.3050.065210.075650.086090.105030.137620.15924
1600.4250.068030.07910.090170.10760.137410.1575
1600.5440.065210.077130.089050.106920.136980.1575
1600.6640.06210.074120.086140.102650.131920.15533
1600.7840.067970.071390.074810.092940.125630.14712
1600.9040.05950.068570.077640.092660.123540.14326
1601.0240.053650.063970.074290.090030.121460.13559
1601.1440.062750.067970.073190.091820.121250.13963
1601.2640.055720.064070.072420.089960.118760.13517
1601.3840.050360.057350.064340.081070.11050.12609
1601.5040.039070.050780.062490.076680.104150.12399
1601.6230.036990.046420.055850.072620.097440.12064
1601.7430.046030.050940.055850.069360.097440.12043
1601.8630.033580.044830.056080.068340.099060.11606
1601.9830.035740.044040.052340.066460.095420.11233
1602.1030.034520.039820.045120.060170.087170.10758
1602.2230.031540.03620.040860.055410.082780.09878
1602.3430.019420.031760.04410.053560.080590.10021
1602.4630.034810.037560.040310.055040.079210.09898
1602.5820.027450.033950.040450.051470.076240.09248
1602.7020.028540.031550.034560.051340.069540.09026
1602.8220.02350.028320.033140.043230.067780.08423
1602.9420.02350.028320.033140.044560.0670.08323
1603.0620.024420.030090.035760.047090.06680.07943
1603.1820.023830.02780.031770.04390.063880.08003
1603.3020.022760.024850.026940.043630.05980.07645
1603.4220.013070.017990.022910.034970.055350.07149
1603.5420.02250.02020.01790.028640.053040.06618
1603.6610.015510.017020.018530.028540.048820.05992
1603.7810.019640.02010.020560.03050.052080.0607
1603.9010.007540.013280.019020.03060.04920.06226
1604.0210.012170.013440.014710.024630.046720.05236
1604.1410.007030.010220.013410.01970.039120.05255
1604.2615.90 × 10−40.007380.014170.014740.041580.05081
1604.3810.004910.011090.017270.017060.038550.05274
1604.50.001880.008140.01440.017960.038930.04908
1604.620.005430.008190.010950.017930.039120.0439
  27 in total

1.  Applications of water stable metal-organic frameworks.

Authors:  Chenghong Wang; Xinlei Liu; Nilay Keser Demir; J Paul Chen; Kang Li
Journal:  Chem Soc Rev       Date:  2016-07-13       Impact factor: 54.564

Review 2.  Lead poisoning: acute exposure of the heart to lead ions promotes changes in cardiac function and Cav1.2 ion channels.

Authors:  Gonzalo Ferreira de Mattos; Carlos Costa; Florencia Savio; M Alonso; G L Nicolson
Journal:  Biophys Rev       Date:  2017-08-23

3.  Mineralogical Evidence of Galvanic Corrosion in Drinking Water Lead Pipe Joints.

Authors:  Michael K DeSantis; Simoni Triantafyllidou; Michael R Schock; Darren A Lytle
Journal:  Environ Sci Technol       Date:  2018-02-28       Impact factor: 9.028

4.  Phenylthiosemicarbazide-functionalized UiO-66-NH2 as highly efficient adsorbent for the selective removal of lead from aqueous solutions.

Authors:  Jiali Tang; Yingbi Chen; Minghu Zhao; Shixing Wang; Libo Zhang
Journal:  J Hazard Mater       Date:  2021-01-30       Impact factor: 10.588

5.  Screening for Elevated Blood Lead Levels in Children and Pregnant Women: US Preventive Services Task Force Recommendation Statement.

Authors:  Susan J Curry; Alex H Krist; Douglas K Owens; Michael J Barry; Michael Cabana; Aaron B Caughey; Chyke A Doubeni; John W Epling; Alex R Kemper; Martha Kubik; C Seth Landefeld; Carol M Mangione; Lori Pbert; Michael Silverstein; Melissa A Simon; Chien-Wen Tseng; John B Wong
Journal:  JAMA       Date:  2019-04-16       Impact factor: 56.272

6.  Four phases of the Flint Water Crisis: Evidence from blood lead levels in children.

Authors:  Sammy Zahran; Shawn P McElmurry; Richard C Sadler
Journal:  Environ Res       Date:  2017-08       Impact factor: 6.498

Review 7.  Lead Poisoning in Children.

Authors:  Laura Mayans
Journal:  Am Fam Physician       Date:  2019-07-01       Impact factor: 3.292

8.  Allicin alleviates lead-induced hematopoietic stem cell aging by up-regulating PKM2.

Authors:  Shi-Zhong Cai; Li-Na Zhao; Jun Liu; Yi-Ting Ji; Xiao-Yan Shi; Zhou-Rui Ma; Xiao-Hua Lv; Ke Chen; Yan Chen
Journal:  Biosci Rep       Date:  2019-07-05       Impact factor: 3.840

9.  A pharmacokinetic model of lead absorption and calcium competitive dynamics.

Authors:  Anca Rădulescu; Steven Lundgren
Journal:  Sci Rep       Date:  2019-10-02       Impact factor: 4.379

Review 10.  Pb neurotoxicity: neuropsychological effects of lead toxicity.

Authors:  Lisa H Mason; Jordan P Harp; Dong Y Han
Journal:  Biomed Res Int       Date:  2014-01-02       Impact factor: 3.411
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  2 in total

1.  Solvent-Free Preparation of Tannic Acid Carbon Dots for Selective Detection of Ni2+ in the Environment.

Authors:  Yan Li; Can Liu; Menglin Chen; Yulong An; Yunwu Zheng; Hao Tian; Rui Shi; Xiahong He; Xu Lin
Journal:  Int J Mol Sci       Date:  2022-06-15       Impact factor: 6.208

Review 2.  Recent Progress in Metal-Organic Framework Based Fluorescent Sensors for Hazardous Materials Detection.

Authors:  Dan Zhao; Shuang Yu; Wen-Jie Jiang; Zhi-Hao Cai; Dan-Li Li; Ya-Lan Liu; Zhi-Zhou Chen
Journal:  Molecules       Date:  2022-03-29       Impact factor: 4.411
  2 in total

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