KR101121739B1 - Rhodamin B derivative compound as the fluorigenic and chromogenic probe for Ag+/Ag Nanoparticles in aqueous media - Google Patents

Abstract

 The present invention relates to a novel rhodamine B derivative compound capable of detecting silver ions and silver nanoparticles, and more particularly, the fluorescence intensity is significantly increased when the silver ions and silver nanoparticles are detected. Rhodamine B derivative compound.

 Rhodamine B derivative compound according to the present invention is represented by the following formula (1),

(1)

(One)

Wherein R ₁ represents hydrogen, halogen or substituted or unsubstituted alkyl, substituted or unsubstituted aryl group, and R ₂ represents hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl group, and R ₃ represents Each independently represents -NEt ₂ , -NHR, or -NH ₂ .

The compound according to the present invention has colorless and fluorescence-free properties. When silver ions or silver ions produced by oxidation of silver nanoparticles are coordinated with iodine, the spirolactam ring opens and an oxazoline ring is formed. -on "shows fluorescence and color development.

Description

Rhodamin B derivative compound as the fluorigenic and chromogenic probe for Ag + / Ag Nanoparticles in aqueous media}

 The present invention relates to a rhodamine B derivative capable of detecting silver ions and silver nanoparticles, and more particularly, to increase the color change and fluorescence intensity of a solution when detecting silver ions and silver nanoparticles in an aqueous solution. It relates to a min B derivative.

The literature information of the prior art is as follows.

(1) (a) Nanotechnologies for the Life Sciences Kumar, CSSR, Ed .; Wiley-VCH; Weinheim, 2007; 10 vols. (b) Dekker Encyclopedia of Nanoscience and Nanotechnology Schwarz, JA, Contescu, CI, Putyera, K., Eds .; Marcel Dekker: 2004; 5 vols.

(2) (a) Feng, QL; Wu, J .; Chen, GQ; Cui, FZ; Kim, TN; Kim, JO J. Biomed. Mater. Res. 2000 , 52 , 662. (b) Lansdown, AB J. Wound Care 2002 , 11 , 125. (c) Yamanaka, M .; Hara, K .; Kudo, J. Appl. En V iron. Microbiol. 2005 , 71 , 7589.

(3) (a) Morones, JR; Elechiguerra, JL; Camacho, A .; Holt, K .; Kouri, JB; Ramı'rez, JT; Yacaman, MJ Nanotechnology 2005 , 16 , 2346. (b) Sambhy, V .; Mac Bride, MM; Peterson, BR; Sen, A. J. Am. Chem. Soc. 2006 , 128 , 9798. (c) Kenawy, E.-R .; Worley, SD; Broughton, R. Biomacromolecules 2007 , 8 , 1359. (d) Kumar, A .; Vemula, PK; Ajayan, PM; John, G. Nat. Mater. 2008 , 7 , 236.

(4) (a) Asharani, PV; Wu, YL; Gong, Z .; Valiyaveettil, S. Nanotechnology 2008 , 19 , 255102. (b) Lee, KJ; Nallathamby, PD; Browning, LM; Osgood, CJ; Xu, X.-HN ACS Nano 2007 , 1 , 133. (c) Silver and Silver Compounds: Environmental Aspects; CICADS 44, 2002; http: // www.inchem.org/.

(5) University of Missouri-Columbia (2008, April 30), Silver Nanoparticles May Be Killing Beneficial Bacteria In Wastewater Treatment, Science-Daily [Online]; http://www.sciencedaily.com/releases/ 2008/04 / z080429135502.htm.

(6) (a) Rains, T .; Watters, R .; Epstein, M. En V iron. International 1984 , 10 , 163. (b) Schildkraut, D .; Dao, P .; Twist, J .; Davis, A .; Robillard, K. En V iron. Toxicol. Chem. 1998 , 17 , 642.

(7) (a) Jiang, P .; Guo, Z. Coord. Chem. Re V. 2004 , 248 , 205. (b) Prodi, L .; Bolletta, F .; Montalti, M .; Zaccheroni, N. Coord. Chem. Re V. 2000 , 205 , 59. (c) Valeur, B .; Leray, I. Coord. Chem. Re V. 2000 , 205 , 3.

(8) (a) Yang, R.-H .; Chan, W.-H .; Lee, AWM; Xia, P.-F .; Zhang, H.-K .; Li, K. J. Am. Chem. Soc. 2003 , 125 , 2884. (b) Liu, L .; Zhang, D .; Zhang, G .; Xiang, J .; Zhu, D. Org. Lett. 2008 , 10 , 2271. (c) Rurack, K .; Kollmannsberger, M .; Resch-Genger, U .; Daub, J. J. Am. Chem. Soc. 2000 , 122 , 968. (d) Schmittel, M .; Lin, H. Inorg. Chem. 2007 , 46 , 9139. (e) Rathore, R .; Chebny, VJ; Abdelwahed, SH J. Am. Chem. Soc. 2005 , 127 , 8012. (f) Ikeda, M .; Tanida, T .; Takeuchi, M .; Shinkai, S. Org. Lett. 2000 , 2 , 1803. (g) Sessler, JL; Tomat, E .; Lynch, VM J. Am. Chem. Soc. 2006 , 128 , 4184.

(9) Shevchenko, GP; Bokshits, JV; Sviridov, VV Physics, Chemistry and Application of Nanostructures. The Effect of Hydrogen Peroxide on the Optical Properties of Ultrafine Sil V er Borisenko, VE; Filonov, AB; Gaponenko, SV; Gurin, VS Eds .; 1999; pp 236-238.

Recently, nanomaterials are widely used in biopharmaceuticals, biosensors, drug delivery systems, and cosmetics. Among them, various products using silver nanoparticles to remove harmful bacteria are in the spotlight. Examples include detergents that control bacteria to reduce the smell of fabrics, and bandages for wound disinfection to control bacteria that cause skin infections. The reason why silver nanoparticles are used in various products is that when silver nanoparticles come in contact with moisture, oxidation reactions occur to generate silver ions. The generated silver ions generate strong free radicals that interfere with the growth and regeneration of bacteria, resulting in antibacterial and bactericidal effects. However, silver ions produced from these used silver nanoparticle products and silver ions flowing from abandoned silver nanoparticle products have been known to flow into sewers and rivers and have a detrimental effect on beneficial marine life. Until now, few chemical sensors have been developed that can detect such silver ions and silver nanoparticles by simple methods such as fluorescence or color change of solution.

 Therefore, there is a need for a method for selective and simple detection of silver ions and silver nanoparticles using fluorescence and color changes.

It is an object of the present invention to provide novel fluorescent and chromogenic rhodamine B derivative compounds.

Another object of the present invention is that when the silver nanoparticles coordinate silver ions produced in the oxidation reaction, the spirolactam ring is opened and the oxazoline ring is formed, which is a novel fluorescence and color development showing “turn-on” fluorescence and color development. It is to provide a rhodamine B derivative compound.

Another object of the present invention is to provide a novel method for detecting silver ions and silver nanoparticles using fluorescence and color development.

Still another object of the present invention is to provide a use of such a material in fluorescent and color chemical sensors.

In order to achieve the above object, the present invention provides a rhodamine B derivative compound represented by the formula (1), or a salt thereof.

(1)

(One)

Wherein R ₁ represents hydrogen, halogen or substituted or unsubstituted alkyl, substituted or unsubstituted aryl group, and R ₂ represents hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl group, and R ₃ Independently represents -NEt _2, -NHR, or -NH ₂ .

In the present invention, R ₁ represents hydrogen, halogen, C1-C30 substituted or unsubstituted alkyl, substituted or unsubstituted aryl group, preferably hydrogen.

In the present invention, R ₂ represents hydrogen, C1-C30 substituted or unsubstituted alkyl, substituted or unsubstituted aryl group, preferably hydrogen.

In the present invention, R ₃ represents -NEt _2, -NHR, or -NH ₂ , and preferably -NEt ₂ .

In a preferred embodiment of the invention, the compound is R1 and R2 are hydrogen, R ₃ is -NEt _2, 3 ', 6'-bis (diethylamino) -2- (beta-iodo-ethyl) - isopropyl Indolin-1,9'-xanthene] -3-one.

In one aspect, the present invention provides a fluorescent and chromogenic Rhodamine B derivative compound represented by the formula (1).

(1)

(One)

here,

R 1 represents hydrogen, halogen, alkyl having 1 to 30 carbon atoms, or an aryl group having 1 to 30 carbon atoms, and R ₂ represents hydrogen, halogen, alkyl having 1 to 30 carbon atoms, or an aryl group having 1 to 30 carbon atoms. R ₃ is independently an amine group substituted with Et, alkyl, aryl or the like.

The compound has colorless and fluorescence-free properties. When the silver ions coordinate, the spirolactam ring is opened and an oxazoline ring is formed to show “turn-on” fluorescence and color development.

(2)

In the present invention, the rhodamine B derivative compound (I) exhibits “turn-on” fluorescence and color development when silver ions are bonded. As shown in Fig. 2, when silver ions coordinate with iodine, The migration opens the spirolactam ring and forms an oxazoline ring, resulting in a drop in silver iodide, resulting in a change in the aqueous solution color and “turn-on” fluorescence.

In the present invention, the coloring and fluorescent rhodamine B derivative compound (1) selectively detects only silver ions when compared with various metal cations to change the color of the solution and increase the fluorescence. Accordingly, the present invention provides a use that can easily detect the presence of silver ions and silver nanoparticles with color and fluorescence with high sensitivity.

In the present invention, the rhodamine B derivative compound represented by the formula (1) may be prepared according to the following scheme.

(3)

The process of forming a spirolactam ring and forming an oxazoline ring by coordinating silver ions to the rhodamine B derivative compound represented by the formula (1) may be explained by the following formula.

Hereinafter, the present invention will be described in detail through examples. However, although the following examples are described in detail, it is to be understood that the above examples are intended to illustrate the invention and are not intended to be limiting.

The present invention introduces iodine capable of coordinating silver ions to rhodamine B derivatives, and when only silver ions are selectively coordinated, a spirolactam ring is opened and an oxazoline ring is formed, thereby producing “turn-on” fluorescence and color development. Rhodamine B derivative compounds that exhibit properties have been provided.

The present invention provides a rhodamine B derivative compound capable of selectively quantitating silver nanoparticles in which silver ions are generated during silver ions and oxidation reactions.

According to the present invention, a chemical sensor for detecting silver ions and silver nanoparticles having high sensitivity and high substrate selectivity for silver ions and silver nanoparticles has been provided.

Example 1

3 ', 6'-bis (diethylamino) -2- (beta-hydroxyethyl)-[isoindolin-1,9'-xanthene] -3-one

Rhodamine B (0.500 g, 1.04 mmol) was dissolved in 40 mL of ethanol and 2-aminoethanol (252 μL, 4.16 mM) was added, followed by stirring under reflux at 120 ° C. for 2 days. After the temperature was lowered to room temperature, the solvent was removed under reduced pressure and dissolved in ethyl acetate. The organic layer was washed with water (20 mL) and saturated aqueous sodium chloride solution (10 mL) and dried over anhydrous sodium sulfate. This was subjected to column chromatography through silica gel (dichloromethane / methanol, 9: 1) to obtain 0.44 g (87% yield) of a white solid product.

Yield: 0.44 g (87%); mp 216 ° C;

¹ H NMR (CDCl ₃ , 300 MHz): δ 1.17 (12H, t, J = 7.1 Hz), 3.27-3.37 (10H, m), 3.47 (2H, t, J = 5.2 Hz), 6.29 (2H, dd , J = 2.6, 8.9 Hz), 6.38 (2H, d, J = 2.6 Hz), 6.49 (2H, d, J = 8.8 Hz), 7.06-7.1 (1H, m), 7.41-7.47 (2H, m) , 7.89-7.92 (1 H, m); 13 C NMR (CDCl ₃ , 75 MHz): δ 13.3, 30.4, 45.1, 45.3, 63.3, 66.6, 98.5, 105.4, 108.9, 123.6, 124.5, 128.8, 129.2, 131.1, 133.4, 149.6, 154.6, 166.0, 170.8; HRMS (FAB): m / z calcd. for C ₃₀ H ₃₆ O ₃ N ₃ [(M ⁺ H < + >)] 486.2757; Found 486.2755.

Example 2

3 ', 6'-bis (diethylamino) -2- (beta-ethylmethanesulfonate)-[isoindolin-1,9'-xanthene] -3-one

3 ', 6'-bis (diethylamino) -2- (beta-hydroxyethyl)-[isoindolin-1,9'-xanthene] synthesized in Example 1 under argon atmosphere in a 100 mL round flask 3-one (0.200 g, 0.41 mmol), triethylamine (0.630 g, 0.62 mmol) and dichloromethane (30 mL) were added and the temperature was reduced to 0 ° C. Methanesulfonyl chloride (38 μL) was slowly added thereto, followed by stirring at room temperature for one day. After washing with water and saturated aqueous sodium chloride solution, the organic layer was dried over anhydrous sodium sulfate and the solvent was removed under reduced pressure. 20 mL of anhydrous acetone and anhydrous iodine chloride (0.076 g, 0.5 mmol) were added, and the mixture was stirred under reflux for 12 hours. After cooling to room temperature, the solvent was removed under reduced pressure, dissolved in dichloromethane, washed with 10% aqueous sodium thiosulfate solution and saturated aqueous sodium chloride solution, and the organic layer was dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure to give 0.205 g (84% yield) of a colorless solid product.

Yield 0.205 g (84%): mp 206 ° C .;

¹ H NMR (CDCl ₃ , 300 MHz): δ 1.18 (12H, t, J = 7.1 Hz), 2.78-2.84 (2H, m), 3.35 (8H, q, J = 7.1 Hz), 3.51-3.57 (2H , m), 6.27 (2H, dd, J = 2.6, 8.9 Hz), 6.39-6.45 (4H, m), 7.05-7.1 (1H, m), 7.42-7.46 (2H, m), 7.88-7.94 (1H m); ¹³ C NMR (CDCl ₃ , 75 MHz): δ 12.8, 29.8, 43.2, 44.5, 64.8, 98.0, 105.4, 108.3, 123.1, 123.9, 128.2, 128.8, 130.7, 132.8, 149.1, 153.3 153.7, 167.9; HRMS: (FAB) m / z calcd. for C ₃₀ H ₃₅ O ₂ N ₃ I [(M ⁺ H ⁺ )] 596.1174; found 596.1776.

Example 3

3 ', 6'-bis (diethylamino) -2- (beta-iodineethyl)-[isoindolin-1,9'-xanthene] -3-one synthesized in Example 2 (50 mg, 0.09 mmol) was dissolved in 2 mL of ethanol and silver nitrate (16 mg, 0.09 mmol) was added. After stirring for 1 hour at room temperature, the solvent was removed under reduced pressure, dissolved in ethyl acetate, filtered through Celite, and dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure to give 47 mg (yield 97%) of oxazoline product.

¹ H NMR (CD ₃ OD, 300 MHz): δ 1.32 (12H, t, J = 7.2 Hz), 3.70 (8H, q, J = 7.2 Hz) 3.84 (2H, t, J = 9.8 Hz), 4.12 ( 2H, t, J = 9.8 Hz), 7.0 (2H, d, J = 2.4 Hz), 7.08 (2H, dd, J = 2.4, 9.5 Hz), 7.26 (2H, dd, J = 1.8, 9.5 Hz), 7.54 (1H, d, J = 7.4 Hz), 7.82-7.88 (2H, m), 8.25 (1H, dd, J = 1.3, 7.2 Hz); ¹³ C NMR (CD ₃ OD, 75 MHz): δ 12.9, 17.4, 47.0, 56.5, 71.1, 97.6, 114.5, 115.9, 129.1, 130.9, 132.0, 132.1, 132.3, 133.4, 133.6, 157.4, 159.3. HRMS: (FAB) m / z calcd. for C ₃₀ H ₃₄ O ₂ N ₃ [M < + >]468.2646; Found 468.2648.

Example 4

UV-Vis titration test for silver ions of the compound Rhodamine B derivative (1)

UV-Vis data were recorded on an HP 8453 spectrophotometer. Experimental solutions were prepared at a 20% ethanol / water ratio.

Figure 1 shows 3 ', 6'-bis (diethylamino) -2- (beta-iodethyl)-[isoindolin-1,9'-k at a concentration of 10 μM in a 20% ethanol / water solution at 25 ° C. The absorbance was measured by adding the equivalents of silver ions to the aciden] -3-one (1), and the absorbance values at the maximum absorption wavelength of 558 nm were compared. The absorbance increases proportionally until one equivalent of silver ions is added, and when one or more equivalents of silver ions are added, the absorbance no longer increases and is saturated.

Example 5

Fluorescence titration test on silver ions of the compound Rhodamine B derivative (1)

In FIG. 2, 3 ', 6'-bis (diethylamino) -2- (10 μM concentration) measured by adding equivalent silver ions (silver nitrate) in a 20% ethanol / water solution at 25 ° C. at 530 nm excitation wavelength. Fluorescence intensity changes of beta-iodineethyl)-[isoindolin-1,9'-xanthene] -3-one (1) were measured. It can be seen that the change in fluorescence intensity is maximized when one equivalent of silver ions is added, and the change in fluorescence intensity is saturated when more than one equivalent is added.

Figure 3 shows 3 ', 6'-bis (diethylamino) -2- (beta-iodethyl)-[isoindolin-1,9'-k at a concentration of 10 μM in a 20% ethanol / water solution at 25 ° C. When 1 equivalent of silver ions (silver nitrate) is added to the aciden] -3-one (1), the color change (left) and the change in fluorescence intensity (right) of the solution can be seen.

In Fig. 4, 3 ', 6'-bis (diethylamino) -2- at a concentration of 10 μM measured by adding 1 equivalent of silver ions (silver nitrate) to a 20% ethanol / water solution at 25 ° C. at a 530 nm excitation wavelength. Fluorescence change of (beta-iodineethyl)-[isoindolin-1,9'-xanthene] -3-one (1) was measured over time. After adding 1 equivalent of silver ions, the intensity of fluorescence increases up to 130 minutes, and after 130 minutes, the intensity of fluorescence is gradually saturated.

Example 6

Selectivity test for the metal cation of the compound rhodamine B derivative (1)

FIG. 5 shows 3 ', 6'-bis (diethylamino) -2- (beta-iodineethyl)-[isoindolin-1 at a concentration of 10 μM in a 20% ethanol / water solution at 25 ° C. at 530 nm excitation wavelength. To, 9'-xanthene] -3-one (1) Ba ²⁺ , Ni ²⁺ , Fe ³⁺ , Cr ²⁺ , Ca ²⁺ , Hg ²⁺ , Mn ²⁺ , Cu ²⁺ , Hg ⁺ , Fluorescence intensity values of 584 nm were measured by adding 1 equivalent of metal cations of Cu ⁺ , Pd ²⁺ , Mg ²⁺ , Cd ²⁺ , Zn ²⁺ , Co ²⁺ , Pb ²⁺ , Ag ⁺ . It can be seen that the fluorescence increases selectively only when silver ions are added.

Example 7

Detection limit test for silver ions of the compound Rhodamine B derivative (1)

In Fig. 6, silver ions of the above-described 3 ', 6'-bis (diethylamino) -2- (beta-iodineethyl)-[isoindolin-1,9'-xanthene] -3-one (1) To determine the limit of detection, 10'M concentration of 3 ', 6'-bis (diethylamino) -2- (beta-iodineethyl)-[iso Various concentrations of silver ions (silver nitrate) were added to indolin-1,9'-xanthene] -3-one (1) to measure the fluorescence intensity value at a wavelength of 584 nm. It can be seen that the rhodamine B derivative (I) can be measured up to a concentration of 0.13 μM (14 ppb). For reference, the maximum contamination level of silver as regulated by the US Food and Drug Administration in 2001 is 100 ppb. Therefore, this fluorescence sensor that can measure up to 14 ppb satisfies high sensitivity.

7 shows 0.13 μM (14 ppb) of the Rhodamine B derivative (1). It can be seen that the intensity of fluorescence increases 10 minutes after the addition of the concentration of silver ions (silver nitrate).

Example 7

Silver Nanoparticle Detection Test of Compound Rhodamine B Derivative (1)

In order to detect the silver nanoparticles using the Rhodamine B derivative compound (1), an equilibrium state of silver nanoparticles and silver ions was induced by oxidation with hydrogen peroxide under acidic conditions. Fluorescence changes were measured after addition of silver nanoparticles (8 ± 1 nm) and rhodamine B derivative compounds (I) at concentrations of 1.0 mM hydrogen peroxide, 1.0 phosphate, and 20% ethanol / water.

8 shows 3 ', 6'-bis (diethylamino) -2- (beta-iodineethyl)-[isoindolin-1,9'-xanthene] -3-one (1) under the conditions described above. After adding 2 equivalents of silver nanoparticles, the fluorescence change over time was measured. After adding silver nanoparticles, the fluorescence intensity increases until 150 minutes, after which the increase in fluorescence intensity is saturated.

In FIG. 9, the intensity change of fluorescence at 584 nm was measured while increasing the concentration of silver nanoparticles in Rhodamine B derivative compound (I) under the conditions described above. As the concentration of silver nanoparticles increases, the intensity of fluorescence also increases proportionally. This suggests that qualitative analysis of silver nanoparticles is possible using a proportional relationship between fluorescence intensity value and silver nanoparticle concentration.

Example 8

Quantitative Analysis of Commercialized Silver Nanoparticle-Containing Products Using the Compound Rhodamine B Derivative (1)

Commercially available using 3 ', 6'-bis (diethylamino) -2- (beta-iodineethyl)-[isoindolin-1,9'-xanthene] -3-one (1) A quantitative analysis of silver nanoparticle containing products was attempted. In the commercially available silver nanoparticle products, an incorrect hand disinfection gel product and fabric softener were selected and analyzed. An amount of gel was taken and added to an acidic hydrogen peroxide solution (1.0 mM hydrogen peroxide, 1.0 phosphate solution, 20% ethanol / water solution). (1 mL / g of gel) Finally, excess 3 ', 6'-bis ( Diethylamino) -2- (beta-iodineethyl)-[isoindolin-1,9'-xanthene] -3-one (1) (20 μM) was added and after 1 hour, extracted with ethyl acetate 530 Fluorescence intensity change at nm excitation wavelength was measured.

In FIG. 10, 0.5 g, 1.0 g, 1.5 g, and 2.0 g of a hand sanitizer gel containing silver nanoparticles were taken and 3 ', 6'-bis (diethylamino) -2- (beta-) was prepared according to the conditions and methods described above. Fluorescence intensity change of the solution of iodineethyl)-[isoindolin-1,9'-xanthene] -3-one (1) was measured and the fluorescence intensity values at 584 nm wavelength were compared. As the amount of gel used increases, the amount of silver nanoparticles contained increases and the fluorescence intensity increases proportionally.

As a second product, a fabric softener containing silver nanoparticles was quantitatively analyzed under the conditions and methods described above.

In FIG. 11, 2 mL of a fiber softener containing silver nanoparticles was taken and 3 ', 6'-bis (diethylamino) -2- (beta-iodineethyl)-[isoindolin-1 was prepared according to the conditions and methods described above. Fluorescence intensity changes at 530 nm excitation wavelength were investigated to determine the fluorescence intensity change of the, 9'-xanthene] -3-one (1) solution and to analyze the concentration of silver nanoparticles contained in the product. A fibrous softener containing silver nanoparticles was prepared using 3 ', 6'-bis (diethylamino) -2- (beta-iodineethyl)-[isoindolin-1,9'-xanthene] -3-one (1 The fluorescence intensity increases with addition to the solution.

In FIG. 12, a linear curve was obtained by obtaining a standard curve between six silver nanoparticle samples having known concentrations and fluorescence intensity values at 584 nm obtained by excitation at 530 nm. This standard curve was used to determine silver nanoparticle concentrations of commercially available products with unknown concentrations. The calculations showed that the hand sanitizer gel products contained silver nanoparticles at 1.9 ppm and the fabric softener at 0.6 ppm.

FIG. 1 shows 3 ', 6'-bis (diethylamino) -2- (beta-iodethyl)-[isoindolin-1,9'-k at a concentration of 10 μM in a 20% ethanol / water solution at 25 ° C. Addition of silver ions to equivalents of xanten-3-one (1) by weight is an absorbance graph.

FIG. 2 is a 10'M concentration of 3 ', 6'-bis (diethylamino)-, measured by adding equivalent silver ions (silver nitrate) in a 20% ethanol / water solution at 25 ° C. at a 530 nm excitation wavelength in FIG. Fluorescence intensity change graph of 2- (beta-iodineethyl)-[isoindolin-1,9'-xanthene] -3-one (1).

FIG. 3 shows 3 ', 6'-bis (diethylamino) -2- (beta-iodethyl)-[isoindolin-1,9'-k at a concentration of 10 μM in a 20% ethanol / water solution at 25 ° C. When 1 equivalent of silver ions (silver nitrate) is added to the Santen] -3-one (1), it is a photograph showing the change in color of the solution (left) and the change in fluorescence intensity (right).

FIG. 4 is a 10 μM concentration of 3 ′, 6′-bis (diethylamino) -2- as measured by adding 1 equivalent of silver ions (silver nitrate) to a 20% ethanol / water solution at 25 ° C. at a 530 nm excitation wavelength. It is a graph showing the fluorescence change of (beta-iodineethyl)-[isoindolin-1,9'-xanthene] -3-one (1) over time.

FIG. 5 shows 10'M concentration of 3 ', 6'-bis (diethylamino) -2- (beta-iodineethyl)-[isoindolin-1 in a 20% ethanol / water solution at 25 ° C. at 530 nm excitation wavelength. It is a graph showing the increase in fluorescence of various metals against, 9'-xanthene] -3-one (1).

FIG. 6 shows 10'M concentration of 3 ', 6'-bis (diethylamino) -2- (beta-iodineethyl)-[isoindolin-1 in a 20% ethanol / water solution at 25 ° C. at 530 nm excitation wavelength. A fluorescence intensity value of 584 nm was measured by adding various concentrations of silver ions (silver nitrate) to, 9'-xanthene] -3-one (1).

7 is 0.13 μM (14 ppb) of the Rhodamine B derivative compound (1). It is a graph measuring the intensity of fluorescence 10 minutes after the addition of the concentration of silver ions (silver nitrate).

FIG. 8 shows 2 equivalents of silver in 3 ', 6'-bis (diethylamino) -2- (beta-iodineethyl)-[isoindolin-1,9'-xanthene] -3-one (1) After adding the nanoparticles is a graph measuring the change in fluorescence over time.

FIG. 9 is a graph measuring the change in intensity of fluorescence at a wavelength of 584 nm while increasing the concentration of silver nanoparticles in Rhodamine B derivative compound (I).

FIG. 10 shows 0.5 g, 1.0 g, 1.5 g and 2.0 g of a hand sanitizer gel containing silver nanoparticles containing 3 ', 6'-bis (diethylamino) -2- (beta-iodineethyl)-[isoin Fluorescence intensity changes of the DOL-1,9'-xanthene] -3-one (1) solution were measured and the fluorescence intensity values at 584 nm were compared.

FIG. 11 is a graph showing fluorescence intensity changes for a 2 mL sample of a fabric softener containing silver nanoparticles.

FIG. 12 is a graph showing standard curves between six silver nanoparticle samples of known concentration and fluorescence intensity values at 584 nm obtained by excitation at 530 nm.

Claims (11)

Rhodamine B derivative compound or its salt represented by following General formula (1).

(I) Wherein R ₁ and R ₂ independently represent hydrogen (H), halogen, alkyl having 1-30 carbon atoms, or an aryl group having 1-30 carbon atoms, and R ₃ independently represents —NEt ₂ , —NHR, or — NH ₂ , wherein R is Et, alkyl of 1-30 carbon atoms, or aryl of 1-30 carbon atoms.  The Rhodamine B derivative according to claim 1, wherein R1 is hydrogen or halogen or a functional group which may be substituted with hydrogen and introduced into the benzene ring, and R2 is hydrogen or a functional group which may be substituted with hydrogen and introduced into the benzene ring. Compounds or salts thereof. The compound of claim 1 or 2, wherein R2 is independently selected from the group consisting of H, OH, -OR'COOH, and -OR'COOR ", wherein R 'and / or R" are 1 to 8 carbon atoms. Rhodamine B derivative compounds or salts thereof that are alkyl or aryl. The rodda of claim 1, wherein the compound is 3 ', 6'-bis (diethylamino) -2- (beta-iodineethyl)-[isoindolin-1,9'-xanthene] -3-one Min B derivative compounds or salts thereof.  Fluorescent and / or chromogenic Rhodamine B derivative compounds represented by the following general formula (1) or salts thereof:

(I) Here, R ₁ represents hydrogen, halogen, alkyl of 1-30 carbon atoms, or an aryl group of 1-30 carbon atoms, and R ₂ represents hydrogen, halogen, alkyl of 1-30 carbon atoms, or an aryl group of 1-30 carbon atoms. R ₃ is a substituted amine group. 6. The rhodamine B derivative compound according to claim 5, wherein the compound of formula (I) has colorless and no fluorescence properties, and when silver ions are coordinated, "turn on" fluorescence and coloring properties are exhibited. 7. The compound according to claim 6, wherein the compound exhibits “turn-on” fluorescence and color development properties due to silver iodide as silver ions coordinate with iodine to open the spirolactam ring by intramolecular electron transfer and to form an oxazoline ring. Min B derivative compounds. 7. The rhodamine B derivative compound according to claim 6, wherein the silver ions are silver ions generated after an oxidation reaction of silver ions and silver nanoparticles during ion bonding. Formula (16) and

(16) (17, wherein X is a leaving group such as -OSO ₂ CH ₃ , -Br, -OSO ₂ CF _3, etc.)

(17) As the intermediate product (1)

(One) Wherein R 1 and R 2 are hydrogen and R ₃ is —NEt ₂ . A method for detecting and quantitating silver ions and silver nanoparticles by reacting a rhodamine B derivative compound according to claim 1 or a salt thereof with silver ions or silver nanoparticles to measure fluorescent changes. A chemical sensor for detecting silver, comprising the rhodamine B derivative compound according to claim 1.

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