A Colorimetric Distinct Color Change Cu(II) 4-{[1-(2,5- dihydroxyphenyl)ethylidene]amino}-1,5-dimethyl-2-phenyl-1,2-dihydro-3H-pyrazol-3-one Chemosensor and its Application as a paper test kit

doi:10.21203/rs.3.rs-1476601/v1

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A Colorimetric Distinct Color Change Cu(II) 4-{[1-(2,5- dihydroxyphenyl)ethylidene]amino}-1,5-dimethyl-2-phenyl-1,2-dihydro-3H-pyrazol-3-one Chemosensor and its Application as a paper test kit

https://doi.org/10.21203/rs.3.rs-1476601/v1

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published 27 Dec, 2022

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A “4-{[1-(2,5-dihydroxyphenyl)ethylidene]amino}-1,5-dimethyl-2-phenyl-1,2-dihydro-3H-pyrazol-3-one” chemosensor (C1) synthesized by Condensation reaction using “4-amino-1,2-dihydro-1,5-dimethyl-2-phenylpyrazol-3-one” and “2,5-dihydroxy Actophenone”. It shows absorption peak at 326 nm due to the C=C bond (π-π* transition), while the absorption peak at 364 nm is caused by the C=O bond (n-π* transition). In the presence of copper C1 only demonstrated a change in absorption peak to higher wavelength (redshift) from 364 to 425 nm. The hue of both the C1+Cu(II) complex changed from bright yellow to dark brown colour with hypochromic shift appearance of a new peak at 425 nm. Even in the presence of other competing metal ions, the hypsochromic shift of the absorption band and the quenching of the fluorescence emission intensity were different for detecting Cu²⁺, in CH₃OH-H₂O (v/v = 6:4). Job's plot was used to compute the binding stoichiometry between C1 and Cu²⁺, and MASS and FTIR spectrophotometry were used to investigate the complexation process. The capacity of the C1 to bind Cu²⁺ was further proven using DFT simulations. The complex S1+Cu²⁺ has a HOMO-LUMO energy gap of 2.8002 eV, which is lesser than S1 (2.9991 eV). From these results, it can be seen that the specific binding of S1 to Cu²⁺ improves the stability of the S1+Cu²⁺ complex and effectively reduces the HOMO-LUMO energy gap. The C1 was successfully used in a real-world water sample analysis. Using the Benesi-Hildebrand and Scatchard plots, the K_b was calculated and found to be 47340M^-1 and 48369M^-1 respectively, showing the creation of stable complexation between Cu²⁺ and S1 with 1:1 Stoichiometry. The LOD of S1 for Cu²⁺ ion analysis was determined to be 649 nM. Strip sheets were also built and tested to detect varying amounts of Cu²⁺ aqueous solution, and their color change suggested that they might be used for on-site Cu²⁺ detection in polluted water.

4-{[1-(2

5-dihydroxyphenyl)ethylidene]amino}-1

5-dimethyl-2-phenyl-1

2-dihydro-3H-pyrazol-3-one

hypsochromic shift

emission spectrum

density functional theory

detection limit

The present rise of chemosensors development has sparked a lot of interest in contemporary research communities to create single organic molecules with the capability to detect a variety of metal ions using a variety of analytical methodologies. Such sensing compounds may become critically important since they play an important function in biological systems and have a high hazardous effect on the environment [1–6].

Over the last several years, inexpensive chemical sensors have played an essential role in monitoring a wide range of physiologically and environmental important species, such as heavy metal ions. Metal ion detection sensors with both fluorescence emission sub units and metal binding are highly sought after. In the case of fluorescent chemosensors for tiny compounds, poor selectivity and fluorescence quenching qualities are common. Although considerable progress has been achieved in this field, new methods for the detection of metal ions are still needed. Organic sensors have a number of advantages over traditional identification techniques, including simplicity of synthesis, high sensitivity, selectivity, and cheap cost.

Molecular sensors are very effective tools for recognizing medicinal, biological, chemical, and environmental species in particular. Despite the fact that chromatography and other analytical methods are widely used, ICP-MS, GFAAS, ICP-AES, AMS, NAA, ETAAS, LAMMA, and so on are available, fluorescence chemosensing is thought to be the best instrument since it is the selective, sensitive, rapid reaction, and low-cost technology that provides significant advantages over other tactics.

Cu is a necessary trace component for all living things, and it participates in a wide range of biological functions including enzyme catalysis, gene expression, and protein synthesis. Cu²⁺ levels in blood and drinking water are allowed to be between 15.7 to 23.6 mM under normal circumstances. A modest amount of Cu²⁺ is necessary for the body's regular operation, but too much Cu²⁺ may lead to a variety of neurological problems, including Wilson's disease and Alzheimer's disease. As a result, developing a simple, quick, and sensitive analytical approach for detecting Cu²⁺ is critical. Some fluorescent sensors can selectively and colorimetrically identify metal ions and offer a number of benefits, including high sensitivity and selectivity, cheap cost, and ease of process, making them appealing for Cu²⁺ detection.

In the current study, we synthesized C1 and explored its absorption and emission properties toward various metal ions. Only Cu exhibits a distinguishing color change due to a hypsochromic shift in the absorption band and a quenching of the fluorescence emission intensity. It possessed a 1:1 Cu²⁺ binding ratio and a LOD of 649 nM, making it suitable for detecting Cu²⁺ in real environmental samples. MASS and FTIR were used to confirm the structures of C1 and C1 + Cu²⁺ and furthermore it was established by the DFT design. Furthermore, the probe was utilized to make the test paper, which changed from yellow to orange-brown when the target ion was discovered.

2.1. Materials and instrumentation

Analytical reagent-grade organic solvents were used throughout. All of the cations utilized had high-quality nitrate and chloride salts and were employed without purification.

Stock solutions for C1 (1 mM) and nitrate and chloride salts of various metals were produced in CH₃OH-H₂O (v/v = 6:4). Absorption and fluorescence titrations were carried out on 10.0 µM C1, with aliquots of newly generated standard aqueous metal ion solutions added to record the absorption and fluorescence spectra.

Absorption spectra and IR spectrum were taken on “UV-1800 UV-Vis spectrophotometer”, Shimadzu and “Brukar IR” spectrophotometer, respectively with an excitation slit of 15.0 nm and an emission slit of 7.0 nm. ¹H-NMR spectra were acquired from Bruker DTX-400 spectrometer in DMSO. Mass spectra were obtained from micrOTOF-Q II mass spectrometer.

2.2 Synthesis of C1

A solution of "4-amino-1,2-dihydro-1,5-dimethyl-2-phenylpyrazol-3-one" (0.609g, 3mmol) in methanol (50 mL) was added to a solution of 2,5-dihydroxy Actophenone (0.456g, 3mmol) and the combination was stirred at room temperature for three hours. The formed yellow crystals were filtered and desiccated. Recrystallization from ethanol was used to purify the acquired yellow-colored crud product (80 percent Yield).

2.3 synthesis of C1 complex with Copper

The C1 (0.337 g, 1 mmol) was added to 30mL of CH₃OH and then 1 mmol of CuNO₃ was added while stirring. The entire mixture was refluxed for 3 hrs with constant stirring. A dark brown solid (C1 + Cu²⁺ Complex) developed after cooling, which was filtered and refined further by recrystallization in ethanol.

2.3 Photophysical studies

The working solution of C1 is scanned for both UV-visible and fluorescence spectrometers first, and then the different metal ions solutions are added one by one in aqueous methanol for cation selectivity on both devices. Metal ions with distinguishing spectrum shifts from other metal ions are used for titration studies. Photometric titrations between C1 and the selected metal ions were used to determine the binding constant for comprehensive research.

2.4 DFT Calculation

The geometry conformation and optimization calculations of the highly functionalized sensor S1 and sensor S1 + Cu²⁺ have been carried out using the “Gaussian 09 program”. The calculation of the density functional theory (DFT-B3LYP) was performed by defining the basis function system 6-311 + + G(d,p) for all atoms.

2.5 LOD calculation

Limits of detection calculation

The standard deviation of blank data was calculated by measuring the emission intensity and absorbance of C1 ten times.

The following calculation was used to compute the detection limit:

LOD = 3δ/S (3)

Where k = slope of the intensity versus Cu²⁺ concentration and

S = Standard deviation of the blank measurement

On the basis of IR, ¹H, and mass spectroscopic techniques the purity of sensor 4 has been determined. ¹H-NMR (CDCl₃, 400 MHz, ppm, δ): 2.39 (s, 3H, CH₃), 2.29 (s, 3H, CH₃), 3.15 (s, 3H, CH₃), 6.980 (s, 1H, Ar-H), 7.82–7.83 (m, 2H, Ar-H), 7.30–7.51 (m, 5H, Ar-H), 6.72 (m, 2H, Ar-H), 9.741 (s, 1H, -OH), 13.94 (s, 1H, -OH), IR (KBr, cm^− 1) υ = 611.58, 641.07, 662.48, 775.18, 831.46, 1217.42, 1579.46, 1597.41, 1634.23, 1679.26, 3230.86, 3302.86, 3397.43, MS (EI): m/z = 337.1426 (C₁₉H₁₉N₃O₃) cald m/z = 338.6032 for C₁₉H₁₉N₃O₃. The spectral examination yielded data that was compatible with the sensor 4 configuration [42–45].

UV-vis spectroscopies of C1 in an aqueous solution were recorded to examine their optical characteristics. Two peaks of absorption at 326 nm and 364 nm can clearly seen in the UV-vis spectrums (Fig. 3a). The absorption peak at 326 nm is due to the C = C bond (π-π* transition), whereas the C = O bond absorption peak is at 364 nm due to n-π* transition [44, 47]. However, after adding 1 equivalent of different metal ions such as Gd(III), Cr(III), Nd(III), Al(III), Mg(II), Hg(II), Mn(II), Cd(II), Pb(II), Co(II), Cu(II), Na(I), Ag(I), K(I), Li(I), and the absorption spectra showed no discernible alterations. Only in the presence of copper, C1 showed a change in absorption peak wavelength to a higher wavelength (red shift) from 364 to 425 nm respectively. The hue of both the C1 + Cu(II) complex changed from bright yellow to dark brown colour with hypochromic shift appearance of a new peak at 425 nm (Fig. 1). Absorbance titrations were used to test the sensitivity of C1. When the concentrations of Cu(II) (0–1 equiv.) in C1 were increased, a progressive rise in the absorbance band at 425 and decreases at 364 nm (Fig. 2), indicating the creation of C1 + Cu(II) complex with high stability and absorption new band indicate ligand to metal charge transfer mechanism. The R² = 0.9547 on the linear plot obtained from the titration reveals that S1 binds linearly to the Cu²⁺ ion (Fig. 3). The ratiometric graph found from the selectivity study demonstrated that the only addition of Cu²⁺ in C1 shows appreciates discriminating absorption shift (Fig. 4). The C1 absorption sensitivity check toward the Cu²⁺ in the presence of various major ions under the same medium and environmental condition. Furthermore, in the presence of Cu(II) ions, the sensor film's competitive sensitivity to several significant metal ions was determined, and the findings demonstrate that the developed sensor film with a high degree of chelation has a high sensitivity to Cu(II) ions. No change is observed in sensor film property (Fig. 5).

When Cu²⁺ ion solution was added to C1, the emission (exc = 425 nm) of C1 was investigated. In aqueous methanol, the emission spectra of C1 exhibit a very faint fluorescence band at 465 nm. The incorporation of the Cu²⁺ ion to C1 resulted in a significant quench in fluorescence (Fig. 6a). Increased fluorescence effect due to Cu²⁺ ion-induced chelation, the fluorescence enhancement is about 5 times larger than the individual receptor. The rise in emission intensity is most likely due to the complexation of the probe with Cu²⁺ through imine nitrogen and thiol SH, this reduces the accessibility of imine nitrogen atom lone pairs, shutting off PET and activating fluorescence. In this instance, the substantial CHEF effect stiffens the chemosensor framework, and inhibiting “isomerization of the C = N double bond of the C1 in an excited state may also result in a considerable increase in the C1's fluorescence intensity.” [27]. Fluorescence quenching refers to the absence of fluorescence. The C1 in aqueous methanol quenches the emission maxima and becomes "TURN-OFF" in this circumstance. When the Cu²⁺ ion was introduced to the C1, the emission maximum was dramatically increased, resulting in fluorescence ON (Fig. 5).

Fluorescence titration studies were carried out in order to have a better grasp of the sensing behaviour of C1 to Cu²⁺. The fluorescence intensity fell progressively as the quantity of Cu²⁺ increased, as seen in Fig. 6b. A considerable quenching of fluorescence was seen with the addition of 10 equiv. of Cu²⁺, with a 99 percent quenching efficiency [(I0 I)/I0 100 percent]. At roughly 0.5 mol fractions, a minimum was seen in the Job plots using fluorescence titrations, showing that sensor 1 formed 1: 1 combination with Cu²⁺ (Scheme 1).

HOMO-LUMO Analysis

The difference in energy between HOMO and LUMO is an important parameter for determining the excitability of molecules. In general, the frontier molecular orbital (FMO) diagram is a vital one to differentiate between the effect of metal binding with the sensors and its electronic characteristics. In this piece of research, to distinguish the same (i.e., effect of binding of Cu²⁺ with highly functionalized sensor S1) and its electronic characteristics, FMOs of Cu²⁺ with highly functionalized sensor S1 and highly functionalized sensor S1 alone have been assessed and the results provided interesting insights into the relevant LUMO/HOMO energy levels and electron distribution. Pictorial representation of electron distribution in LUMO and HOMO of the highly functionalized sensor S1 and its metal coordinated one (sensor S1 + Cu²⁺) are depicted in Fig. 6 and the associated energy values are furnished in Table 1. In the present case, the energy difference between the LUMO and HOMO of the highly functionalized sensor S1 is noted to be 3.00 eV which is higher than that of the distinction in energy between HOMO and LUMO of the sensor S1 + Cu²⁺ (2.80 eV). The results imply that the firmness of the highly functionalized S1 + Cu²⁺ complex is superior as a result of the explicit binding of highly functionalized sensor S1 with Cu²⁺ which meritoriously decreases the HOMO-LUMO energy difference (i.e., precise binding of highly functionalized sensor S1 to metal Cu²⁺ increases the stability of the sensor S1 + Cu²⁺ complex). In the HOMO of the highly functionalized sensor S1, the electron density is localized on the pyrazole unit and aryl moiety integrated at the N-position of pyrazole structural motif while in LUMO of the same, the electron density is localized mainly on the imino structural motif bridging between pyrazole and dihydroxyaryl scaffolds. On the other hand, in the HOMO of the highly functionalized sensor S1 + Cu²⁺, the electron density is denser on the dihydroxyaryl moiety, imino functionality as well as the pyrazole structural motif along with metal whereas in the LUMO of the same, the electron density is denser over the aryl moiety tethered at the N-of the pyrazole unit along with pyrazole structural motif. These observations imply that electron transfer from one part to another takes place within the molecules as for as HOMO and LUMO are concerned. Overall, the DFT results are in good harmony with the experimental outcomes of the metal binding. Broadbands were found in the FTIR spectra of pure ligand at 3238cm^− 1 and 3062cm^− 1, respectively, which correspond to the –OH and –NH stretching frequencies. At 1625cm^− 1 and 1498cm^− 1, respectively, carbonyl and imine stretching frequency characteristic bands developed clearly. In the FTIR spectra of the matching C1-Cu²⁺ combination (Figure S4 in supplement file), the unique bands associated with -OH and -NH are diminished/decreased, and the bands for carbonyl and imine stretching are relocated to a lower wavelength in the complex at 1662cm^− 1 and 1492cm^− 1, respectively. According to the above facts, the ligand's amide functionality must have been subjected to amido-imidol tautomerism for the imidol structure to become dominant during complexation. Because of the presence of N in the C = N with Cu, the band for the carbonyl and imine functional groups likewise moves to a shorter wavelength. m/z = 417.9258 (C₁₉H₂₀CuN₃O₄) cald m/z = 419.7101 for (C₁₉H₂₀CuN₃O₄) (Figure S5 in supplement file).

Table 1

Energies value of C1and **C1 + Cu**²⁺
Parameter	Energies (eV)
Parameter	C1	C1 + Cu²⁺
HOMO	-6.1759	-4.9479
LUMO	-3.1768	-2.1477
ΔE	2.9991	2.8002

Ka was calculated using “Benesi-Hildebrand” and “Scatchard Plot” at 47340M^− 1 and 48369M^− 1 respectively (Figs. 8 and 9), showing the formation of stable complexation between Cu²⁺ and C1 with 1:1 Stoichiometry. From the equation LOD 3s/m, it was discovered that the detection limit is 649 nM. Job's receptor plot reveals peaks corresponding to 0.5 mole fraction for C1-Cu²⁺ complex formation, indicating 1:1 complex formation (Fig. 10). To assess the binding stoichiometry between C1 and Cu²⁺, a Job's plot for C1 with metal ions was built. It reached a climax at a mole ratio fraction of 1/2, showing that the binding mode of C1 with Cu²⁺ is 1:1 stoichiometry. Figure 9 displays a jobs plot of the host's absorbance H/([H]+[G]) at various concentrations. Where H stands for host and G for guest Cu²⁺ metal ions. The finding indicates that a 1:1 stoichiometry combination formed between C1 and Cu²⁺ [32]. The visible color shift that occurs when Cu²⁺is added to the C1 is an important component of this work, which looked at ONSITE Cu²⁺detection in water samples and the reversibility test with the addition of EDTA, and successful formation of EDTA + Cu and C1 (Figs. 11 and 12) [33].

We made test strips by dipping filter papers (3× 1 cm²) in the CH₃OH-H₂O (v/v = 6:4) solution of C1 (1 × 10^− 3 M) and then drying them in air to see whether a "dip-stick" approach for the detection of Cu2+, similar to that typically used for pH testing, was suitable. The evident color shift from yellow to Orange was noticed when the test strips coated with LX (1 × 10^− 3 M) were submerged in pure water solutions of Cu2 + with varied concentrations (Fig. 13). The creation of a "dip-sticks" method was very appealing for "in-the-field" measurements that did not need any extra equipment. As a result, the C1 test strips offer a high applicability value for detecting Cu2+.

A Schiff-base “4-{[1-(2,5-dihydroxyphenyl)ethylidene]amino}-1,5-dimethyl-2-phenyl-1,2-dihydro-3H-pyrazol-3-one” colorimetric and fluorescence chemosensor C1 for Cu²⁺ was developed. UV-vis spectrums show two peaks of absorption at 326 nm and 364 nm clearly. Only in the presence of copper, from 364 to 425 nm, C1's absorption peak shifted to a higher wavelength (red shift). Even in the presence of other competing metal ions, the hypsochromic shift of the absorption band and the quenching of the fluorescence emission intensity were unique for the detection of Cu²⁺, in “CH₃OH-H₂O (v/v = 6:4)”. The capacity of the C1 to bind Cu2 + was further proven using DFT simulations. The complex S1 + Cu²⁺ has a HOMO-LUMO energy gap of 2.8002 eV, which is lesser than S1 (2.9991 eV). From these results, it can be seen that the specific binding of S1 to Cu²⁺ improves the stability of the S1 + Cu²⁺ complex and effectively reduces the HOMO-LUMO energy gap. Using the Benesi-Hildebrand and Scatchard plots, the K_b was calculated and found to be 47340M^− 1 and 48369M^− 1 respectively, showing the formation of stable complexation between Cu²⁺ and S1 with 1:1 Stoichiometry. S1 detection limit for Cu²⁺ ion analysis was found to be 649 nM.

“Author Declarations”

Author Contributions: Umesh Fegade, Nilima Patil, and Rajesh Dhake designed the concept and methodology for the experiment and wrote the paper. Vadivel Saravanan and Chennan Ramalingan for DFT calculation. Tariq Altalhi, Inamuddin, and Raju Phalak contributed to analyzing the results and finalize the paper.

Conflicts of interest/Competing interests

Authors have no conflict of interest

Funding (information that explains whether and by whom the research was supported)

The authors thank Taif University for financial support through the research grant Supporting Project number (TURSP-2020/04), Taif University, Taif, Saudi Arabia.

Ethics Declaration statement

Conflict of Interest: The authors declare no conflict of interest.

Consent to Participate

Not applicable

Consent for publication

Not applicable

Data availability statements

Data is available on request from the authors.

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Scheme 1 is available in the Supplementary Files section.

No competing interests reported.

Scheme1.png
Scheme 1: Synthesis of C1.
SupplementofUMBA1923032022.docx

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A Colorimetric Distinct Color Change Cu(II) 4-{[1-(2,5- dihydroxyphenyl)ethylidene]amino}-1,5-dimethyl-2-phenyl-1,2-dihydro-3H-pyrazol-3-one Chemosensor and its Application as a paper test kit

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Abstract

Figures

1. Introduction

2. Materials And Method

2.1. Materials and instrumentation

2.2 Synthesis of C1

2.3 synthesis of C1 complex with Copper

2.3 Photophysical studies

2.4 DFT Calculation

2.5 LOD calculation

3. Result And Discussion

4. Application As A Test Kit

5. Conclusions

Declarations

References

Scheme

Additional Declarations

Supplementary Files

Status:

Journal Publication

Version 1